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เกี่ยวกับ น้ามันปาล์ ม สกัด (Palm oil Extract)
เยาวภา เธียรศิลากุล, ปราโมทย์ ธรรมรัตน์ และคณะ
หน่วยสร้างสานึกและพัฒนาประโยชน์
จากเอกสารสิ ทธิบตั รเพื่อการวิจยั และพัฒนา (สสวพ) สกว
สถาบันค้นคว้าและพัฒนาผลิตภัณฑ์อาหาร มหาวิทยาลัยเกษตรศาสตร์
0-2942-8629 ต่อ 626,908
ผลการสืบค้ นบทคัดย่อ โดยใช้ คาสืบค้ น “น ้ามันปาล์ม สกัด (Palm oil extract)” มีทงสิ
ั ้ ้น
85 เรื่ อง ดังนี ้
1. CH680570 - 30/9/1992
ALLERGEN-FREE ST. JOHNS WORT EXTRACT PRODN. TO PREVENT SKIN
TUMOUR - BY MACERATING MECHANICALLY COMMINUTED ST. JOHNS
WORT AND CAMOMILE WITH A PLANT OIL E.G. WHEAT GERM, THISTLE,
SUNFLOWER SEED, ETC.
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=CH680570
Inventor(s):
SCHAEFER ROLF (--)
Applicant(s):
FLINT AG (--)
IP Class 4 Digits: A61K; A61Q
IP Class:A61K8/92; A61K8/97; A61Q19/00; A61K8/96; A61K7/40; A61K35/78
E Class: A61K8/92C; A61K8/97; A61K35/78; A61Q19/00
Application Number:
CH19900003463 (19901030)
Priority Number: CH19900003463 (19901030)
Family: CH680570
Abstract:
Abstract of CH680570
Prodn. of allergen-free St. John's wort oil extract comprises macerating together (i) a mixt. of
mechanically comminuted St. John's wort with mechanically comminuted camomile in a wt. ratio of
1:20 to 20:1, esp. 10:1 and (ii) a plant oil in a ratio (i):(ii) of 1:1 to 1:50, esp. 1:10. The plant oil used is
esp. wheat germ oil, thistle oil, maize germ oil, palm kernel oil, soya oil, sunflower seed oil, rape oil or
groundnut oil. USE/ADVANTAGE - The prod. can be applied to the human skin without causing lightinduced allergies. It is useful for prodn. of cosmetics and pharmaceutical agents, esp. for prophylaxis of
ozone- and UV induced (via radical formation) skin tumors.
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2. CN1073969
- 7/7/1993
PREPARATION METHOD OF PALM-KERNEL OIL AND PLASTIC FAT
SUBSTITUTE
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=CN1073969
Inventor(s):
XIEPING TAI (CN)
Applicant(s):
DANYANG GRAINS OIL FOOD INDUST (CN)
IP Class 4 Digits: C11B
IP Class:C11B1/14; C11B1/00
Application Number:
CN19921014437 (19921212)
Priority Number: CN19921014437 (19921212)
Family: CN1073969
Abstract:
Abstract of CN1073969
Chinese tallow and other vegetable oil are used as raw materials. After degumming and deacidification,
they are mixed proportionally. Sodium alcoholate is used as catalyst for ester exchange. After
decolorizing and deodorizing, the substitute of maripa oil is obtained. In other way, After ester
exchange, it is decolorized, deodorized and wintered to respectively extract the substitutes of maripa oil
and plastic fat, whose physiochemical indexes conform to national and international standards.
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3. CN1126586
- 17/7/1996
MOSQUITO REPELLING BATH LOTION OF NATURAL PLANT MATERIAL
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=CN1126586
Inventor(s):
SHAOHUA JIANG (CN)
Applicant(s):
JIANG SHAOHUA (CN)
IP Class 4 Digits: A61K
IP Class:A61K7/50
Application Number:
CN19931014831 (19931119)
Priority Number: CN19931014831 (19931119)
Family: CN1126586
Abstract:
Abstract of CN1126586
The said bath lotion is compounded with the alcohol extract liquid of sweetgrass, star anise, Agastache
rugosa, pricklyash and menthol, the water extract liquid of Zhucao grass, chrysanthemum indicum and
honeysuckle, dodecanol sodium sulphate, palm oil, diethanol amide, salt and distilled water. Other than
the detergency, the present invention can repel mosquito and is fragrant.
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4. CN1163137
- 29/10/1997
SOFT EXTRACT FOR CURING SCALD
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=CN1163137
Inventor(s):
LIN CHUHONG (CN)
Applicant(s):
LIN CHUHONG (CN)
IP Class 4 Digits: A61K; A61P
IP Class:A61K31/047; A61K31/34; A61K38/48; A61P17/02; A61K31/045; A61K38/43; A61P17/00;
A61K35/78
Application Number:
CN19971004022 (19970417)
Priority Number: CN19971004022 (19970417)
Family: CN1163137
Abstract:
Abstract of CN1163137
The said medicine is compounded with sulfamethylfurazole, lysozyme, palm oil, glycerine, Coptis
extraction liquid, Popozhen extraction liquid and valleyh lily. It is suitable for scald of fire and water
scald, diaphetic skin infection, pest bite and skin disease, and has high effect of antiphlogosis,
eliminating prickly heat and stopping pain. It can also prevent wound from festering and cure skin
tissue necrosis.
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5. CN1240598
- 12/1/2000
INSTANT NOODLES HAVING TASTES OF COCONUT MILK, SEAFOOD AND
CURRY
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=CN1240598
Inventor(s):
LIANG PING (CN); MA ZHIXIN (CN); ZHANG CHAOXI (CN)
Applicant(s):
ZHANG CHAOXI (CN)
IP Class 4 Digits: A23L
IP Class:A23L1/162
Application Number:
CN19981002720 (19980625)
Priority Number: CN19981002720 (19980625)
Family: CN1240598
Abstract:
Abstract of CN1240598
A kind of instant noodles having the tastes of coconut milk, seafood and curry is composed of noodles
and flavouring. Said noodles are prepared from wheat flour, palm oil, water, table salt, Ca, Fe and Zn.
Said flavouring includes butter, wheat flour, onion, curry powder, milk powder, vegetable oil, water,
coconut extract, garlic powder, table salt, ginger powder, tomato sauce, fruit jam, nutrients including
alpha-linolenic acid, VA, VD, VE VB1, VB2 and taurine, and vanillin.
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6. CN1240601
- 12/1/2000
INSTANT NOODLES WITH BAMBOO SHOOT AND MEAT AS SEASONING
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=CN1240601
Inventor(s):
LIANG PING (CN); MA ZHIXIN (CN); ZHANG CHAOXI (CN)
Applicant(s):
ZHANG CHAOXI (CN)
IP Class 4 Digits: A23L
IP Class:A23L1/162
Application Number:
CN19981002723 (19980625)
Priority Number: CN19981002723 (19980625)
Family: CN1240601
Abstract:
Abstract of CN1240601
A kind of instant noodles with bamboo shoot and meat is composed of noodles and flavouring. Said
noodles comprises wheat flour, palm oil, water, table salt, Ca, Fe and Zn. Said flavouring includes
edible oil, wheat flour, peanut paste, onion, bamboo shoot, soy, champignon, champigenon extract
liquid, garlic powder, ginger powder, table salt, sugar, gourmet powder, tomato sauce, coriander,
powdered beef, nutrients including alpha-linolenic acid, VA, VD, VE, VB1, VB2 and taurine, and
vanillin.
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7. CN1307823 - 15/8/2001
ROAST FLOUR PRODUCTION PROCESS
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=CN1307823
Inventor(s):
PANG SHUANGKUI (CN); LEI JIYING (CN)
Applicant(s):
SHAANXI YIWU GROUP CO LTD (CN)
IP Class 4 Digits: A23L
IP Class:A23L1/162; A23L12/21
Application Number:
CN20001035456 (20001128)
Priority Number: CN20001035456 (20001128)
Family: CN1307823
Abstract:
Abstract of CN1307823
The production method of cuminum roasted meat noodles includes the following steps: dough-making,
rolling, forming, steaming, deep-frying, cooling and packaging, and is characterized by adding dusting
and spraying processes between the dough deep-frying process and cooling process, and the described
dusting process is that the flavouring powder is uniformly applied on the dough sheet by means of
dusting machine according to a certain quantity, and the spraying process is that a layer of palm oil is
sprayed on the above-mentioned dough sheet, its oil temp. is 158 deg.c to 162 deg.c. and its flavouring
powder contains (by weight portion) 50-70 portions of cuminum powder, 8-12 portions of
xanthoxylum powder, 8-22 portions of chilli powder, 8-12 portions of monosodium glutamate, 8-12
portionsof beef extract of refined beef powder, 45-55 portions of salt and 0.5 portion of (I+G).
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8. CN1394523
- 5/2/2003
RED FLAVOUR LARGE INTESTINE INSTANT VERMICELLI AND ITS
PRODUCTION PROCESS
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=CN1394523
Inventor(s):
CHEN ZHAOHUI (CN)
Applicant(s):
CHEN ZHAOHUI (CN)
IP Class 4 Digits: A23L
IP Class:A23L1/16; A23L1/22
Application Number:
CN20021033584 (20020806)
Priority Number: CN20021033584 (20020806)
Family: CN1394523
Equivalent:
CN1181751C
Abstract:
Abstract of CN1394523
The present invention provides a Chinese Sichuan local flavour food-red flavour pig's large intestines
convenient vermicelli, including sauce bag formed from pork fat, soybean paste, Yibin Yacai, spice
powder, edible salt, refined paste of pig's large intestines and refined paste of pork fat; oil bag formed
from rape oil, palm oil, Hanyuan red xanthoxylum powder, star anise powder, Guizhou red cluster
pepper powder and capsaicine; powder bag formed from edible salt, monosodium glutamate,
nucleotide, Hanyuan red xanthoxylum powder, meat flavour extract, Hai'nan pepper powder, white
granulated sugar and pork essence; and onion sobyean bag formed from stir-fried soybean, carrot slices
and dried onion sheets. Said invention also provides its production process.
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9. CN1650910
- 10/8/2005
NATURAL PRODUCT FOR TREATING IMPROVING AND PREVENTING
PROSTATAUXE AND ITS MANUFACTURING PROCESS
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=CN1650910
Inventor(s):
XIAO ZILI (CN); CUI CHUNLI (CN); YU HAN (CN)
Applicant(s):
XIAO ZILI (CN)
IP Class 4 Digits: A61K; A61P
IP Class:A61K9/20; A61K9/48; A61P13/08; A61P13/00; A61K35/78
Application Number:
CN20041016052 (20040203)
Priority Number: CN20041016052 (20040203)
Family: CN1650910
Abstract:
Abstract of CN1650910
A natural medicine for preventing and treating prostatoplasia is prepared from the extract of a palm tree,
the extract of pollen, pumpkin seed oil, VE, VD, polyose selenate, and auxiliaries.
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10. DE4419783
- 7/12/1995
MEDICATED SHAMPOO FOR HAIR CARE AND TREATMENT
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=DE4419783
Inventor(s):
WEISCHER CARL HEINRICH DR (DE); ULRICH HEINZ DR (DE);
SCHINDLER HEWARD DR (DE)
Applicant(s):
ASTA MEDICA AG (DE)
IP Class 4 Digits: A61K; A61Q
IP Class:A61K8/23; A61K8/36; A61K8/46; A61K8/49; A61K8/64; A61K8/97; A61Q5/00; A61Q5/02;
A61Q7/00; A61K8/19; A61K8/30; A61K8/96; A61K7/06
E Class: A61K8/23; A61K8/36; A61K8/46F; A61K8/49L; A61K8/64; A61K8/97; A61Q5/00;
A61Q5/02; A61Q7/00
Application Number:
DE19944419783 (19940606)
Priority Number: DE19944419783 (19940606)
Family: DE4419783
Abstract:
Abstract of DE4419783
A shampoo (I) for treatment and care of hair contains at least the following active agents: (A) oxidised
or reduced enantiomers of alpha -lipoic acid, dihydrolipoic acid (racemate) or their esters, 6,8-bis-norlipoic acid, tetra-nor-lipoic acid, or 1,2-dithiacyclopentane-3-butylsulphonic acid or their alkali metal
salts, at a concn. of 0.2-10%; and (B) one or more combination partners such as selenium salts,
disodium salts, potassium salts of a condensation product of lauric acid and protein hydrolysate, palmkernel fatty acid sarcoside of methyltaurine, palm kernel oil fatty acid sarcoside of triethanolamine,
sodium salt of a condensation product of undecylenic acid, water-soluble vitamin E or F, ascorbic acid,
beer extract, camomile flower extract or dye concentrates.Description:
Description of DE4419783
Die vorliegende Erfindung betrifft ein Haarkur-Pflege-Shampoo, das sich insbesondere zur Behandlung
von Haarausfall, Haarwuchsst๖rungen, zytostatika induzierte Alopezie, Haarbr chigkeit,
Kopfschuppen bei trockener und ๖liger Seborrhoe, impetignisierter Ekzeme und Pyodermien der
Kopfhaut, seborrhoisches Ekzem des Haarbodens, seborrhisches Begleitsymptome der
androgenetischen Alopezie und zur Verlไngerung der Lebensdauer der Haare eignet.
Als Krankeitsbild wird beispielsweise Haarausfall, Haarwuchsst ๖rungen, Seborrhoe, Kopfschuppen
oder eine chronische Haarbodenentz
ekzemat๖se Kopfhautverไnderung beobachtet.
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Die Aufgabe der vorliegenden Erfindung ist es, hier Abhilfe zu schaffen und ein Haarkur-PflegeSchampoo mit synergistischer Wirkung durch Kombination von Wirkstoffen zur Verf gung zu stellen.
Erfindungsgemไss wird das dadurch erreicht, dass man ein Haarkur-Pflege-Shampoo, bestehend aus
mindestens den Wirkstoffen:
a) oxidierte oder reduzierte Enantiomere der alpha -Liponsไure, Dihydroliponsไure (Racemat) oder
deren Ester, 6,8-Bisnorliponsไure, Tetranorliponsไure oder die 1,2- Dithiacyclopentan-3butylsulfonsไure oder ihre Alkalisalze in einer Konzentration von beispielsweise 0,2 bis 10%,
vorzugsweise 0,5 bis 4% und
b) ein oder mehrere Kombinationspartner, wie Selensalzen, Dinatriumsalz, Kaliumsalz eines
Kondensationsproduktes aus Laurinsไure und Eiweisshydrolysaten, Palmkernfetts ไure-Sarkosid des
Methyltaurins, Palm๖lkernfettsไure-Sarkosid des Triethanolamins, Natriumsalz eines
Kondensationsproduktes aus Undecylensไure, wasserl๖slichen Vitamin E oder F, Ascorbinsไure,
Bierextrakt, Kamillenbl tenextrakt oder Farbkonzentraten einsetzt.
Das Haarkur-Pflegeschampoo kann beispielsweise bestehen aus:
a) oxidierten oder reduzierten Enantiomeren der alpha -Liponsไure, Dihydroliponsไure (Racemat)
oder deren Ester, 6,8-Bisnorliponsไure, Tetranorliponsไure oder die 1,2- Dithiacyclopentan-3butylsulfonsไure oder ihren Alkalisalze in einer Konzentration von beispielsweise 0,2 bis 8%,
vorzugsweise 0,5 bis 4% und
b) Natrium-Selenit, wasserl๖slichen Vitamin E oder F, KM BRONIDOX L TM ,
Kamillenbl tenextrakt, TEXAPON EVR TM , TEXAPON N25 TM , TEXAPON MLS TM ,
TEXAPON N40 TM , TEXAPON N70 TM , TEXAPON MG TM , EUPERLAN PK 776 TM ,
EUPERLAN PK 771 TM , COMPERLAN KD TM , COMPERLAN 100 TM , COMPERLAN LS TM ,
DEHYTON K TM , Kokosfettsไure-diethanolamid, Fettalkoholethersulfat, Na-Laurylethersulfat,
NUTRILAN I TM , LAMERCIN 50-80 TM , Natriumchlorid, Konservierungsmittel, Parf m๖l,
Bierextrakt oder Farbkonzentraten.
Die alpha -Liponsไure ist chemisch gesehen 1,2-Dithia-cyclopentan-3-valerieansไure und ist in Form
des R-Enantiomers in Pflanzen und Tieren weit verbreitet. Sie wirkt in vielen enzymatischen
Reaktionen als Coenzym, stellt einen Wachstumsfaktor f r manche Bakterien und Protozoen dar und
wird bei der Behandlung von Knollenblไtterpilzvergiftungen eingesetzt.
Weiterhin weist das alpha -Liponsไure-Racemat antiphlogistische, antinociceptive (analgetische)
sowie zytoprotektive, neuroprotektive, antiallergische und antitumor Eigenschaften auf.
Die reinen, optischen Enantiomeren der alpha -Liponsไure (R- und S-Form, das heisst R- alpha Liponsไure und S- alpha -Liponsไure) sind im Gegensatz zu dem Racemat wirksamer. Das REnantiomer ist vorwiegend antiphlogistisch und das S-Enantiomer antinociceptiv wirksam, wobei die
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antiphlogistische Wirkung des R-Enantiomer beispielsweise um einen Faktor 10 stไrker ist als
diejenige des Racemats.
Die antinociceptive (analgetische) Wirkung des S-Enantiomer ist beispielsweise um bis 6 Faktoren
stไrker als diejenigen des Racemats.
Die Enantiomeren der alpha -Liponsไure stellen daher im Vergleich zu dem Racemat sehr viel
spezifischere und stไrkerer wirksame Wirkstoffe dar.
Diese Wirkungen sind in EP-A 901 213 405 beschrieben.
Dieser Synergismus wird vermutet durch den Schutz des Elastins, einem Bestandteil des Bindegewebes
der Kopfhaut, durch die erfindungsgemไsse Kombination mit der alpha -Liponsไure. Durch die
beschriebene bekannte antiphlogistische und Kalziumf ไngereigenschaften der alpha -Liponsไure
kommt es zur Hemmung der katabolen Enzyme.
Das Haarkur-Pflege-Schamoo kann beispielsweise in Tuben, Flaschen oder verschweissten
Kunststoffbeuteln zur ไusserlichen Anwendung vorliegen.
Ausf hrungsbeispiele
Beispiel 1
100 g L๖sung enthไlt:
EMI3.1
Beispiel 2
100 g L๖sung enthไlt:
EMI3.2
Beispiel 3
100 g L๖sung enthไlt:
EMI4.1
Beispiel 4
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100 g L๖sung enthไlt:
EMI4.2
Beispiel 5
100 g L๖sung enthไlt:
EMI5.1
Beispiel 6
100 g L๖sung enthไlt:
EMI5.2
Beispiel 7
100 g L๖sung enthไlt:.
EMI6.1Data supplied from the esp@cenet database - Worldwide
Claims of DE4419783
Claims:
1. Haarkur-Pflege-Shampoo bestehend aus mindestens den Wirkstoffen:
a) oxidierte oder reduzierte Enantiomere der alpha -Liponsไure, Dihydroliponsไure (Racemat) oder
deren Ester, 6,8-Bisnorliponsไure, Tetranorliponsไure oder die 1,2- Dithiacyclopentan-3butylsulfonsไure oder ihre Alkalisalze in einer Konzentration von 0,2 bis 10% und
b) einem oder mehreren Kombinationspartnern wie Selensalzen, Dinatriumsalz, Kaliumsalz eines
Kondensationsproduktes aus Laurinsไure und Eiweisshydrolysaten, Palmkernfetts ไure-Sarkosid des
Methyltaurins, Palm๖lkernfettsไure-Sarkosid des Triethanolamins, Natriumsalz eines
Kondensationsproduktes aus Undecylensไure, wasserl๖slichen Vitamin E oder F, Ascorbinsไure,
Bierextrakt, Kamillenbl tenextrakt oder Farbkonzentraten.
2.Haarkur-Pflege-Shampoo nach Anspruch 1 dadurch gekennzeichnet, dass es mindestens aus
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a) oxidierten oder reduzierten Enantiomeren der alpha -Liponsไure, Dihydroliponsไure (Racemat)
oder deren Ester, 6,8-Bisnorliponsไure, Tetranorliponsไure oder die 1,2- Dithiacyclopentan-3butylsulfonsไure oder ihren Alkalisalze in einer Konzentration von 0,2 bis 8% und
b) einem oder mehreren Kombinationspartnern wie Natrium-Selenit, wasserl๖slichen Vitamin E oder
F, KM BRONIDOX L TM , Kamillenbl tenextrakt, TEXAPON EVR TM , TEXAPON N25 TM ,
TEXAPON MLS TM , TEXAPON N40 TM , TEXAPON N70 TM , TEXAPON MGOR, EUPERLAN
PK 776 TM , EUPERLAN PK 771 TM , GOMPERLAN KD TM , COMPERLAN 100 TM ,
COMPERLAN LS TM , DEHYTON K TM , Kokosfetts ไurediethanolamid, Fettalkoholethersulfat, NaLaurylethersulfat, NUTRILAN I TM , LAMERCIN 50-80 TM , Natriumchlorid, Konservierungsmittel,
Parf m๖l, Bierextrakt oder Farbkonzentraten besteht.
3. Haarkur-Pflege-Shampoo nach Anspruch 1 dadurch gekennzeichnet, dass es insbesondere zur
Behandlung von Haarausfall, Haarwuchsst๖rungen, Zytostatika induzierte Alopezie, Haarbr chigkeit,
Kopfschuppen bei trockener und ๖liger Seborrhoe, impetignisierter Ekzeme und Pyodermien der
Kopfhaut, seborrhoisches Ekzem des Haarbodens, seborrhoisches Begleitsymptome der
androgenetischen Alopezie und zur Verlไngerung der Lebensdauer der Haare verwendet wird.
4. Haarkur-Pflege-Shampoo nach Anspruch 1 dadurch gekennzeichnet, dass die Wirkstoffe in Tuben,
Flaschen oder verschweissten Kunststoffbeuteln zur ไusserlichen Anwendung vorliegen.Data supplied
from the esp@cenet database - Worldwide
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11. FR2832631 - 30/5/2003
USE OF COMMON REED IN COSMETIC FORMULATIONS FOR THE SKIN,
BODY AND HAIR
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=FR2832631
Inventor(s):
AGUADISH LOUIS MICHEL JACQUES (--); MANE JEAN MAURICE EUGENE
(--); BERTHON JEAN YVES ANTONIN (--)
Applicant(s):
GREENTECH SA (FR); MANE FILS V (FR)
IP Class 4 Digits: A61K
IP Class:A61K7/48; A61K7/06; A61K7/40
Application Number:
FR20010015405 (20011127)
Priority Number: FR20010015405 (20011127)
Family: FR2832631
Abstract:
Abstract of FR2832631
Common reed (Phragmites communis) is used in cosmetic formulations for the skin, body and hair,
especially as a concentrated extract in water, alcohol, acetone, aqueous alcohol, aqueous glycol, glycol
or oil. An Independent claim is also included for the use of sweet flag (Acorus calamus), giant reed
(Arundo donax) and cabbage palm (Cordyline terminalis) in cosmetic formulations for the skin, body
and hair.Description:
Description of FR2832631
>;Desc/Clms Page number 1;
La pr้้sente invention concerne l'utilisation du roseau ou de ses ingr ้้dients sous forme d'extraits pour
des formulations เ usage cosm้้tique.
On entendra par la suite sousl'appellation"roseau"la d้้nomination et l'usage des esp้่ces v้้g้้tales
fra้ches ou s้่ches ci-apr้่s d้้crites (voir Annexe 1) sous forme d'extraits aqueux, alcooliques,
ac้้toniques, hydroalcooliques, hydroglycoliques, glycoliques ou huileux.
Dans une forme restreinte, la description de la plante d'int ้้r้t cosm้้tique ou cosm้้tologique
concerne le roseau commun appel้้ aussi phragmite (Phragmites communis), appel้้ Lu-Gen en Chine,
I-Gesba ou Aganim au Maroc, common reed en anglais, Carrizo en espagnol et cannucia en italien. Le
roseau, ou phragmite, ou roseau เ balai, pousse partout dans le monde jusqu'เ une altitude de 2200
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m้่tres dans les zones humides, marais, bords d'้้tangs et de rivi้่res. Dans une consid้้ration limit้้e
de son utilisation, la racine ou rhizome est inscrite en France au Codex en1818. Dans d'autres pays, ce
sont plut๔t les parties a้้riennes, voire les inflorescences qui sont utilis้้es dans de nombreuses
applications pharmacop้้es coutumi้่res aussi diverses que : boissons ้้nerg้้tiques et
rafra้chissantes, pousse des cheveux, blanchiment de la peau, anti-bact้้rien, fongicide, diur้้tique.
Le roseau phragmite est une plante herbac ้้e p้้renne de la famille des Graminac้้es rencontr้้e dans
les lieux humides. Cette plante se propage grโce เ un syst้่me racinaire souterrain appel้้ rhizome et
les repousses peuvent appara้tre toute l'ann้้e selon les conditions climatiques.
Comme la plupart des plantes herbac้้es เ tige charnue, les tiges de roseau sont d'une fa ้on g้้n้้rale
riches en saccharose comme la canne เ sucre (Saccharum officinarum). C'est pour cette raison que la
plante peut survivre aux variations hydriques pouvant survenir lors des phases de croissance
v้้g้้tative. La plante s'adapte ้้galement เ son environnement min้้ral par l'adsorption et le relargage
s้้lectif de m้้taux tels que le calcium et le sodium, mais ้้galement de m้้taux lourds tels que le
plomb ou le nickel. Cette derni้่re caract้้ristique des roseaux en a fait des candidats potentiels pour
des ้้tudes de d้้pollution des sols, g้้n้้ralement appel้้e biorem้้diation.
>;Desc/Clms Page number 2;
EMI2.1
Les roseaux sont riches en ph้้nols et polyph้้nols tels que les acides vanillique, f้้rulique,
coumarique et en ald้้hydes tels que le p-hydroxybenzald้้hyde.
Les feuilles et la tige contiennent des flavanols, des flavones telles que la luteoline, l'acide aconitique et
plus sp้้cifiquement la tricine, divers alcalo๏des tels que hord้้nine, gramine, tryptamine, indol-3-
้้thylamine, et des di-et tri-terp้่nes tels que a-amicine. Les roseaux sont deux เ trois fois plus riches
en vitamine C (acide ascorbique) que l'orange. Enfin, les inflorescences renferment des anthocyanines.
Dans une description plus sp้้cifique de l'utilisation du roseau sous forme d'extraits aqueux,
alcooliques, ac้้toniques, hydroalcooliques, hydroglycoliques, glycoliques ou huileux, enrichis en l'un
ou plusieurs de ses composants chimiques et biochimiques caract้้ristiques เ applications
pharmaceutiques et plus pr้้cis้้ment cosm้้tiques, on entendra par stimulation de propri้้t้้s
antiradicalaires pour ralentir le vieillissement cutan้้, la pr้้sence de flavono๏des et de polyph้้nols,
par stimulation de propri้้t้้s hydratantes, la pr้้sence de polysaccharides tels que les lucanes et les
xylanes et de sucres libres tels que le saccharose, par limitation de la chute des cheveux, la pr ้้sence de
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st้้rols, flavones et flavanols, par stimulation de propri้้t้้s immunomodulatrices, la pr้้sence de
polysaccharides, par stimulation de processus inhibiteurs du vieillissement ้้pidermique et dermique,
la pr้้sence de polysaccharides sp้้cifiques tels que les arabinoglucanes, par stimulation du cuir
chevelu, la pr้้sence de flavono๏des, flavanols et anthocyanosides, par stimulation de propri้้t้้s
amincissantes locales ou diminution de la charge lipidique des adipocytes sous-cutan้้s, la pr้้sence
concomitante de compos้้s ph้้noliques inhibiteurs de l'AMP cyclique-phosphodiest้้rase et de di-et
tri-terp้่nes, certains flavono๏des, coumarines et ph้้nols activateurs de 1'ad้้ny1ate cyclase r้้sultant
en une augmentation significative de la concentration intracellulaire locale en AMP cyclique dans les
adipocytes conduisant เ un effet lipolytique puissant grโce เ l'effet stimulateur de l'AMP cyclique via la
prot้้ine kinase AMP cyclique d้้pendante sur la triglyc้้ride lipase, par augmentation de propri้้t้้s
d้้toxifiantes naturellement pr้้sent้้es par le roseau dans son environnement, la pr้้sence de
flavono๏des et de polyph้้nols permettant la complexation et
>;Desc/Clms Page number 3;
l'้้limination de m้้taux lourds et de polluants agressifs pour1'้้piderme, par augmentation de
propri้้t้้s rafra้chissantes et tonifiantes naturellement reconnues pour le roseau, la pr้้sence de
polysaccharides, de saccharose et de vitamine C (acide ascorbique). Une application particuli ้่re sous
forme d'extraits aqueux, alcooliques, ac ้้toniques, hydroalcooliques, hydroglycoliques, glycoliques ou
huileux de roseau d'int้้r้t cosm้้tique ou cosm้้tologique concerne le contr๔le et le
traitementr้้sorptif de 1a surcharge lipidique des adipocytes souscutan ้้s par adsorption des compos้้s
actifs du roseau appliqu้้s en une formulation appropri้้e relevant de l'homme de l'art. Cette
application particuli้่re r้้pond เ un besoin de l'immense majorit้้ des femmes qui se plaignent de
pr้้senter des signes de cellulite ou hypertrophie du tissu adipeux r ้้sultant du stockage massif de
graisses เ la suite d'un d้้s้้quilibre souvent localis้้, voire g้้n้้ralis้้, entre captation (lipog้้n้่se)
et mobilisation (lipolyse) des dites graisses. Cons ้้quemment, la modification du tissu sous-cutan้้,
structure, nombre et volume des adipocytes, r้้sulte en une d้้t้้rioration durable et souvent
irr้้versible du tissu conjonctif accompagn้้e d'une r้้tention et d'une accumulation d'eau et de toxines
due เ des troubles de la microcirculation. Dans le tissu adipeux, les triglyc ้้rides stock้้s dans la
vacuole de l'adipocyte se regroupent avec d'autres adipocytes en lobules puis en lobes. Les adipocytes
sont responsables de l'้้quilibre ้้nerg้้tique de l'organisme selon deux m้้canismes essentiels : la
lipog้้n้่se et la lipolyse. La lipog้้n้่se r้้sulte de la synth้่se des triglyc้้rides เ partir soit de
glucose sanguin qui conduit เ une n้้osynth้่se d'acides gras เ travers la glycolyse et la synth้่se de
l'interm้้diaire ac้้tyl-coenzyme A, soit เ partir du captage de lipoprot้้ines sanguines circulantes. La
p้้n้้tration du glucose dans la cellule est facilit ้้e par deux types de syst้่mes de
transporteursmembranaires : OLUT-1 assurant le transport basal et GLUT-4, transporteur
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insulinod้้pendant. Toutefois la voie pr้้dominante conduisant chez l'homme เ la biosynth้่se de
triglyc้้rides est la voie utilisant le captage des acides gras เ partir des chylomicrons et des
lipoprot้้ines de tr้่s faible densit้้ d'origine h้้patique. La lipoprot้้ine lipase est l'enzyme cl้้ de
cette r้้action contr๔l้้e par l'insuline. Les acides gras ainsi lib้้r้้s par la lipoprot้้ine lipase sont
ensuite est้้rifi้้s par le syst้่me glyc้้rol acyltransf้้rase, apr้่s avoir ้้t้้ transport้้s เ travers la
membrane plasmique par une
>;Desc/Clms Page number 4;
translocase et des prot้้ines de transport sp้้cifiques des acides gras puis une prot้้ine intracellulaire
liant sp้้cifiquement les acides gras. L'expression de tous les acteurs du captage des acides gras au
niveau des adipocytes est induite au cours de la diff้้renciation de ces derniers, expression en outre
r้้gul้้e par les hormones et diverscytor้้gulateurs. A l'inverse, la lipolyse est l'hydrolyse des
triglyc้้rides en acides gras libres effectu้้e par la triglyc้้ride lipase. L'activit้้ de cette enzyme
est ้้troitement contr๔l้้e par phosphorylation sp้้cifique de deux sites, l'un par une prot้้ine kinase
AMP cyclique d้้pendante, l'autre par une prot้้ine kinase 5'-AMP d้้pendante. Il en r้้sulte donc que
l'activit้้ de la triglyc้้ride lipase d้้pend directement du tauxd'AMP cyclique intracellulaire, donc
de1'activit้้ ad้้nylate cyclase qui accroit ce taux et de l'AMP cyclique phosphodiest้้rase qui diminue
ce taux.
Dans les extraits aqueux, alcooliques, ac้้toniques, hydroalcooliques, hydroglycoliques, glycoliques ou
huileux de roseau d'int้้r้t cosm้้tique ou cosm้้tologique, la pr้้sence de compos้้s ph้้noliques
inhibiteurs del'AMP cyclique-phosphodiest้้rase et de di-et triterp้่nes, certainsflavono๏des,
coumarines et ph้้nols activateurs de l'ad ้้nylate cyclase r้้sultant en une augmentation significative
de la concentration intracellulaire locale en AMP cyclique dans les adipocytes conduisant เ un effet
lipolytique puissant grโce เ l'effet stimulateur del'AMP cyclique via la prot้้ine kinase AMP cyclique
d้้pendante sur la triglyc้้ride lipase, permet l'utilisation avantageuse de ces extraits aqueux,
alcooliques, ac้้toniques, hydroalcooliques, hydroglycoliques, glycoliques ou huileux de roseau
comme un moyen naturel, inoffensif, et externe de rem้้dier เ l'apparition d'accumulation localis้้e,
voire g้้n้้ralis้้e et disgracieuse de graisses conduisant เ l'apparition de cellulite, apr้่s formulation
des dits extraits par l'homme de l'art.
Comme preuve de l'argumentation ci-dessus pr้้sent้้e, et afin d'้้tayer cette argumentation, il a ้้t้้
recherch้้ avec succ้่s la pr้้sence de compos้้s ph้้noliques inhibiteurs del'AMP cycliquephosphodiest้้rase et de di-et tri-terp้่nes, certains flavono๏des, coumarines et ph้้nols activateurs de
l'ad้้nylate cyclase r้้sultant en une augmentation significative de la concentration intracellulaire
locale en AMP cyclique dans les adipocytes.
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Pr้้sence d'une activit้้ inhibitrice del'AMP cyclique-phosphodiest้้rase dans les extraits
EMI5.1
aqueux, alcooliques. ac้้toniques. hydroa1coo1iques. hydrog1yco1iques. glycoliques ou huileux de
roseau.
Dans une forme particuli้่re de l'invention, une extraction hydroalcoolique s้้lective des compos้้s
ph้้noliques du roseau a ้้t้้ mise au point selon une m้้thode sp้้cifiquement adapt้้e au roseau.
Bri้่vement, l'extrait hydroalcoolique titrant 47 % d'alcool ้้thylique est trait้้ เ la temp้้rature
ambiante avec de l'hydroxyde de calcium satur ้้. Le pr้้cipit้้ jaunโtre form้้ au cours du temps est
r้้cup้้r้้ par les techniques physiques appropri้้es de filtration et/ou de centrifugation. Cette fraction
est enfin resolubilis้้e par neutralisation de l'hydroxyde de calcium par une acide fort tel que acide
chlorhydrique ou dans une forme particuli ้่re de l'invention par de l'acide phosphorique qui permet
l'้้limination subs้้quente du phosphate de calcium form้้ insoluble, afin d'obtenir une produit final
satisfaisant et exempt d'un apport de sels min้้raux exog้่nes. Cet extrait final contient donc les
compos้้s ph้้noliques recherch้้s et pr้้sentant une forte activit้้ inhibitrice de l'AMP cycliquephosphodiest้้rase. Cette derni้่re activit้้ enzymatique est inhib้้e เ plus de 60% par une dilution de
la fraction susd้้crite เ 2 % o (Annexe II : dosage de1'AMPcyc1ique phosphodiesterase). Cette
observation indique en outre que les compos้้s inhibiteurs de1'AMP cyclique phosphodiest้้rase
pr้้sents dans l'extrait ci-dessus d้้crit, sont ้้galement pr้้sents dans l'extrait hydroalcoolique initial
et trait้้ tel que d้้crit dans la forme particuli้่re de l'invention.
Pr้้sence d'une activit้้ activatrice de1'Ad้้ny1atecyclane dans les extraits aqueux. alcooliques.
ac้้toniques. hydroalcooliques,hydrog1yco1iques. glycoliques ou huileux de roseau.
L'extrait hydroalcoolique de roseau titrant 47 % d'alcool ้้thylique pr้้sente une forte activit้้
activatrice del'Ad้้nylate cyclase. Cette derni้่re activit้้ enzymatique est activ้้e เ plus de 70 % par
une dilution de la fraction sus-d้้crite เ 2,3 % o (Annexe III : dosage del'Ad ้้nylatecyclase).
>;Desc/Clms Page number 6;
Recherche et titration des compos้้s pr้้sentant une activit้้ d'inhibition del'AMP cyclique
phosphodiest้้rase (Voir Annexe IV).
Recherche et titration des compos้้s pr้้sentant une activit้้ d'activation derAd้้ny1ate cyclase (Voir
Annexe V).
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Dans une description particuli้่re de la pr้้sente invention telle que pr้้sent้้e ci-dessus, la pr้้sence
de compos้้s ph้้noliques inhibiteurs deFAMP cyclique-phosphodiest้้rase et de diet tri-terp้่nes,
certains flavono๏des, coumarines et ph้้nols activateurs de1'ad้้ny1ate cyclase r้้sultant en une
augmentation significative de la concentration intracellulaire locale en AMP cyclique dans les
adipocytes n'exclut pas la pr้้sence d'autres compos้้s chimiques particuliers et sp้้cifiques du roseau
montrant des propri้้t้้s antiradicalaires pour ralentir le vieillissement cutan้้ par la pr้้sence de
flavono๏des et de polyph้้nols, des propri้้t้้s hydratantes par la pr้้sence de polysaccharides et de
sucres libres tels que le saccharose, des propri้้t้้s immunomodulatrices par la pr้้sence de
polysaccharides, des propri้้t้้s d'inhibition du vieillissement ้้pidermique et dermique par la
pr้้sence de vitamine C, d'acides organiques et de polysaccharides sp้้cifiques tels que
lesarabinoglucanes,, des propri้้t้้s d้้toxifiantes naturellement pr้้sent้้es par le roseau dans son
environnement par la pr้้sence de flavono๏des et de polyph้้nols permettant la complexation et
l'้้limination de m้้taux lourds et de polluants agressifs pour l'้้piderme, des propri้้t้้s
rafra้chissantes et tonifiantes naturellement reconnues pour le roseau par la pr้้sence de
polysaccharides, de saccharose et de vitamine C (acide ascorbique).
L'ensemble de ces propri้้t้้s rassembl้้es en un extrait bioactif de roseau constitue la pr้้sente
invention.
>;Desc/Clms Page number 7;
Annexe 1 Le roseau et les plantes apparent้้es.
Les plantes du type roseau (Phragmites communs), Acore ou roseau odorant (Acoruscalamus), roseau
ou"canne"de Provence (Arundo dorax), roseau des Indes (Cordyline terminalis), sont des plantes
herbac้้es p้้rennes de la famille des Graminac้้es rencontr้้es dans les lieux humides. Ces plantes se
propagent grโce เ un syst้่me racinaire souterrain appel้้ rhizome et les repousses peuvent appara้tre
toute l'ann้้e selon les conditions climatiques.
Comme la plupart des plantes herbac้้es เ tige charnue, les tiges de roseau sont d'une fa ้on g้้n้้rale
riches en saccharose comme la canne เ sucre(Saccharum officinarum).
C'est pour cette raison que la plante peut survivre aux variations hydriques pouvant survenir lors des
phases de croissance v้้g้้tative. La plante s'adapte ้้galement เ son environnement min้้ral par
l'adsorption et le relargage s้้lectif de m้้taux tels que le calcium et le sodium, mais ้้galement de
m้้taux lourds tels que le plomb ou le nickel. Cette derni ้่re caract้้ristique des roseaux en a fait des
candidats potentiels pour des ้้tudes de d้้pollution des sols, g้้n้้ralement appel้้e biorem้้diation.
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Les roseaux sont riches en ph้้nols et polyph้้nols tels que les acides vanillique, f้้rulique,
coumarique et en ald้้hydes tels que le p-hydroxybenzald้้hyde.
Les feuilles et la tige contiennent des flavanols, des flavones telles que la luteoline, l'acide aconitique et
plus sp้้cifiquement la tricine, divers alcalo๏des tels que hord้้nine, gramine, tryptamine, indol-3-
้้thylamine, et des di-et tri-terp้่nes tels que a-amicine. Les roseaux sont deux เ trois fois plus riches
en vitamine C (acide ascorbique) que l'orange.
Enfin, les inflorescences renferment des anthocyanines.
Les roseaux ont ้้t้้ utilis้้s en m้้decine populaire et coutumi้่re pour purifier l'organisme et comme
tonifiants et rafra้chissants seuls ou en combinaison avec d'autres mac ้้rations de plantes.
>;Desc/Clms Page number 8;
Phragmites communis.
Le roseau commun ou phragmite contient des substances azot้้es libres (5 %) dont l'asparagine (0,1 %),
des prot้้ines (5 %), des min้้raux dont des silicates repr้้sentant 60 % des min้้raux totaux et enfin
des hydrates de carbone dont du saccharose (6%).
Le roseau commun a ้้t้้ utilis้้ dans la pharmacop้้e traditionnelle comme diur้้tique, s้้datif et
sudorifique ainsi que dans le traitement d'affections urinaires et de goutte. Au Maroc, le roseau
commun est utilis้้ comme anticonceptionnel mais ้้galement pour combattre la calvitie et stimuler la
croissance des cheveux, deux utilisations qui permettent de penser que le roseau renferme des
substances pr้้sentant des activit้้s de type hormonal comme st้้rols, flavones ou flavonols. Ces effets
sont เ rapprocher de ceux d'autres plantes telles que soja, tr ้่fle, houblon, fenugrec ou yam.
Acorus calamus ou roseau odorant.
Le roseau odorant contient des saponines, huiles essentielles, acides gras, sesquiterp ้่nes, saccharose,
azul้้ine, isoengenol, limone, tanins et mucilage.
Cette vari้้t้้ de roseau est largement utilis้้e en Malaise comme tonique et stimulant, insecticide,
bact้้ricide et fongicide (ex : hygi้่ne buccale) ainsi que pour traiter les d้้sordres digestifs et
pulmonaires. Le roseau odorant est ้้galement utilis้้ en Chine et au Maghreb.
Cependant les extraits de A. calamus peuvent contenir de la cis-isoasarone, substance potentiellement
canc้้rig้่ne, d'o๙ l'interdiction aux USA de son utilisation pour la pr้้paration d'huiles essentielles.
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Arundo dorax La canne de Provence a ้้t้้ traditionnellement utilis้้e comme diur้้tique et
antigalactog้่ne.
Certains cas d'allergie ont ้้t้้ observ้้s lors de la r้้colte de la canne de Provence. En r้้alit้้ ces
allergies sont dues เ la pr้้sence d'un champignon phytopathog้่ne de la canne et non aux constituants
de la plante.
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Cordyline terininalis Le roseau des Indes se rencontre dans la for ้t humide amazonienne, notamment
en Guyane.
Cette vari้้t้้ de roseau contient en particulier de la tyramine et des saponines st ้้ro๏diques. Les
feuilles sont utilis้้es traditionnellement pour soigner les plaies et elles pr้้sentent des propri้้t้้s
hypotensives.
Annexe II : dosage de l'AMP cyclique phosphodiesterase.
L'activit้้ AMP cyclique phosphodiesterase est mesur้้e par l'apparition deS'-AMP partir d'AMP
cyclique, en pr้้sence de magn้้sium et de calcium dans un milieu tamponn้้ เ pH 7, 5.
Le S'-AMP est mesur้้ par chromatographie liquide haute pression.
Conditions de l'activit้้ enzymatique : l'enzyme (0,1 unit้้) est incub้้e dans un tampon Tris-HC1 0,2
M pH 7, 5 en pr้้senced'AMPcyc1ique 0,1 mM, de chlorure de magn ้้sium 10 mM et de chlorure de
calcium 0,05 mM, pendant 20 minutes เ 35 C en pr้้sence ou non d'extraits v้้g้้tauxd'int้้r้t. La
r้้action est arr้t้้e par chauffage pendant 10 minutes เ65 C.
Un ้้chantillon de 0, 05 ml est analys้้ par chromatographie liquide haute pression sur une colonne de
phase r้้verse (octad้้cyl silice) dans un tampon phosphate de potassium 0.08 M, pH 6,0. Les
nucl้้otides pr้้sents sont้้ludes s้้quentiellement par un gradient de m้้thanol et leurs quantit้้s
respectives d้้termin้้es par rapport เ des quantit้้s de standards de r้้f้้rence connues.
AnnexeIII : dosage de1'ad้้ny1ate cyclase.
L'activit้้ ad้้nylate cyclase est mesur้้e par l'apparition d'AMP cyclique เ partir d'ATP, en pr้้sence
de magn้้sium dans un milieu tamponn้้ เ pH 8, 5. l'AMP cyclique est mesur ้้ par chromatographie
liquide haute pression.
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Conditions de l'activit้้ enzymatique : l'enzyme (0,1 unit้้) est incub้้e dans un tampon TrisHC10, 2
M pH 8,5 en pr้้sence d'ATP 1 mM et de chlorure de magn้้sium 50 mM, pendant 20 minutes เ35 C
en pr้้sence ou non d'extraits v้้g้้taux d'int้้r้t. La r้้action est arr้t้้e par chauffage pendant 10
minutes เ65 C.
>;Desc/Clms Page number 10;
Un ้้chantillon de 0,05m1 est analys้้ par chromatographie liquide haute pression sur une colonne de
phase r้้verse (octad้้cyl silice) dans un tampon phosphate de potassium 0.08 M, pH 6,0. Les
nucl้้otides pr้้sents sont ้้lu้้s s้้quentiellement par un gradient de m้้thanol et leurs quantit้้s
respectives d้้termin้้es par rapport เ des quantit้้s de standards de r้้f้้rence connues.
Annexe IV Recherche et titration des compos้้s pr้้sentant une activit้้ d'inhibition de l'AMP
cyclique phosphodiest้้rase.
La fraction concentr้้e d'extrait de roseau est ้้vapor้้e et reprise dans du m้้thanol et/ou du
dichlorom้้thane(100 J. 11 pour 1 ml). 25 เ 40J. 11 d้้pos้้s. R้้f้้rences en solution เ 0.1 % dans
EMI10.1
du m้้thanol. 5 J. 11 d้้pos้้s.
Migration sur gel de silice 60F254 par le syst ้่me ac้้tated'้้thyle/acide formique/acide ac้้tique/eau :
100/11/11/27 ou Migration sur gel de silice60F254 par le syst ้่mebutanol/acide ac้้tique/eau :
50/10/40 R้้v้้lation par le chlorure d'antimoine เ 20% dans le chloroforme ou R้้v้้lation par le
r้้actifdiphenylbory1oxy้้thy1amine เ 1% dans le m้้thanol, amplifi้้ par poly้้thyl้่ne glycol 4000
5% dans le m้้thanol.
Annexe V Recherche et titration des compos้้s pr้้sentant une activit้้ d'activation de1'ad้้nylate
cyclase.
La fraction concentr้้e d'extrait de roseau est ้้vapor้้e et reprise dans de1'้้thano170% (1/lOe du
volume initial), 25 เ 40ui sont d้้pos้้s.
La fraction concentr้้e d'extrait de roseau (1 ml) est extraite par 3 fois 0,5 ml de chloroforme.
Les extraits sont r้้unis et ้้vapor้้s et redissous dans 0,1 ml de chloroforme / m้้thanol 1/1.
>;Desc/Clms Page number 11;
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Une hydrolyse est effectu้้e en ajoutant 1.5 ml d'acide sulfurique 0,5 M suivie d'un chauffage เ100 C
pendant 1 heure.
Le m้้lange est r้้extrait par du chloroforme (3 fois 0,75 ml), ้้vapor้้ et repris dans 100111
dechloroforme/m้้thanol 1/1,10ici sont appliqu้้s. Tests 0,1 % dans m้้thanol (ex : gibberreline).
Migration sur gel de silice60F254 par le syst ้่me ac้้tated'้้thyle/acide formique/acide ac้้tique/eau :
100/11/11/27.
R้้v้้lation par le r้้actifdiphenylboryloxy้้thylamine1 % dans le m้้thanol, amplifi้้ par
poly้้thyl้่ne glycol 4000 5% dans le m้้thanol.Data supplied from the esp@cenet database Worldwide
Claims:
Claims of FR2832631
Revendications. l-Utilisation du roseau commun, ou phragmite (Phragmites communis) pour des
formulations cosm้้tiques (peau, corps, cheveux).
2-Utilisation du roseau commun, ou phragmite (Phragmites communis) sous forme d'extraits aqueux
concentr้้s pour des formulations cosm้้tiques (peau, corps, cheveux).
3-Utilisation du roseau commun, ou phragmite (Phragmites communis) sous forme d'extraits
alcooliques concentr้้s pour des formulations cosm้้tiques (peau, corps, cheveux).
4-Utilisation du roseau commun, ou phragmite (Phragmites communs) sous forme d'extraits
ac้้toniques concentr้้s pour des formulations cosm้้tiques (peau, corps, cheveux).
5-Utilisation du roseau commun, ou phragmite (Phragmites communis) sous forme d'extraits
hydroalcooliques concentr้้s pour des formulations cosm้้tiques (peau, corps, cheveux).
6-Utilisation du roseau commun, ou phragmite (Phragmites communis) sous forme d'extraits
hydroglycoliques concentr้้s pour des formulations cosm้้tiques (peau, corps, cheveux).
7-Utilisation du roseau commun, ou phragmite (Phragmites communis) sous forme d'extraits
glycoliques concentr้้s pour des formulations cosm้้tiques (peau, corps, cheveux).
8-Utilisation du roseau commun, ou phragmite (Phragmites communis) sous forme d'extraits huileux
concentr้้s pour des formulations cosm้้tiques (peau, corps, cheveux).
9-Utilisation selon les revendication 1 เ 8 de l'Acore ou roseau odorant (Acorus calamus) pour des
formulations cosm้้tiques (peau, corps, cheveux).
10-Utilisation selon les revendications 1 เ 8 de la canne de Provence (Arundo dorax) pour des
formulation cosm้้tiques (peau, corps, cheveux).
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EMI12.1
11-Utilisation selon les revendications 1 เ 8 du roseau des Indes (Cordyline terminalis) pour des
formulations cosm้้tiques (peau, corps, cheveux).
12-Utilisation selon les revendications 1 เ 11 du roseau pour la pr้้paration de formulations
cosm้้tiques caract้้ris้้es par la pr้้sence d'une ou plusieurs substances inhibitrices del'AMP
cyclique phosphodiest้้rase (AMP : ad้้nosine 3' : 5'monophosphate cyclique).
13-Utilisation selon les revendications 1 เ 11 du roseau pour la pr้้paration de formulations
cosm้้tiques caract้้ris้้es par la pr้้sence d'une ou plusieurs substances activatrices de
>;Desc/Clms Page number 13;
l'ad้้ny1ate cyc1ase.
14-Utilisation selon les revendications 12 et 13 du roseau pour la pr ้้paration de formulations
cosm้้tiques pr้้sentant des propri้้t้้s amincissantes locales par diminution de la charge lipidique
des adipocytes sous-cutan้้s.
15-Utilisation selon les revendications 1 เ 11 du roseau pour la pr้้paration de formulations
cosm้้tiques pr้้sentant des propri้้t้้s antiradicalaires ralentissant le vieillissement cellulaire par la
pr้้sence de polyph้้nols et de flavono๏des.
16-Utilisation selon les revendications 1 เ 11 du roseau pour la pr้้paration de formulations
cosm้้tiques pr้้sentant des propri้้t้้s hydratantes par la pr้้sence de polysaccharides et de sucres
libres tels que le saccharose.
17-Utilisation selon les revendications 1 เ 11 du roseau pour la pr้้paration de formulations
cosm้้tiques pr้้sentant des propri้้t้้s immunomodulatrices par la pr้้sence de polysaccharides.
18-Utilisation selon les revendications 1 เ 11 du roseau pour la pr้้paration de formulations
cosm้้tiques pr้้sentant des propri้้t้้s inhibitrices du vieillissement ้้pidermique et dermique par la
pr้้sence de polysaccharides sp้้cifiques tels que les arabinoglucanes et la pr้้sence de vitamine C et
d'acides organiques.
19-Utilisation selon les revendications 1 เ 11 du roseau pour la pr้้paration de formulations
cosm้้tiques pr้้sentant des propri้้t้้s d้้toxifiantes naturellement reconnues pour le roseau dans son
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environnement, par la pr้้sence de flavono๏des et de polyph้้nols permettant la complexation et
l'้้limination de m้้taux lourds et de polluants agressifs pour l'้้piderme.
20-Utilisation selon les revendications 1 เ 11 du roseau pour la pr้้paration de formulations
cosm้้tiques pr้้sentant des propri้้t้้s rafra้chissantes et tonifiantes naturellement reconnues pour
le roseau, par la pr้้sence de polysaccharides, de saccharose et de vitamine C (acide ascorbique).
21-Utilisation selon les revendications 14 เ 20 du roseau pour la pr้้paration de formulations
cosm้้tiques pr้้sentant des propri้้t้้s rajeunissantes g้้n้้rales pour l'้้piderme le derme et les
cheveux.Data supplied from the esp@cenet database - Worldwide
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12. GB1314870
- 26/4/1973
PRODUCTION OF DAIRY PRODUCTS
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=GB1314870
Applicant(s):
ARKADY NEW FOODS LTD (--)
IP Class 4 Digits: A23C
IP Class:A23C11/10; A23C11/00
E Class: A23C11/10B
Application Number:
GBD1314870 (19701010)
Priority Number: GB19700048255 (19701010)
Family: GB1314870
Equivalent:
FR2110350
Abstract:
Abstract of GB1314870
1314870 Synthetic milk ARKADY NEW FOODS Ltd 4 Oct 1971 [10 Oct 1970] 48255/70 Heading
A2B Ground soya is added to water, a sugar, preferably maltose, is added, the mixture is heated to
effect peptisation, insoluble material is removed, the mixture boiled to coagulate proteins, cooled, and
homogenised with a stabiliser, for example glyceryl monostearate, a portion of the homogenised
mixture has a fat, for example palm kernel or ground nut oil, and a stabiliser, for example glyceryl
monostearate and lecithin, added thereto to form a cream, which cream is then homogenised with the
remainder of the mixture to form a synthetic milk, the pH of the ground soya, sugar and water mixture
being adjusted before or after peptisation such that the milk produced has an acidity of about 0.005,
being the wt% of lactic acid present, and a pH of about 7.5, for example by the addition of a mild alkali
such as sodium or calcium carbonate. The product may be used as milk or in the production of
condensed or evaporated milk, milk powder, protein extract, cheese, ice cream or
chocolate.Description:
Description of GB1314870
(54) PRODUCTION OF DAIRY PRODUCTS
(71) We, ARKADY NEW FOODS LIMITED, a British Company of Arkady Soya Mills,
Old Trafford, Manchester, England, do hereby declare the invention, for which we pray that a patent
may be granted to us and the method by which it is to be performed, to be particularly described in and
by the followingstatement:
This invention relates to the production of dairy products such as milk and cheese from soya beans.
Milk as conventionally produced by cows or other animals is in fact a very uneconomical process. It
has been shown that a cow converts into milk only one eighth by weight of the foodstuffs ingested.
Further, the use of conventional milk causes certain difficulties in food manufacturing process, these
difficulties arising from the lactose in milk. Lactose is a disaccharide which is readily crystallisable and
when milk is in a condensed form, the lactose is, in effect, in the form of a supersaturated solution. As
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with any supersaturated solution, crystallisation can readily occur particularly on ageing.
Crystallisation of the lactose sugar in condensed milk is undesirable in any event but is even more
disadvantageous when condensed milk is employed in the manufacture of for example chocolate and
ice cream.
In such manufacturing processes a high total solids content is required but this requirement naturally
creates the conditions where crystallisation of lactose may result.
Moreover smoothness of the mix is a requirement of both chocolate and ice cream and this criteria is
difficult to obtain if lactose crystals are present. In normal circumstances therefore, smooth mixes are
only obtained after prolonged whipping or beating.
The present invention has been made from a consideration of the above-mentioned disadvantages.
According to the invention there is provided amethod of synthesising milk comprising adding ground
soya to water, adding a sugar thereto, heating the mixture to effect peptisation, removing insoluble
material from the mixture, boiling the mixture to co-agulate the proteins, cooling the mixture,
homogenising the mixture with a stabiliser, taking a portion of the homogenised mixture and adding a
fat and stabiliser thereto to produce a cream and homogenising the cream with the remainder of the
homogenised mixture to produce milk, the pH of the mixture of ground soya, sugar and water being
adjusted before or after peptisation such that the milk produced has apM of about 7.5 and an acidity of
about0.005.
Acidity is used herein in the percentage by weight of lactic acid present.
The preferred sugar is a disaccharide such as maltose; in particular it is preferred to use maltose
produced by enzymatic hydrolysis of starch, a process which is known per se.
It has been found that the mixture of ground soya and water has a pH of from6.3-6.4 and an acidity of
about 0.15 and therefore a mild alkali such as calcium carbonate or sodium carbonate is preferably
added to bring the pH to a value of about 7.1 to ensure that thepM of the final product is about 7.5.
ThepEI of the sugar is generally about 7.5 and it will be understood that the addition of the sugar to the
mixture will effect some adjustment of the pH, the remaining adjustment being made by the addition of
the required amount of mild alkali. The use of calcium carbonate as mild alkali for adjusting the pH is,
in fact, highly desirable since calcium is required in the synthesised milk if its analysis is to be
substantially the same as that of milk produced by cows.
The mixture of ground soya, water and sugar has an extremely beany flavour and the colour does not
look much like milk.
Boiling of the mixture diminishes the beany flavour and as previously indicated co-agulates the
proteins. The said co-agulation in effect increases the particle size of the proteins and the
subsequenthomogenisation with a stabiliser produces a stable emulsion having a colour substantially
the same as natural milk.
The stabiliser used to stabilise the emulsion may be any suitable emulsifying agent such as stearate, for
example glyceryl monostearate which may if desired be coupled with lecithin, or egg yolk and fat.
In order to produce the cream a portion of the homogenised mixture is combined with a fat such as
palm kernel or ground nut oils hydrogenated to a melting point of from32--34"C and with a stabilizer
of the kind above exemplified.
The cream thus produced is added to the remainder of the homogenised mixture and the cream and
mixture re-homogenised and cooled if a stable liquid milk is required.
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Synthetic milk produced according to the invention looks and tastes similar to natural milk from cows
and in many cases can be used for substantially the same purposes.
Thus the milk produced according to the invention may be condensed, or evaporated, used in the
manufacture of ice cream, chocolate orcheese, or milk powder or a protein extract prepared therefrom,
the methods used to produce such products being substantially the same as those used to produce such
products from cow's milk.
The following examples illustrate the invention.
EXAMPLE 1
200 gms. of soya beans having90%, total dry solids were ground and added to 1800mls. of water
together with 60 gms. of maltose produced by enzymatic hydrolysis of starch and 1.5 gms. of calcium
carbonate.
The resulting mixture was heated at55"C for about 1 hour. After cooling the mixture was passed
through a sieve and centrifuge and the fibrous and insoluble material removed therefrom. (The fibrous
and insoluble material was found to contain310/, protein, 20% fat, 10% fibres the balance being sugar
and minerals and after drying yielded a valuable animal foodstuff.)
The sieved mixture was then boiled to co-agulate the protein and thereafter cooled to about6OOC at
which temperature the mixture was homogenised in the presence of1 X ๓ by weight ofglycerol monostearate based on the weight of fat contained in the mixture.
Between 10 and305/, of this homogenised mixture was combined with hydrogenated palm kernel oil,
glyceryl monostearate and lecithin to form a cream and the cream thereafter added to the remainder of
the homogenised mixture and re-homogenised.
The re-homogenised mixture was cooled to ambient temperature and aged, the resulting product
having a pH of7.5 and resembling milk in taste, appearance and analysis.
EXAMPLE2
To 300 lb. water at50"C containing 0.34 lb. sodium carbonate was added 45 lb. enzyme active, full
fat soya flour. The mixture was stirred vigorously for 1 hour. After this the insoluble material was
removed by centrifugation. The resulting liquor was boiled and thereafter cooled to approximately70 C
12 ib. of a high maltose containing corn syrup was added and sodium carbonate was added to achieve
a pH of 7.5.
6-1- lb. hydrogenated palm kernel oil were melted together with 1 oz. glyceryl monostearate and 1
oz.lecithin, and a cream formed with approximately twice the volume of hot liquor.
The cream was recombined with the majority of the liquor and the whole homogenised and cooled.
290 lb. milk was obtained with the appearance and proximate analysis of cow's milk.
The invention is not restricted to the above described specific examples many variations thereof being
possible without departing from the scope thereof.
WHAT WE CLAIMIS:1. A method of synthesising milk comprising adding ground soya to water, adding a sugar thereto,
heating the mixture to effect peptisation, removing insoluble material from the mixture, boiling the
mixture to co-agulate the proteins, cooling the mixture, homogenising the mixture with a stabiliser,
taking a portion of the homogenised mixture and adding a fat and stabiliser thereto to produce a
creamaild homogenising the cream with the remainder of the homogenised mixture to produce milk,
the pH of the mixture of ground soya, sugar and water being adjusted before or after peptisation such
that the milk produced has a pH of about 7.5 and an acidity of about 0.005.
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2. A method as claimed in Claim 1,wherein the sugar is a disaccharide.
3. A method as claimed in Claim2, wherein the sugar is maltose.
4. A method as claimed in Claim 3, wherein the sugar is a maltose produced by enzymatic hydrolysis
of starch.
5. A method as claimed in any preceding
Claimwherein the adjustment of the pH of the mixture is effected by the addition of a mild alkali
thereto.
6. A method as claimed in Claim 5, wherein the mild alkali is calcium carbonate or sodium carbonate.
7. A method as claimed in any preceding
Claim wherein the stabiliser is glyceryl mono-stearate.
8. A method as claimed in any preceding
Claim, wherein the fat is palm kernel oil or ground nut oil.
9. A method of synthesising milk sub
**WARNING** end of DESC field may overlap start of CLMS **.Data supplied from the esp@cenet
database - Worldwide
Claims:
Claims of GB1314870
**WARNING** start of CLMS field may overlap end of DESC **.
a stabiliser produces a stable emulsion having a colour substantially the same as natural milk.
The stabiliser used to stabilise the emulsion may be any suitable emulsifying agent such as stearate, for
example glyceryl monostearate which may if desired be coupled with lecithin, or egg yolk and fat.
In order to produce the cream a portion of the homogenised mixture is combined with a fat such as
palm kernel or ground nut oils hydrogenated to a melting point of from32--34"C and with a stabilizer
of the kind above exemplified.
The cream thus produced is added to the remainder of the homogenised mixture and the cream and
mixture re-homogenised and cooled if a stable liquid milk is required.
Synthetic milk produced according to the invention looks and tastes similar to natural milk from cows
and in many cases can be used for substantially the same purposes.
Thus the milk produced according to the invention may be condensed, or evaporated, used in the
manufacture of ice cream, chocolate orcheese, or milk powder or a protein extract prepared therefrom,
the methods used to produce such products being substantially the same as those used to produce such
products from cow's milk.
The following examples illustrate the invention.
EXAMPLE 1
200 gms. of soya beans having90%, total dry solids were ground and added to 1800mls. of water
together with 60 gms. of maltose produced by enzymatic hydrolysis of starch and 1.5 gms. of calcium
carbonate.
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The resulting mixture was heated at55"C for about 1 hour. After cooling the mixture was passed
through a sieve and centrifuge and the fibrous and insoluble material removed therefrom. (The fibrous
and insoluble material was found to contain310/, protein, 20% fat, 10% fibres the balance being sugar
and minerals and after drying yielded a valuable animal foodstuff.)
The sieved mixture was then boiled to co-agulate the protein and thereafter cooled to about6OOC at
which temperature the mixture was homogenised in the presence of1 X๓ by weight ofglycerol monostearate based on the weight of fat contained in the mixture.
Between 10 and305/, of this homogenised mixture was combined with hydrogenated palm kernel oil,
glyceryl monostearate and lecithin to form a cream and the cream thereafter added to the remainder of
the homogenised mixture and re-homogenised.
The re-homogenised mixture was cooled to ambient temperature and aged, the resulting product
having a pH of7.5 and resembling milk in taste, appearance and analysis.
EXAMPLE2
To 300 lb. water at50"C containing 0.34 lb. sodium carbonate was added 45 lb. enzyme active, full
fat soya flour. The mixture was stirred vigorously for 1 hour. After this the insoluble material was
removed by centrifugation. The resulting liquor was boiled and thereafter cooled to approximately70 C
12 ib. of a high maltose containing corn syrup was added and sodium carbonate was added to achieve
a pH of 7.5.
6-1- lb. hydrogenated palm kernel oil were melted together with 1 oz. glyceryl monostearate and 1
oz.lecithin, and a cream formed with approximately twice the volume of hot liquor.
The cream was recombined with the majority of the liquor and the whole homogenised and cooled.
290 lb. milk was obtained with the appearance and proximate analysis of cow's milk.
The invention is not restricted to the above described specific examples many variations thereof being
possible without departing from the scope thereof.
WHAT WE CLAIMIS:1. A method of synthesising milk comprising adding ground soya to water, adding a sugar thereto,
heating the mixture to effect peptisation, removing insoluble material from the mixture, boiling the
mixture to co-agulate the proteins, cooling the mixture, homogenising the mixture with a stabiliser,
taking a portion of the homogenised mixture and adding a fat and stabiliser thereto to produce a
creamaild homogenising the cream with the remainder of the homogenised mixture to produce milk,
the pH of the mixture of ground soya, sugar and water being adjusted before or after peptisation such
that the milk produced has a pH of about 7.5 and an acidity of about 0.005.
2. A method as claimed in Claim 1,wherein the sugar is a disaccharide.
3. A method as claimed in Claim2, wherein the sugar is maltose.
4. A method as claimed in Claim 3, wherein the sugar is a maltose produced by enzymatic hydrolysis
of starch.
5. A method as claimed in any preceding
Claimwherein the adjustment of the pH of the mixture is effected by the addition of a mild alkali
thereto.
6. A method as claimed in Claim 5, wherein the mild alkali is calcium carbonate or sodium carbonate.
7. A method as claimed in any preceding
Claim wherein the stabiliser is glyceryl mono-stearate.
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8. A method as claimed in any preceding
Claim, wherein the fat is palm kernel oil or ground nut oil.
9. A method of synthesising milk sub
stantially as described herein with reference to any one of the Examples.
10. Milk synthesised by the method as claimed in any preceding Claim.
11. Condensed milk produced from the synthesised milk as claimed in Claim 10.
12. Evaporated milk produced from the synthesised milk as claimed in Claim 10.
13. Milk powder produced from the synthesised milk as claimed in Claim 10.
14. Protein extract produced from the synthesised milk as claimed in Claim 10.
15. Cheese produced from the synthesised milk as claimed in Claim 10.Data supplied from the
esp@cenet database - Worldwide
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13. GB1334204
- 17/10/1973
PREPARATION OF FATTY ACID ESTER MIXTURES ENRICHED IN
UNSATURATES
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=GB1334204
Applicant(s):
PROCTER and GAMBLE (--)
IP Class 4 Digits: C11B; C11C; C07C
IP Class:C11B7/00; C11C3/04; C11C3/00; C07C67/06
E Class: C11B7/00B4; C11C3/04
Application Number:
GB19720013119 (19720321)
Priority Number: US19710127753 (19710324)
Family: GB1334204
Equivalent:
US3755385; NL7203930; FR2131565; DE2214120; BE781120
Abstract:
Abstract of GB1334204
1334204 Fatty acid esters PROCTER & GAMBLE CO 21 March 1972 [24 March 1971] 13119/72
Heading C2C Mixtures of alkyl (1-4C) esters of unsaturated fatty acids are enriched in unsaturates by
contacting with a two phase solvent system comprising a liquid hydrocarbon and [gamma]butyrolactone at between 0 and 110 F., and separating the butyrolactone extract and hydrocarbon
raffinate and recovering the esters from the extract. The alkyl (1-4C) esters are obtained by
transesterification of a fat or oil with the 1-4C alcohol in the presence of mineral acids or a basic
catalyst. Alkyl esters derived from soybean, safflower, corn, palm, tung, lard and tallow oil may be
treated. Hydrocarbon solvents may be hexane, octane, nonane, hexadecane, cyclohexene, petroleum
ether, kerosene and light mineral oil.Description:
Description of GB1334204
PATENT SPECIFICATION
( 11) 1334204 NO DRAWINGS ( 21) Application No 13119/72 ( 22) Filed 21 March 1972 ( 31)
Convention Application No 127 753 ( 32) Filed 24 March 1971 in ( 33) United States of America (US)
( 44) ( 51)
Complete Specification published 17 Oct 1973
International Classification C 07 C 67/06 ( 52) Index at acceptance C 2 C 3 A 10 E 3 B 1 3 A 10 E 5
B 3 A 10 E 5 Fll D 3 A 1 OE 5 F 2 A 3 A 1 OE 5 F 3 A 3 A 10 E 5 F 3 B 3 A 10 E 5 F 3 C ( 72)
Inventor JAMES PEYTON HUTCHINS ( 54) PREPARATION OF FATTY ACID ESTER
MIXTURES ENRICHED IN UNSATURATES ( 71) We, THE PROCTER & GAMBLE COMPANY,
a Company organised under the laws of the State of Ohio, United States of America, of 301 East Sixth
Street, Cincinnati, Ohio 45202, United States of America, do hereby declare the invention, for which
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we pray that a patent may be granted to us, and the method by which it is to be performed, to be
particularly described in and by the following statement:The present invention relates to a process for separating lower alkyl esters on the basis of their degree
of saturation Preferably the process of the invention includes first preparing the lower alkyl esters of
fatty acids from fat or oil and then separating the esters on the basis of their degree of unsaturation The
term "lower alkyl" is used herein to mean alkyl groups having 1 to 4 carbon atoms.
Natural fats and oils, for example soybean oil, safflower oil, corn oil, palm oil, tung oil, lard oil and
tallow oil consist of mono-, di-, and tri-glycerides of fatty acids containing from 10 to 22 carbon atoms
Certain of these fatty acids are unsaturated, that is, they contain one or more carbon-to-carbon olefinic
double bonds The more double bonds they contain, the higher their "degree" of unsaturation The
presence of the double bonds causes the more highly unsaturated fatty acids to have unique and
desirable properties in comparison with their more saturated counterparts For example, the melting
points of the unsaturated fatty acids and their esters are lower than those of the corresponding saturated
acids, and such unsaturated fatty acids are useful in the preparation of liquid shortenings, usually in the
form of glyceride esters enriched in unsaturates Likewise, the unsaturated fatty acids are used in drying
oils in the paint industry, said drying properties being related to the cross-linking of olefinic bonds by
air and hence, to the degree of unsaturalPrice 25 pl tion of the oils It may therefore be seen that the
utility of unsaturated fatty acids and their 45 esters is well recognized in the art, and a method for
separating the more highly unsaturated materials from their more saturated counterparts present in
natural fats and oils is of commercial interest 50 Separation of esters of fatty acids having various
degrees of unsaturation has long been recognized as being difficult, and ordinary distillative procedures
for this purpose are not suitable for use on a commercial scale At the 55 same time, these unsaturated
materials are detrimentally discolored by excessive heat, and polymerization sometimes occurs at high
temperatures by reaction with oxygen; hence, separation is best achieved by extraction pro 60 cedures,
usually carried out at temperatures near room temperature For most commercial purposes it is nor
necessary to achieve complete separation of the saturated and unsaturated fatty materials, and it is not
necessary to 65 separate them into an extract fraction which is enriched in the desired unsaturated
material and a corresponding raffinate fraction which is depleted in unsaturated material The fraction
enriched in unsaturates is suitable for use in 70 the preparation of glycerides and other esters and fatty
acids needed to impart desirable properties to drying oils, liquid shortenings, etc, as mentioned above,
or is useful per se in such compositions 75 It is an object of this invention to provide a process for
obtaining mixtures of fatty acid esters enriched in unsaturates from natural fats and oils of the type
hereinabove detailed.
(The fatty acid esters having one or more 80 olefinic double bonds prepared herein are of various
types and are referred to collectively as "unsaturates") The process of the invention employs a twophase solvent system comprising a hydro 85 carbon phase and a y-butyrolactone phase 1 e 1,334,204
capable of separating lower alkyl esters of fatty acids in a y-butyrolactone extract phase enriched in
unsaturates and a hydrocarbon raffinate phase depleted in unsaturates.
The concurrently filed application No.
13120/72 (Serial No 1,334,205) of Hutchins discloses another solvent system suitable for separating
unsaturated fatty esters from less unsaturated fatty esters.
According to the invention a process of preparing mixtures of lower alkyl esters of fatty acids
enriched in unsaturates comprises contacting a mixture of the lower alkyl esters of unsaturated fatty
acids and less unsaturated fatty acids with a two-phase solvent system comprising a liquid hydrocarbon
and)y-butyrolactone at a temperature within the range from 0 OF to 1101 F, separating the resultant
ybutyrolactone extract phase and hydrocarbon raffinate phase and recovering the lower alkyl esters of
fatty acids from the extract phase.
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Preferably, the mixture of lower alkyl esters of unsaturated fatty acids and less unsaturated fatty acids,
which is used as starting material for the above separation process, is obtained from fats or oils by a
process which comprises trans-esterifying a fat or oil containing glycerides of unsaturated and less
unsaturated fatty acids with a lower alcohol at a temperature of from SOF to 3500 F, in the presence of
a mineral acid or a basic catalyst to yield the lower alkyl esters of the fatty acids present in said fat or
oil.
The fats and oils disclosed hereinabove as suitable sources for unsaturated fatty acids all contain said
fatty acids primarily in the form of glyceride esters These fatty glyceride esters may be converted into
the corresponding alkyl esters so that the unsaturates can be more readily removed from the less
unsaturated materials From the foregoing discussion it will be recognized that unsaturated acids and
esters having different degrees of unsaturation have very similar properties to one another and to the
corresponding saturated acids and esters, respectively, and that extractive separation of these various
materials depends on very minor solubility differences.
For example, the free acid forms of both the saturated and unsaturated materials are relatively soluble
in the polar solvent used herein and separation of these materials is not satisfactory when the extraction
is carried out with the polar acid form of the fatty materials.
For this reason, the fats and oils are converted into the alkyl ester form of the saturated and
unsaturated fatty acids, which is less polar than the acid form, so that minor solubility differences can
be exploited to achieve separation At the same time, however, it is necessary that the ester form of the
fatty materials be chosen so that the non-polar characteristics of the two classes of materials are not
unduly accentuated For example, both the saturated and unsaturated fatty acids esterified with long
chain alcohols tend to remain in the non-polar raffinate fraction after extraction since such materials do
not have sufficient polar solvent solubility to be extracted For this reason, it is necessary when using
the extraction systems described herein to convert the acids to their lower alkyl esters, preferably the
methyl, ethyl and propyl esters.
Such lower alkyl esters are neither excessively polar so as to be unduly soluble in the polar extract
solvent herein, nor are they so highly non-polar as to remain exclusively in the nonpolar raffinate
solvent.
The lower alkyl esters of the unsaturated and saturated fatty acids are prepared from the natural fats
and oils of the type hereinbefore noted by heating said fat or oil with a lower alcohol in the presence of
a mineral acid (for example H 2 SO 4, HCI, H 1 PO,), or basic catalyst at a temperature within the
range from 501 F to 350 OF for 10 minutes to 24 hours and recovering the lower alkyl esters from the
glycerol which is formed, by physical separation, all by methods well-known to those skilled in the art
Preferred catalysts used herein include the alkali metal salts of lower alcohols In this transesterification, it is preferable to employ at least three equivalents of the lower alcohol per equivalent of
glyceride ester to provide sufficient reactant to completely convert the acids in any triglycerides in the
fat or oil to the lower alkyl ester form.
Less alcohol can be used if product yield is not particularly important; a two-fold to three-fold excess
of alcohol can be used to provide both reactant and reaction solvent.
The catalyst, for example the alkali metal alcoholate, is used in amounts ranging from 0.1 equivalent
per equivalent of alcohol Large excesses of the catalyst represent an economic waste and are to be
avoided for this reason.
It is suitable to use from 0 01 to 1 0 equivalents of the mineral acid or basic catalyst, for example
alcoholate, for each equivalent of acid present in the fat or oil.
The alkali metal alcoholate catalysts preferred herein can be prepared by reacting the appropriate
alkali metal (usually sodium or potassium for economic reasons) with the lower alcohol, for example
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methanol, ethanol 1 or propanol Alternatively, a solution of alkali metal hydroxide, for example
sodium hydroxide, potassium hydroxide or lithium hydroxide in the lower alcohol serves the same
purpose herein as the metal alcoholate, 1, and provides lower alkyl esters of saturated and unsaturated
fatty acids by heating with the glycerides present in the fats and oils in the aforementioned manner
Alkali metal alcoholates especially suitable for use herein 1 i include: sodium methoxide, sodium
ethoxide and sodium propoxide Preferably sodium methoxide is used Methanol, ethanol and propanol,
and mixtures thereof, are the preferred lower alcohols A solution of sodium 13 L 20 hydroxide in
methyl alcohol, ethyl alcohol or propyl alcohol is likewise preferred herein for converting the fatty
glycerides to a mixture of glycerol and lower alkyl fatty acid esters suitable for use in the extraction
procedure.
A solution of sodium methoxide in methanol is especially preferred for use in the transesterification
herein.
In the extraction step of this process there is employed a two-phase solvent system comprising a
hydrocarbon, as described below and y-butyrolactone, which is commercially available Up to about
20 % by weight of water can be present in the y-butyrolactone to enhance the selective solvent
properties thereof.
However, since water reduces ester solubility, thereby decreasing the extraction rate, about % water
(based on weight of y-butyrolactone) is preferred, both to increase selectivity and to maintain
extraction capacity.
The hydrocarbon used herein to enhance the selectivity of the process may be any of the hydrocarbons
which are liquid at the extraction temperatures in the range noted, or mixtures thereof Hydrocarbons
suitable for use herein include: saturated linear and cyclic hydrocarbons having from 5 to 20 carbon
atoms, unsaturated liquid cyclic and linear hydrocarbons in the same range, and the liquid aromatic
hydrocarbons, for example benzene and toluene Branched chain and straight chain hydrocarbons are
equally suitable for use herein: saturated hydrocarbons are preferred Examples of hydrocarbons which
can be used herein include: pentane, cyclopentane, hexane, cyclohexane, octane, 3-methyl-octane,
decane, undecane, dodecane, benzene, eicosane, cyclo-eicosane, 4,5-diethyldecane, and mixtures
thereof Hydrocarbon mixtures such as mineral oils, liquid paraffins, and distilled kerosene fractions,
are also suitable for forming the raffinate phase in the extraction step of the present process Hexane is
especially preferred for use herein.
In the extraction procedure, the mixture of lower alkyl esters of saturated and unsaturated fatty acids
is contacted with the two-phase solvent system and the phases are allowed to separate Contact between
the two-phase solvent system and the mixture of fatty acid esters can be achieved by batch mixing, or
by use of any of the commercially available extraction apparatus involving countercurrent, cocurrent
continuous, and crosscurrent continuous, extraction techniques Contact time between the two-phase
solvent system and the ester mixture is usually in the range from 0 5 minutes to 60 minutes, preferably
from 2 minutes to 4 minutes The extraction is carried out at temperatures within the range from 0 F to
110 F, preferably from 40 F to 75 F.
At temperatures higher than 110 F, the selectivity of the y-butyrolactone phase for the unsaturated
esters is reduced.
The amount of the two-phase solvent system 65 used herein is not critical for achieving selective
extraction, but is commonly based on the total weight of the esters being extracted In order to maintain
optimum selectivity, the weight of esters dissolved in the y-butyro 70 lactone preferably should be no
greater than %, by weight of said -y-butyrolactone Most generally, from 5 to 40 parts of the /butyrolactone is used per part of ester; a ratio of parts of y-butyrolactone to one part ester 75 is
preferred About 0 5 to 3 parts of hydrocarbon phase is used for each part of ester.
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The final step of the process involves separating the y-butyrolactone extract phase from the
hydrocarbon raffinate phase and recovering 80 the ester mixture enriched in unsaturates.
More highly saturated esters can be recovered from the hydrocarbon solvent, if so desired.
Alternatively, the hydrocarbon phase can be re-extracted with y-butyrolactone to recover 85
additional unsaturated esters Physical separation of the two phases is achieved by simply drawing-off
one phase from the other.
Recovery of the desired unsaturated esters is accomplished by physical methods, for 90 example by
evaporation of the extract solvent.
The exemplary fats and oils hereinabove described as suitable sources for unsaturated fatty esters
contain a variety of fatty acids such as oleic acid, linolenic acid, eleostearic 95 acid, linoleic acid,
ricinoleic acid, palmitoleic acid, petroselenic acid and vaccenic acid, primarily in the form of glyceride
esters Common saturated fatty acid glycerides present in such fats and oils include those of lauric 100
acid, myristic acid, palmitic acid, and stearic acid By the process of this invention, the fatty materials
containing these various acids are converted to mixtures of the lower alkyl esters of said adds, and the
esters are separ 105 ated into one fraction enriched in unsaturates and another depleted in unsaturates
That is to say, there will be more olefinic double bonds in the esters in the extract phase than in the
raffinate phase Different fats and oils contain 110 different unsaturated and saturated fatty acids, in
different proportions For example, soybean oil contains major amounts of oleic and linoleic acids,
while whale oil contains major amounts of palmitoleic and palmitic acids 115 It is immaterial to the
process of this invention as to which unsaturated and saturated acids are present in the mixture of lower
alkyl esters being prepared and separated For example, the process of the invention may be used for
120 separating the lower alkyl esters of oleic acid from the lower alkyl esters of stearic acid; the lower
alkyl esters of linoleic acid from the lower alkyl esters of lauric acid and the lower alkyl esters of
linoleic acid from the lower 125 alkyl esters of stearic acid In addition, fatty acids having a multiplicity
of double bonds can be separated from fatty acids having fewer 1,334,204 1,334,204 double bonds For
example, by this process S the lower alkyl esters of linoleic acid, which have two double bonds, can be
separated from the lower alkyl esters of oleic acid, which have one double bond Likewise, the lower
alkyl esters of linolenic acid, which have three double bonds, can be separated from the lower alkyl
esters of linoleic acid It can therefore be seen that by the process of this invention, it is possible to
prepare extract fractions which are enriched in unsaturates It is to be further recognized that the
extraction and recovery processes herein can be repeated on the enriched material to achieve nearly
complete separation of the individual fatty acid esters based on their degree of unsaturation if so
desired.
Although the lower alkyl esters of any of the fats and oils herein disclosed may be extracted and
separated into fractions enriched in various unsaturates by this invention, soybean oil lower alkyl fatty
acid esters, especially methyl esters, are preferred herein Likewise, while this process can be used in
general to obtain ester fractions enriched in the lower alkyl esters of unsaturated fatty acids, it is
particularly suitable for separating the lower alkyl esters, especially the methyl esters, of oleic and
linolenic acids and for separating the lower alkyl esters, especially the methyl esters, of linoleic and
linolenic acids, thereby affording, in each instance, an extract phase enriched in unsaturates.
From the foregoing it can be seen that this process may be used to separate all manner of mixtures of
the lower alkyl esters of fatty acids into an extract phase enriched in unsaturates.
The following Examples illustrate the invention.
EXAMPLE I.
Step 1.
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The methyl esters of soybean oil were prepared as follows: 1500 g of soybean oil was heated at a
temperature from 250 F to 300 F for 30 minutes with nitrogen sparge under vacuum After cooling the
oil, 285 g of methanol containing 10 2 g of sodium methoxide (mixed under nitrogen) was added
thereto.
The total mixture was refluxed for one hour and the layers separated in a separatory funnel to yield
the methyl esters of the soybean oil fatty acids including methyl oleate, methyl linoleate, and methyl
linolenate.
1.0 g of the ester mixture obtained in step ( 1) was contacted with an extraction medium comprising
20 g of y-butyrolactone (BLO) and 2 g of hexane at 75 F In a second run, 1.0 g of the ester mixture
obtained above was contacted with an extraction medium comprisester was contacted with 21 g of
BLO at C In a third run, 1 0 g of the fatty acid methyl ester mixture was contacted with an extraction
mixture comprising 2 g of hexane and 20 g of BLO containing 5 % by weight of water at 75 C In a
fourth run, 1 0 g of the ester mixture was contacted with 1 0 g of hexane and 10 g of BLO containing
5 % water In still another run, 2 1 g of the above ester was contacted with 21 g of BLO at 0 F.
Step 3.
The BLO extract phases from the above procedures were drawn off The BLO phase and the hexane
phase were chromatographed to separate the various fatty acid methyl ester fractions The extraction
data from this series of extractions appear in Table 1.
In a second series of experiments, the effects of temperature, water in the BLO phase and removal of
the raffinate phase on selectivity were assessed using essentially the same procedure as that given
above The results appear in Table 2 The ft-factor appearing in Table 2 was calculated as follows:
Wt fraction A in y-butyrolactone Wt fraction B in y-butyrolactone Wt fraction A in hydrocarbon Wt
fraction B in hydrocarbon wherein A and B represent the lower alkyl ester of the fatty acids being
separated For example, L 83/2 is the,8 factor for the separation of an ester having three double bonds
from the one having two; P,/, is the factor for the separation of di-unsaturates from monounsaturates At
1 t-factors of about 1 5, and less, the process becomes uneconomical because it necessitates using
cumbersome extraction equipment Since the 13-factor remains above 1.5 when the total amount of
ester in the extract phase is not greater than about 10 % by weight, of said extract phase, conditions are
preferably adjusted to maintain this percentage.
-h TABLE 1
Ester Composition, wt % BLO Phase Hexane Phase gm gm gm gm Ester in gnm Ester in Lino Lino
Lino LinoEster Hexane BLO BLO Phase Hexane Phase Oleate leate lenate Oleate leate lenate A) 1 2
20 0 39 0 57 20 3 68 1 11 5 33 7 59 1 7 1 B) 1 1 10 0 40 0 56 19 7 66 0 14 3 30 5 61 9 7 6 C) 1 2 20 0
19 0 76 15 4 67 3 17 3 29 4 62 7 8 0 D) 1 1 10 0 18 0 79 15 4 67 2 17 3 28 6 62 4 9 0 E) 2 1 0 21 1 85 0
23 24 8 64 2 11 0 34 3 59 5 6 2 BLO with 5 % water Expt E run at O F, all others at 75 F.
ui ui I.0 1,334,204 TABLE 2
Run gm Ester in BLO Phase 1 0 0095 2 0 0180 3 0 0185 4 0 0360 0 0400 gm Ester in Hexane Phase
0.38 0.79 0.28 0.66 0.56 Temp F 32/1 P 33/2 2 05 1 99 1 93 1 69 1 65 6 0 0925 7 0 106 8 0 179 9 0
300 0 408 BLO containing ca.
No hexane used.
0 1 52 1 62 34 1 58 1 30 1 32 1 49 1 14 1 12 0 99 1.22 % water, by weight.
38/321
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The data indicate that the selectivity of the extraction is increased: (a) by use of a hydrocarbon solvent
in conjunction with the BLO; (b) at lower temperatures within the range; and (c) by adding water to the
BLO phase.
A compromise between extraction selectivity and capacity can be achieved by varying these
conditions.
In the above process the BLO was used, at a 50: 1, 5: 1, 2:1 and 1:1 weight ratio to the esters being
extracted, respectively, with equivalent results The hexane was respectively used at ratios of 50: 1, 20:1
and 1: 1, based on ester, with equivalent results.
In the above process, the soybean oil was replaced by an equivalent amount of palm oil, safflower oil,
whale oil, corn oil, lard oil, tallow oil, tung oil, and cottonseed oil, respectively, and equivalent results
were obtained in that the methyl esters of the fatty acids of these oils were separated into an extract
phase enriched in unsaturates and a raffinate phase depleted in unsaturates.
In the above process, the methanol-sodium methoxide was replaced by an equivalent amount of
ethanol-sodium ethoxide, propanolpotassium propoxide, a 1 molar solution of sodium hydroxide in
methyl alcohol, and a 1 molar solution of sulfuric acid in ethyl alcohol, respectively, and equivalent
results were secured in that the fatty glyceride esters were converted to their respective methyl-, ethyl-,
and propyl esters and separated into an extract fraction enriched in unsaturates and a raffinate fraction
depleted in unsaturates.
In the above process, the hexane was replaced by an equivalent amount of octane, nonane,
hexadecane, cyclohexene, petroleum ether, kerosene, and light mineral oil, respectively, and the
extraction was carried out at 0 F, 50 F and 1100 F, respectively, and equivalent results were
obtained.Data supplied from the esp@cenet database - Worldwide
Claims:
Claims of GB1334204
WHAT WE CLAIM IS:1 A process for preparing mixtures of lower alkyl esters of fatty acids enriched in unsaturates, which
comprises contacting a mixture of lower alkyl esters of unsaturated and less unsaturated fatty acids
with a two phase solvent system comprising a liquid hydrocarbon and 7-butyrolactone at a temperature
within the range from O F to 1 O F, separating the resultant 7-butyrolactone extract phase and
hydrocarbon raffinate phase and recovering the lower alkyl esters of fatty acids from the extract phase.
2 A process as claimed in claim 1, wherein the starting mixture of lower alkyl esters of unsaturated
and less unsaturated fatty acids 2.02 1.79 1.60 1.64 1.78 1,334,204 is obtained by trans-esterifying a fat
or oil containing unsaturated fatty esters or unsaturated fatty glyceride esters with a lower alcohol at a
temperature within the range from 50 F to 350 F in the presence of a mineral acid or a basic catalyst to
yield the lower alkyl esters of the fatty acids present in the fat or oil.
3 A process as claimed in claim 2, wherein the trans-esterification is carried out with at least three
equivalents of lower alcohol per equivalent of glyceride ester.
4 A process as claimed in claim 2 or 3, wherein the catalyst used is an alkali metal salt of a lower
alcohol.
5 A process as claimed in claim 4, wherein the catalyst used is sodium methoxide, sodium ethoxide or
sodium propoxide.
6 A process as claimed in any one of claims 2 to 5, wherein the catalyst is used in an amount from 0
01 to 1 0 equivalent for each equivalent of acid present in the fat or oil.
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7 A process as claimed in any one of claims 2 to 6, wherein trans-esterification is carried out by using
a solution of sodium methoxide in methanol.
8 A process as claimed in any one of claims 1 to 7, wherein the y-butyrolactone based on the weight
of the butyrolactone.
9 A process as claimed in any one of claims 1 to 8, wherein the liquid hydrocarbon used is hexane,
light mineral oil, petroleum ether or kerosene.
A process as claimed in any one of claims 1 to 9, wherein the total esters dissolved in the 7butyrolactone is not greater than 10 percent by weight of the y-butyrolactone.
11 A process as claimed in claim 10, wherein a ratio of 20 parts of y-butyrolactone to one part of ester
is used.
12 A process as claimed in any one of claims 1 to 11, wherein 0 5 to 3 parts of liquid hydrocarbon is
used for each part of ester.
13 A process as claimed in any one of claims 1 to 12 wherein the extraction is carried out at a
temperature within the range from F to 75 O F.
14 A process as claimed in any one of claims 1 to 13, wherein the lower alkyl esters are methyl, ethyl
or propyl esters.
A process as claimed in any one of claims 2 to 14, wherein the fat or oil comprises soybean oil,
cottonseed oil, safflower oil, corn oil, palm oil, tung oil, lard oil, or tallow oil.
16 A process as claimed in claim 2, wherein the oil is soybean oil, the lower alcohol is methyl alcohol,
the catalyst is sodium methoxide, the two-phase solvent comprises hexane and y-butyrolactone and the
extraction temperature is 75 F.
17 A process for preparing a mixture of lower alkyl esters of fatty acids enriched in unsaturates
according to claim 1 and substantially as herein described with reference to the lExamples.
18 Mixtures of lower alkyl esters of fatty acids enriched in unsaturates whenever prepared by the
process as claimed in any one of claims 1 to 17.
For the Applicants, CA 3 RPMAELS & RANSFORD, Chartered Patent Agents, 24, Southampton
Buildings, Chancery Lane, London, W C 2.
Printed for Her Majesty's Stationery Office by the Courier Press, Leamington Spa, 1973.
Published by the Patent Office, 25 Southampton Buildings, London, WC 2 A l AY, from which
copies may be obtained.Data supplied from the esp@cenet database - Worldwide
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14. GB1334205
- 17/10/1973
PREPARATION OF FATTY ACID ESTER MIXTURE ENRICHED IN
UNSATURATES
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=GB1334205
Applicant(s):
PROCTER and GAMBLE (--)
IP Class 4 Digits: C11B; C11C; C07C
IP Class:C11B7/00; C11C3/04; C11C3/00; C07C67/06
E Class: C11B7/00B10; C11C3/04
Application Number:
GB19720013120 (19720321)
Priority Number: US19710127754 (19710324)
Family: GB1334205
Equivalent:
NL7203929; FR2131564; DE2214179; BE781121
Abstract:
Abstract of GB1334205
1334205 Fatty acid esters PROCTER & GAMBLE CO. 21 March 1972 [24 March 1971] 13120/72
Heading C2C Mixtures of alkyl (1-4C) esters of unsaturated fatty acids are enriched in the unsaturates
by contacting with a two-phase solvent system comprising a liquid hydrocarbon and a homogeneous
liquid lower alkyl sulphoxide-lower alcohol solution at a temperature within the range 0 to 110 F.,
separating the resultant sulphoxide-alcohol extract phase and hydrocarbon raffinate and recovering the
esters from the extract. The alkyl (1-4C) esters are obtained by transesterification of a fat or oil with the
1-4C alcohol in the presence of mineral acids on a basic catalyst. Alkyl esters derived from soybean,
safflower, corn, palm, tung, lard and tallow oil may be treated. Hydrocarbon solvents may be pentane,
cyclopentane, hexane, octane, 3-methyloctane, hexadecane, cyclohexane, petroleum ether, kerosene
and light mineral oil. A dimethyl sulphoxide and methyl alcohol in a weight ratio of 100:1 to 10: 6 may
be used.Description:
Description of GB1334205
(54) PREPARATION OF FATTY ACID ESTER MIXTURES
ENRICHED IN UNSATURATES
(71) We, THE PROCTER & BR>;
GAMBLE COMPANY, a Company organised under the laws of the State of Ohio,
United States of America, of 301 East Sixth
Street, Cincinnati, Ohio 45202, United States of America, do hereby declare the invention, for which
we pray that a patent may be granted to us, and the method by which it is to be performed, to be
particularly described in and by the following statement:
The present invention relates to a process for separating lower alkyl esters of fatty acids on the basis of
their degree of unsaturation.
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In a further embodiment, the invention relates to a process of preparing the lower alkyl esters of fatty
acid from fat or oil and then separating the esters on the basis of their degree of unsaturation. The term
"loweralkyl is used herein to mean alkyl groups having from 1 to 4 carbon atoms.
Natural fats and oils, for example soybean oil, safflower oil, corn oil, palm oil, tung oil, lard oil and
tallow oil consist of mono-, diand tri-glycerides of fatty acids containing from 10 to 22 carbon atoms.
Certain of these fatty acids are unsaturated, that is, they contain one or more carbon-to-carbon olefinic
double bonds, the more double bonds, the higher the "degree" of unsaturation. The presence of the
double bonds causes the more highly unsaturated fatty acids to have unique and desirable properties in
comparison with their more saturated counterparts. For example, the melting points of the unsaturated
fatty acids and their esters are lower than those of the corresponding saturated acids and such
unsaturated fatty acids are useful for the preparation of liquid shortenings, usually in the form of
glyceride esters enriched in unsaturates.Likewise, the unsaturated fatty acids are used in drying oils in
the paint industry, said drying properties being related to the cross-linking of olefinic bonds by air
and hence, to the degree of unsaturation of the oils. It may therefore be seen that the utility of
unsaturated fatty acids and their esters is well recognized in the art, and a method for separating the
more highly unsaturated materials from their more saturated counterparts present in natural fats and
oils is of commercial interest.
Separation of esters of fatty acids having various degrees of unsaturation has long been recognized as
being difficult, and ordinary distillative procedures are unsuitable for carrying out this separation
commercially. At the same time, these unsaturated materials are detrimentally discoloured by excessive
heat, and polymerization sometimes occurs at high temperatures by reaction with oxygen; hence,
separation is best achieved by extraction procedures, usually carried out at temperatures near room
temperature. For most commercial purposes it is not necessary to achieve complete separation of the
saturated and unsaturated fatty materials, and it is only necessary to separate them into an extract
fraction which is enriched in the desired unsaturated material and a corresponding raffinate fraction
which is depleted in unsaturated material.The fraction enriched in unsaturates is suitable for use in the
preparation of glycerides and other esters and fatty acids needed to impart desirable properties to
drying oils, liquid shortenings, etc., as noted above, or is useful per se in such compositions.
It is an object of this invention to provide a process for obtaining mixtures of fatty acid esters enriched
in unsaturates from natural fats and oils of the type hereinabove detailed.
(The fatty acid esters having one or more olefinic double bonds prepared herein are of various types
and are referred to collectively
as"unsaturates)').
In the process of the invention there is employed a two-phase solvent system comprising a
hydrocarbon phase and a lower alcohollower alkyl sulfoxide phase capable of separat ing lower alkyl
esters of fatty acids into a lower alkylsulfoxide-lower alcohol extract phase enriched in unsaturates and
a hydrocarbon raffinate phase depleted in unsaturates.
The concurrently filed Application No.
13119/72 (Serial No. 1,334,204) (Hutchins) discloses another solvent system suitable for separating
unsaturated fatty esters from less unsaturated fatty esters.
According to the invention, a process of obtaining mixtures of lower alkyl esters of fatty acids
enriched in unsaturates comprises contacting a mixture of the lower alkyl esters of unsaturated and less
unsaturated fatty acids with a two phase solvent system comprising a liquid hydrocarbon and a
homogeneous liquid lower alkyl sulfoxide-lower alcohol solution at a temperature fromOOF to 1100F
and separating the resultant lower alkyl sulphoxide-lower alcohol extract phase and hydrocarbon
raffinate phase and recovering the lower alkyl esters of fatty acids from the extract phase.
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Preferably, the mixture of lower alkyl esters
of unsaturated and less unsaturated fatty acids, which is the starting material for the above process, is
obtained from fats or oils by a process which comprises trans-esterifying a fat or oil containing
glycerides of unsaturated and less unsaturated fatty acids with a lower alcohol at a temperature of from
500F to 3500F in the presence of a mineral acid or a basic catalyst to prepare the lower alkyl esters of
the fatty acids present in said fat or oil.
The fats and oils disclosed hereinabove as suitable sources for unsaturated fatty acids all contain said
fatty acids primarily in the form of glyceride esters. These fatty glyceride esters may be converted into
the corresponding alkyl esters so that the unsaturates can be more readily removed from the less
unsaturated materials. From the foregoing discussion it will be recognized that unsaturated acids and
esters having different degrees of unsaturation have very similar properties to one another and to the
corresponding saturated acids and esters, respectively, and that extractive separation of these various
materials depends on very minor solubility differences.For example, the free acid forms of both the
saturated and unsaturated materials are relatively soluble in the polar solvent used herein and
separation of these two classes of materials is not satisfactory when the extraction is carried out with
the polar acid form of the fatty materials. For this reason, the fats and oils are converted into the alkyl
ester form of the saturated and unsaturated fatty acids, which is less polar than the acid form, so that
minor solubility differences can be exploited to achieve separation. At the same time, however, it is
necessary that the ester form of the fatty materials be chosen so that the non-polar characteristics of the
two classes of materials are not unduly accentuated.For example, both the saturated and unsaturated
fatty acids esterified with long chain alcohols tend to remain in the nonpolar raffinate fraction after
extraction, since such materials do not have sufficient polar solvent solubility to be extracted. For this
reason, it is necessary when using the extraction systems, described herein to convert the acids to their
lower alkyl esters, preferably the methyl, ethyl and propyl esters. Such lower alkyl esters are neither
excessively polar so as to be unduly soluble in the polar extract solvent herein, nor are they so highly
nonpolar as to remain exclusively in the nonpolar raffinate solvent.
The lower alkyl esters of the unsaturated and saturated fatty acids may be prepared from the natural
fats and oils of the type hereinbefore noted by heating the fat or oil with a lower alcohol in the presence
of a mineral acid (e.g. H2SO4, HCI,H,PO4) or basic catalyst at a temperature within the range from
500F to 3500F for 10 minutes to 24 hours, and recovering the lower alkyl esters from the glycerol
which is formed, by physical separation, all in the manner well-known to those skilled in the art.
Preferred catalysts herein include the alkali metal salts of lower alcohols.In this trans-esterification it is
preferable to employ at least about three equivalents of the lower alcohol per equivalent of glyceride
ester to provide sufficient reactant to completely convert the acids in any triglycerides in the fat or oil
to the lower alkyl ester form, Less alcohol can be used if product yield is not important; a two-fold to
three-fold excess of alcohol can be used to provide both reactant and reaction solvent.
The catalyst, for example the alkali metal alcoholate, is used in amounts ranging from 0.1 equivalent
per equivalent of alcohol. Large excesses of the catalyst represent an economic waste, and should be
avoided for this reason.
It is suitable to use from 0.01 to 1.0 equivalents of the mineral acid or basic catalyst, for example
alcoholate, for each equivalent of acid present in the fat or oil.
The alkali metal alcoholate catalysts preferred herein can be prepared by reacting the appropriate
alkali metal, usually sodium or potassium for economic reasons, with the lower alcohol, for example
methanol, ethanol or propanol. Alternatively, a solution of alkali metal hydroxide, for example, sodium
hydroxide, potassium hydroxide or lithium hydroxide, in the lower alcohol serves the same purpose
herein as the metal alcoholate, and provides lower alkyl esters of saturated and unsaturated fatty acids
by heating with the glycerides present in the fats and oils in the aforementioned manner. Alkali metal
alcoholates especially suitable for use herein include sodium methoxide, sodium ethoxide, and sodium
propoxide, with sodiummetboxide being preferred. Methanol, ethanol, and propanol, and mixtures,
thereof, are the preferred lower alcohols.A solution of sodium hydroxide in methyl alcohol, ethyl
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alcohol or propyl alcohol is likewise preferred herein for converting the fatty triglycerides to a mixture
of glycerol and lower alkyl fatty acid esters suitable for use in the extraction procedure. A solution of
sodium methoxide in methanol is especially preferred for use in the trans-esterification described
herein.
In the extraction step of this process, a two-phase solvent system is employed comprising a
hydrocarbon phase, as described below, and a second phase comprising a solution of an alcohol and a
sulfoxide having the formulaR-S(O)-R. In order to be suitable for use herein, such sulfoxides must be
liquids and must possess the requisite polarity to provide selective extraction of the more highly
unsaturated esters from the more saturated esters. At the same time, the sulfoxides used herein must be
miscible with the alcohols hereinbelow described. For this reason, the sulfoxides useful herein are
limited to those wherein each group R in the above formula is lower alkyl, for example methyl, ethyl,
propyl and butyl. It is preferable to use dimethyl-sulfoxide.
When the sulfoxides of the type described above are used singly, some separation of fatty acid esters
based on degree of unsaturation occurs. However, the total solubility of both saturated and unsaturated
esters in sulfoxides is low, and when these sulfoxides are used singly, the total ester capacity of the
phase is low. For this reason, it is preferred to employ a lower alcohol to provide the requisite solubility
of the fatty esters in the phase. However, care must be taken to select an alcohol which is sufficiently
polar so as to maintain selectivity in the extraction of the various saturated and unsaturated materials.
At the same time, the alcohol must be miscible with the lower alkyl sulfoxide being used.Lower
alcohols, for example methanol, ethanol and propanol, are suitable herein for use in conjunction with
the lower alkyl sulfoxides noted above, to provide a homogeneous phase capable of at least partially
separating the lower alkyl esters of fatty acids according to their degree of unsaturation. It is preferable
to use methyl alcohol.
One phase used herein consists of a homogeneous liquid solution of a lower alcohol and a lower
sulfoxide of the type hereinabove disclosed, preferably a solution of dimethylsulfoxide and methyl
alcohol. The relative; weight ratio of sulfoxide: alcohol is from 100:1 to 10:6, more preferably from
10:1 to 10: 6. It is preferred to use a ratio of about 10:3. For example, the following combinations of
alcohol and sulfoxide can be employed herein: a mixture of methanol and dimethylsulfoxide (20: 80
weight ratio); a mixture of ethanol and dimethylsulfoxide (10:90 weight ratio); a mixture of methanol
and dipropylsulfoxide (10: 90 weight ratio).
It is preferable to use herein a homogeneous mixture of methanol and dimethylsulfoxide at a weight
ratio of alcohol: sulfoxide of20: 80. Some water, usually 5% to 10% by weight, can optionally be
present in the sulfoxide-alcohol phase.
The hydrocarbon phase used herein to enhance the selectivity of the process comprises any of the
hydrocarbons which are liquid at the extraction temperatures in the range noted, and mixtures thereof.
Hydrocarbons suitable for use herein include: saturated linear and cyclic hydrocarbons containing from
5 to 20 carbon atoms, unsaturated liquid cyclic and linear hydrocarbons in the same range, and the
liquid aromatic hydrocarbons, for example benzene and toluene. Branched chain and straight chain
hydrocarbons are equally suitable for use herein. It is preferable to use saturated hydrocarbons.
Exemplary hydrocarbons which can be used herein include: pentane, cyclopentane, hexane,
cyclohexane, octane, 3-methyloctane, decane, undecane, dodecane, benzene, eicosane, cycloeicosane,
4,5-diethyldecane and mixtures thereof.Hydrocarbon mixtures such as mineral oils, liquid paraffins,
and distilled kerosene fractions are also suitable for forming the raffinate phase in the extraction step of
the present process. Hexane is especially preferred for use herein.
In the extraction procedure, the mixture of lower alkyl esters of saturated and unsaturated fatty acids is
contacted with the two-phase solvent system, and the phases allowed to separate. Contact between the
twophase solvent system and the mixtures of fatty acid esters can be achieved by batch mixing or by
use of any of the commercially available extraction apparatus involving countercurrent, cocurrent
continuous, and crosscurrent continuous, extraction techniques.
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Contact time between the two-phase solvent system and the ester mixture is usually in the range from
0.5 minutes to 60 minutes, more preferably from 2 minutes to 4 minutes. The extraction is carried out
at temperatures fromOOF to 1100F, more preferably from 200F to 750F. At temperatures higher
than1100F, the selectivity of the sulfoxide-alcohol phase for the unsaturated esters is reduced.
The amount of the two-phase solvent system used herein is not critical to achieve selective extraction,
but is usually based on the total weight of the esters being extracted. Most generally, from 10 to 20
parts of the sulfoxide-alcohol phase is used per one part of ester. From 0.5 to 3 parts of the hydrocarbon
phase is used for each part of ester.
The final step of the process involves separating the sulfoxide-alcohol extract phase from the
hydrocarbon raffinate phase and recovering the ester mixture enriched in unsaturates.
More highly saturated esters can be recovered from the hydrocarbon, if desired. Alternatively, the
hydrocarbon phase can be reextracted with the sulfoxide-alcohol to secure additional unsaturated esters.
Physical separation of thetwo phases is achieved by simply drawing-off one phase from the other.
Recovery of the desired unsaturated esters is accomplished by physical methods, for example by
evaporation of the extract solvent.
The exemplary fats and oils hereinabove described as suitable sources for unsaturated fatty esters
contain a variety of fatty acids such as oleic acid, linolenic acid, eleostearic acid, linoleic acid,
ricinoleic acid, palmitoleic acid, petroselenic acid, and vaccenic acid, primarily in the form of glyceride
esters. Common saturated fatty acid glycerides present in such fats and oils include those of lauric acid,
myristic acid, palmitic acid, and stearic acid.
By the process of this invention, the fatty materials containing these various acids are converted into
mixtures of the lower alkyl esters of said acids, and said esters are separated into a fraction enriched in
unsaturates and one depleted in unsaturates.
That is to say, there will be more olefinic double bonds in the esters in the extract phase than in those in
the raffinate phase.
Different fats and oils contain different unsaturated and saturated fatty acids, and differing proportions
thereof. For example, soybean oil contains major amounts of oleic and linoleic acids, while whale oil
contains major amounts of palmitoleic and palmitic acids. It is immaterial in the practice of this
invention which unsaturated and saturated acids are present in the mixture of lower alkyl esters being
prepared and separated. For
Example, the lower alkyl esters of oleic acid can be separated from the lower alkyl esters of stearic acid
by the extraction system used herein; the lower alkyl esters of linoleic acid can be separated from the
lower alkyl esters of lauric acid, while the lower alkyl esters of linoleic acid can be separated from the
lower alkyl esters of stearic acid.In addition, fatty acids having a multiplicity of double bonds can be
separated from fatty acids having fewer double bonds. For example, by this process the lower alkyl
esters of linoleic acid, which have two double bonds, can be separated from the lower alkyl esters of
oleic acid, which have one double bond. Likewise, the lower alkyl esters of linolenic acid, which have
three double bonds, can be separated from the lower alkyl esters of linoleic add.
It can therefore be seen that by this invention it is possible to prepare extract fractions which are
enriched unsaturates. It is to be further recognized that the extraction and recovering processes herein
can be repeated on the enriched material so that a nearly complete separation of the individual fatty
esters based on their degree of unsaturation is obtained if so desired.
While the lower alkyl esters of any of the fats and oils herein disclosed are suitably extracted and
separated into fractions enriched in various unsaturates by this invention, soybean oil lower alkyl fatty
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acid esters, especially the methyl esters, are especially preferred herein. Likewise while this process
can be used in general to obtain ester fractions enriched in the lower alkyl esters of unsaturated fatty
acids, it is particularly suitable for separating the lower alkyl esters, especially the methyl esters, of
oleic and linolenic acids, and for separating the lower alkyl esters, especially the methyl esters, of
linoleic and linolenic acids, thereby affording, in each instance, an extract phase enriched in unsaturates.
From the foregoing, it can be seen that this process separates all manner of mixtures of lower alkyl
esters of fatty acids into an extract phase enriched in unsaturates. The following Examples illustrate the
invention.
Example I
Step 1. The methyl esters of soybean oil were prepared as follows: 1500 g. of soybean oil were heated
at 2500F to 3000F for 30 minutes with nitrogen sparge under vacuum.
After cooling the oil, 285 g. of methanol containing 10.2 g. of sodium methoxide (mixed under
nitrogen) were added thereto. The total mixture wasreflexed for one hour, and the layers separated in a
separatory funnel to yield the methyl esters of the soybean oil fatty acids including methyl oleate,
methyl linoleate, and methyl linolenate.
Step 2. One and two-gram samples of the ester mixture prepared in Step 1 were extracted with
dimethyl-sulfoxide(DMSO) methyl alcohol (MeOH)/hexane mixtures by stirring the ester with said
mixture at room temperature(ce. 75 F). The various ratios of solvents and extractants are shown in
Table
I.
Step 3. The methyl estersoi: the fatty acids separated in Step 2 were recovered from both the extract
phase and the raffinate phase, and the ester components present in each phase were estimated by their
gas chromatographic peak areas. The selectivity of the extraction procedure is listed in Table I, below,
as the linolenate/linoleate selectivity and was calculated on the basis of the following formula::
Wt. fraction linolenate in DMSO-MeOH
Wt. fraction linolenate in hexane
Selectivity =
Wt. fraction linoleate inDMSO-MeOH
Wt. fraction linoleate in hexane
TABLE I
#Ester Linolenate/
%MeOH DMSO-MeOH/ Extracted/ Linoleate in DMSO Hexane/Ester Ratio#DMSO-MeOH
Selectivity
0 20/2/1 0.008 1,74
20 20/2/1 0.015 1.56
10 20/1/2 0.028 1.75
20 20/1/2 0.045 1.60
0 10/2/1 0.011 1.85
40 10/2/1 0.022 1.63
The foregoing data indicate the good separation of the methyl esters of the fatty acids on the basis of
their degree of unsaturation. The data in column 3 indicate the increased extraction capacity when the
lower alcohol-sulfoxide mixtures are used in place of the sulfoxide, alone.
In the above process, the soybean oil was replaced by an equivalent amount of palm oil, safflower oil,
whale oil, corn oil, lard oil, tallow oil, tung oil and cottonseed oil, respectively, and equivalent results
were obtained in that the methyl esters of the fatty acids of these oils were separated into an extract
phase enriched in unsaturates and a raffinate phase depleted in unsaturates.
In the above process, the methanol-sodium methoxide was replaced by an equivalent amount of
ethanol-sodium ethoxide, propanolpotassium propoxide, a 1 molar solution of sodium hydroxide in
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methyl alcohol, and a 1 molar solution of sulfuric acid in ethyl alcohol, respectively, and equivalent
results were obtained in that the glyceride esters were converted to their respective methyl-, ethyl-, and
propyl- esters and were separated into an extract fraction enriched in unsaturates and a raffinate
fraction depleted in unsaturates.
In the above process, the hexane was replaced by an equivalent amount of octane, nonane,
cyclohexane, hexadecane, petroleum ether, kerosene, toluene and light mineral oil, respectively, and
the extraction was carried out atOOF, 500F and 1100F, respectively, and equivalent results were
obtained.
In the above process, the DMSO-MeOH extract phase was replaced by an equivalent amount of 1:1
(wt.)DMSO-ethanol, 2: 1(wt.) DMSO-propanol, 3:1(wt.) DMSOisopropanol, 1:1 (wt.)
diethylsulfoxidemethanol and 30:1 (wt.) dipropylsulfoxidepropanol, respectively, and equivalent
results wereobtained.
In the above process, the DMSO-MeOH solution was used, at weight ratios of 50:1, 5:1, 2:1 and 1:1
based on the weight of esters being extracted, respectively, with equivalent results. The hexane was
used at weight ratios of 50: 1,20:1, and 1:1, respectively, and good separations were achieved.
WHAT WE CLAIM IS:
1. A process for preparing mixtures of lower alkyl esters of fatty acids enriched in unsaturates,
comprising contacting a mixture of lower alkyl esters of unsaturated and less unsaturated fatty acids
with a two phase solvent system comprising a liquid hydrocarbon and a homogeneous liquid lower
alkyl sulfoxide-lower alcohol solution at a temperature within the range fromOOF to 1100F,
separating the resultant lower alkyl sulphoxide-lower alcohol extract phase and hydrocarbon raffinate
phase, and recovering the lower alkyl esters of fattv acids from the extract phase.
2. A process as claimed in claim 1, wherein the starting mixture of lower alkyl esters of unsaturated
and less unsaturated fatty acids is obtained by trans-esterifying a fat or oil containing esters or
glyceride esters of unsaturated fatty acids with a lower alcohol at a temperature of from 500F to35QOF
in the presence of a mineral acid or a basic catalyst to give the lower alkyl esters of the fatty acids
present in said fat or oil.
3. A process as claimed in claim 2, wherein the catalyst is an alkali metal salt of a lower alcohol.
4. A process as claimed in claim 3, wherein the catalyst is sodium methoxide, sodium ethoxide or
sodium propoxide.
5. A process asclaimed in any one of claims 2 to 4, wherein a solution of sodium methoxide in
methanol is used for the transesterification.
6. A process as claimed in any one of claims 2 to 5, wherein the amount of catalyst present is from
0.01 to 1.0 equivalent of catalyst for
**WARNING** end of DESC field may overlap start of CLMS **.Data supplied from the esp@cenet
database - Worldwide
Claims:
Claims of GB1334205
**WARNING** start of CLMS field may overlap end of DESC **.
Wt. fraction linolenate in DMSO-MeOH
Wt. fraction linolenate in hexane
Selectivity =
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Wt. fraction linoleate inDMSO-MeOH
Wt. fraction linoleate in hexane
TABLE I
#Ester Linolenate/
%MeOH DMSO-MeOH/ Extracted/ Linoleate in DMSO Hexane/Ester Ratio#DMSO-MeOH
Selectivity
0 20/2/1 0.008 1,74
20 20/2/1 0.015 1.56
10 20/1/2 0.028 1.75
20 20/1/2 0.045 1.60
0 10/2/1 0.011 1.85
40 10/2/1 0.022 1.63
The foregoing data indicate the good separation of the methyl esters of the fatty acids on the basis of
their degree of unsaturation. The data in column 3 indicate the increased extraction capacity when the
lower alcohol-sulfoxide mixtures are used in place of the sulfoxide, alone.
In the above process, the soybean oil was replaced by an equivalent amount of palm oil, safflower oil,
whale oil, corn oil, lard oil, tallow oil, tung oil and cottonseed oil, respectively, and equivalent results
were obtained in that the methyl esters of the fatty acids of these oils were separated into an extract
phase enriched in unsaturates and a raffinate phase depleted in unsaturates.
In the above process, the methanol-sodium methoxide was replaced by an equivalent amount of
ethanol-sodium ethoxide, propanolpotassium propoxide, a 1 molar solution of sodium hydroxide in
methyl alcohol, and a 1 molar solution of sulfuric acid in ethyl alcohol, respectively, and equivalent
results were obtained in that the glyceride esters were converted to their respective methyl-, ethyl-, and
propyl- esters and were separated into an extract fraction enriched in unsaturates and a raffinate
fraction depleted in unsaturates.
In the above process, the hexane was replaced by an equivalent amount of octane, nonane,
cyclohexane, hexadecane, petroleum ether, kerosene, toluene and light mineral oil, respectively, and
the extraction was carried out atOOF, 500F and 1100F, respectively, and equivalent results were
obtained.
In the above process, the DMSO-MeOH extract phase was replaced by an equivalent amount of 1:1
(wt.)DMSO-ethanol, 2: 1(wt.) DMSO-propanol, 3:1(wt.) DMSOisopropanol, 1:1 (wt.)
diethylsulfoxidemethanol and 30:1 (wt.) dipropylsulfoxidepropanol, respectively, and equivalent
results wereobtained.
In the above process, the DMSO-MeOH solution was used, at weight ratios of 50:1, 5:1, 2:1 and 1:1
based on the weight of esters being extracted, respectively, with equivalent results. The hexane was
used at weight ratios of 50: 1,20:1, and 1:1, respectively, and good separations were achieved.
WHAT WE CLAIM IS:
1. A process for preparing mixtures of lower alkyl esters of fatty acids enriched in unsaturates,
comprising contacting a mixture of lower alkyl esters of unsaturated and less unsaturated fatty acids
with a two phase solvent system comprising a liquid hydrocarbon and a homogeneous liquid lower
alkyl sulfoxide-lower alcohol solution at a temperature within the range fromOOF to 1100F,
separating the resultant lower alkyl sulphoxide-lower alcohol extract phase and hydrocarbon raffinate
phase, and recovering the lower alkyl esters of fattv acids from the extract phase.
2. A process as claimed in claim 1, wherein the starting mixture of lower alkyl esters of unsaturated
and less unsaturated fatty acids is obtained by trans-esterifying a fat or oil containing esters or
glyceride esters of unsaturated fatty acids with a lower alcohol at a temperature of from 500F to35QOF
in the presence of a mineral acid or a basic catalyst to give the lower alkyl esters of the fatty acids
present in said fat or oil.
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3. A process as claimed in claim 2, wherein the catalyst is an alkali metal salt of a lower alcohol.
4. A process as claimed in claim 3, wherein the catalyst is sodium methoxide, sodium ethoxide or
sodium propoxide.
5. A process asclaimed in any one of claims 2 to 4, wherein a solution of sodium methoxide in
methanol is used for the transesterification.
6. A process as claimed in any one of claims 2 to 5, wherein the amount of catalyst present is from
0.01 to 1.0 equivalent of catalyst for
each equivalent of acid present in the fat orevil.
7. A process as claimed in any one of claims 1 to6, wherein methyl alcohol is used for forming the
lower alkyl sulfoxide-lower alcohol solution.
8. A process as claimed in claim 7, wherein the homogeneous liquid lower alkyl sulfoxide-lower
alcohol solution contains a relative weight ratio of sulfoxide: alcohol within the range from 10:1 to
10:6.
9. A process as claimed in claim 8, wherein the relative weight ratio of sulfoxide: alcohol is10: 3.
10. A process as claimed in any one of claims 1 to 9, wherein a homogeneous mixture of methanol and
dimethyl sulfoxide in a weight ratio of alcohol: sulfoxide of 20: 80 is used for the extraction.
11. A process as claimed in any one of claims 1 to 10, wherein the liquid hydrocarbon used is hexane,
a light mineral oil, petroleum ether or kerosene.
12. A process as claimed in any one of claimst to 11, wherein the extraction is carried out at a
temperature within the range from 200F to750F;
13. A process as claimed in any one of claims 1 to 12 wherein from 10 to 20 parts of the sulfoxidealcohol solvent phase is used per one part of the weight of the esters being extracted.
14. A process as claimed in any one of claims 1 to 13, wherein from 0.5 to 3 parts of liquid
hydrocarbon is used for each part of the esters being extracted.
15. A process as claimed in any one of claims 1 to 14, wherein the lower alkyl esters are methyl, ethyl
or propyl esters.
16. A process as claimed in any one of claims 2 to 15, wherein the fat or oil is soybean oil, safflower
oil, com oil, palm oil, tung oil, lard oil, cottonseed oil or tallow oil.
17. A process as claimed in any one of claims 1 to 16, wherein the lower alkyl esters of oleic and
linolenic acids are separated.
18. A process as claimed in any one of claims 1 to 16, wherein the lower alkyl esters of linoleic and
linolenic acids are separated.
19. A process as claimed in any one of claims 2 to 16 wherein the oil is soybean oil, the lower alcohol
is methyl alcohol, the catalyst is sodium methoxide, the two - phase solvent system comprises hexane
and a mixture of dimethyl sulfoxide and methyl alcohol in a weight ratio of 10:1 and the extraction is
carried out at a temperature of750F.
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20. A process for preparing mixtures of lower alkyl esters of fatty acids enriched in unsaturates
according to claim 1 substantially as herein described with reference to the
Example.
21. Mixtures of lower alkyl esters of fatty acids enriched in unsaturates whenever prepared by the
process as claimed in any one of claims 1 to 20.Data supplied from the esp@cenet database Worldwide
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15. GB1474367
- 25/5/1977
TREATMENT OF OLEOUGENOUS MATERIALS
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=GB1474367
Applicant(s):
KLINGER R (--)
IP Class 4 Digits: C11B
IP Class:C11B1/04; C11B1/00; C11B1/06
E Class: C11B1/04
Application Number:
GB19730009962 (19740516)
Priority Number: GB19730009962 (19740516)
Family: GB1474367
Abstract:
Abstract of GB1474367
1474367 Recovery of oils from oleogeneous materials R V KLINGER 16 May 1974 [1 March 1973]
9962/73 Heading C5C [Also in Division B1] Oleogeneous material, e.g. palm fruit, is treated to remove
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the oil therefrom by feeding it through a sterilizer 17 comprising a closed vessel 42 containing a steam
atmosphere via a series of conveyers 43A to 43F arranged to transport the material lengthwise of the
vessel 42 and feed it to the next lower conveyer where, via vertical conveyer 18, it is delivered to a
screw press 20 to express the oil. Before entering 17, the material is passed, via descending and
ascending legs 13 and 14 of a conveyor, through hot water and after leaving 17 passes through a
thresher 20, digester 28 and the screw press 21, wherein gravity separators 22 to 25 separate the oil and
pass it to driers 26 and 27. The solids from press 21 are fed to a depericarper 29 to extract the nuts,
which are then delivered to a cleaner and grader 31, silo 32, nut cracker 33, hydrocyclones 34 and
thence to a kernel oil solvent extraction equipment 37. The sterilizer 17 contains hot water to level 15
therein and each conveyer may be adjusted to an individual delivery rate.Description:
Description of GB1474367
(54) TREATMENT OF OLEOGENEOUS MATERIALS
(71) I, RUBEN VALDEMERLINGER, an
Israeli national of 4, Westbourne Avenue,
London, W.3 (formerly of 36 Buxton Gardens, London, W.3) do hereby declare the invention for
which I pray that a patent may be granted to me and the method by which it is to be performed to be
particularly described in and by the following statement :
This invention relates to the treatment of oleogeneous materials and particularly such materials of
vegetable origin, such as palm fruit. The invention is directed to providing a process, and apparatus, for
treating the oleogeneous materials.
The present practice of extracting oil from palm fruit entails the treatment of the bunches in a batchtype steriliser with steam at high pressure to soften the fruit.
After sterilising, the fruit isdestalked, treated in a digestor and fed to a screw press, the pressed liquid
from which is separated into the required oil and waste water in one or more centrifuges.
The treatment of the palm fruit prior to entry to the screw press is time-consuming and requires a great
deal of manual control and handling.
In the present invention, the oleogeneous material is treated in a continuous process to prepare the
material for screw pressing.
In that way, a large rate of throughput is possible without undue capital expenditure on plant and with a
minimum of labour.
Thus one aspect of the invention residesm a method of treating oleogeneous material for the
extraction of oil in which the material is fed into a continuously operating steriliser vessel, in which the
material is continuously moved through a steam atmosphere on a succession of vertically spaced
conveyors, and from which the material is passed to a screw press for removing contained liquid.
Preferably the steriliser vessel comprises a plurality of sections which are removably attached to one
another and each of which contains at least one conveyor. The steriliser is with advantage operated at
sub-atmospheric pressure to minimise damage to the oleogeneous material.
Another aspect of the invention resides in apparatus for treating oleogeneous material for the
extraction of oil including a screw press, and, for conditioning the material for pressing in the press, a
continuously operable steriliser vessel, in which the material is continuously moved through a steam
atmosphere and which includes a plurality of continuously operable conveyors located one below
another within the -vessel and each arranged to transport material lengthwise of the vessel and then to
cause transported material to be transferred to the next lower conveyor, a continuously operable feed
mechanism for feeding the material to the upper, or uppermost, conveyor, and a continuously operable
delivery mechanism for receiving material from the lower or lowermost conveyor and for removing it
from the vessel.
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A preferred form of the apparatus comprises a steriliser vessel formed of a vertical succession of
sections, which are removably attached to one another and each of which contains at least one
transversely movable conveyor, each conveyor being arranged to transport material lengthwise of the
vessel and then to cause transported material to be transferred to the next lower conveyor; a
continuously operable feed mechanism for feeding the material to the uppermost conveyor; a screw
press; a continuously operable delivery mechanism for receiving material from the lowermost conveyor
of the steriliser vessel and delivering it to the screw press; and means for supplying steam to the
steriliser vessel.
The invention will be more readily un derstood by way of example from the following description of a
process and apparatus for removing oil from oleogeneous material, reference being made to the
drawings accompanying the provisional specification (Figures 1 to 4) and to the accompanying
drawings (Figures 5 to 8), inwhich::>;/RTI;
Figure 1 schematically illustrates the complete apparatus,
Figure 2 schematically illustrates the continuous steriliser used in the apparatus of Figure 1,
Figure 3 is a side view of one section of the -steriliser,
Figure 4 is a plan view of part of one of the conveyors of the continuous steriliser,
Figure 5 shows one of the gravity separators 22, 23 of Figure 1,
Figure 6 shows one of the gravity separators 24, 25 of Figure 1,
Figure 7 shows the mechanism for adjusting the oil take-off line from a separator of Figure 6, and
Figure 8 diagrammatically illustrates oildrying equipment.
Referring first to Figure 1 the palm fruit, or other oleogeneous material, is supplied continuously to a
screw or bucket elevator 12which delivers the material to a vertical conveyor system having a
descending leg 13 and an ascending leg 14.
Chain-carried and perforated buckets pass continuously round the conveyor system, descending down
leg 13 and ascending up leg 14; leg 13 is filled with hotwater while leg 14 contains hot water up to the
level 15 of the water in the steriliser vessel, to be described. At the bottom of the conveyor system is a
trap 16 (Figure 2) in which stones, sand and other foreign bodies washed out of the oleogeneous
material collect and from which they can be removed at intervals.
The upper leg 14 of the conveyor system raises the oleogeneous material above the level of the
elevator 12 and delivers the material to an entry conveyor 19 for a continuous steriliser indicated
generally at 17 in Figure 2 the entry conveyor 19 is shown -as a screw conveyor, but other forms mayte
employed.
The continuous steriliser 17 will be de -scribed in detail hereinafter. The oleogeneous material moves
continuously through the steriliser 17, which is filled with saturated steam, the transit time being
sufficient to heat the material properly for
subsequent treatment. From the continuous
steriliser, the material is fed out to the bottom of a second vertical conveyor 18, which is similar to the
ascending leg 14,
also filled with hot water, and which de
livers the material to a thresher 20 of known form. From the thresher, the comminuted material is fed
through a digester 28 to a screw press 21, designed to express the majority of the liquid constituents
from the material, the expressed liquid being fed to a system for purifying and drying the contained
oil.That system may comprise gravity separators 22, 23 to be described in connection with Figure 5,
followed by tank-type gravity separators 24, 25 to be described in connection with Figure 6.
Finally, the separated oil is dried in oil driers 26, 27 as shown in detail in Figure 8.
The solids from the screw press 21 are passed to known equipment for separating the fibrous
constituents of the fruit from the nuts and for recovering oil from the kernels. That equipment is
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illustrated schematically in Figure 1 and includes various equipment of known design and a solvent
extraction plant.
In particular, the solids from the screw press 21, consisting essentially of the fibrous constituents of the
palm fruit and the nuts, are fed to a depericarper 29 in which the fibres are remover from the nuts. The
fibres are passed to a fibre silo 36 for eventual use in the boilers of the plant.
The separated nuts pass from the depericarper 29 to a cleaner and grader 31and -thence to a nut silo 32
in which they are dried. The dried nuts then pass to a nut cracker 33 and through two hydrocyclones 34
in series which separate the kernels from the shells. The separated kernels are collected in a kernel silo
and drier 35, and the dried kernels are supplied from the silo 35 to solvent extraction equipment 37
from whence extracted oil leaves through line 38. If necessary a further supply of kernels from an
external source may be introduced into the solvent extraction equipment 37, with the kernels from the
silo 35. Some of the extracted oil in line 38 is recycled through line 39 to the input of equipment 37.
The plant may include equipment for the further treatment of the oil expressed from the fruit and
extracted from the kernels.
That equipment is illustrated schematically at 40 in Figure 1 and may include a palm oil mill, a refinery,
a soap factory, a margarine factory, a fertiliser plast and a dried protein supplement factory.
Turning now to Figure 2, the continuous steriliser 17 consists of a closed vessel 42, containing a series
of independent conveyors 43A-43F arranged one below the
other and extending alternatively from the
two ends of the vessel 42 and terminating
short of the other vessel end. Thus, the
oleogenous material supplied by the entry conveyor 19 is conveyed from right to left across the length
of the vessel 42 by the horizontal conveyor 43A. The material then falls from the end of conveyor43S
onto conveyor 43B, which moves it from left to right before allowing it to fall onto conveyor 43C.The
material is thus conveyed backwards and forwards across the vessel sixtimes in the arrangement
shown in Figure 2, although of course the number of conveyors 43 used in practice is dependent on the
operating conditions, and in particular on the speed at which the conveyors 43 operate. From the
lowermost conveyor43F, the material falls on to an exit conveyor44 which passes downwardly
through the water at the bottom of the vessel, indicated by the level 15, and leaves through the exit
passage 45, delivering the sterilised material to the vertical conveyor 18. Conveyor 44 is arranged so as
to receive any of the palm fruit or any other oleogeneous material that may have fallen off one of the
higher conveyors 43 without being transferred to a lower conveyor.
As shown in Figure 3, the steriliser 17 is formed in sections, two of which are shown at 17A, 17B, and
each of which contains one of the conveyors 43. Each section contains walls 46 so arranged as to mate
with the walls of adjacent sections, so that a vessel of required size can be readily made by
superimposing the requisite number of sections and securing them together.
As before mentioned, the vessel 17 is filled with saturated steam and the vesselmay be maintained at
an above-atmospheric pressure. It is, however, preferred to maintain the vessel at below atmospheric
pressure, so that the temperature may be retained at a relatively low value to prevent damaging the
oleogeneous material.
The number of conveyors 43 and their speed are chosen to ensure a required residence time of the
oleognous material within the sterilising vessel 17; for palm fruit, that residence time is about 40
minutes.
The construction of one of the conveyors 43 is illustrated in Figure 4. The conveyor has two endless
chains 48, each of which meshes with a sprocket wheel at each end of the conveyor, at the end shown
in
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Figure 4, the sprocket wheels are carried on a shaft 50 coupled at one end through a heat resistant
coupling 51 to a drive shaft 52 connected to a hydraulic or other motor, arranged to give a variable
speed drive. The other, non-driven, sprockets are carried on a similar shaft carried in bearings which
can slide in the direction of movement of the chains 48 and which can be positioned in that direction by
screws facilitating the tensioning of the chains.
A gap 53 is arranged between each sidewall 46 of the chamber and the conveyor, to permit the free
flow of steam around the conveyor to the material carried thereon, and to higher conveyors: the
conveyor 43 itself consists of a number of steel sections 54, each of which is carried between the two
chains 48 and has an upstanding edge wall 55 to prevent the material transported falling off the
conveyor. Both the sections 54 and the walls 55 are perforated, being made of mesh, or perforated
stainless steel strip. The width of each section, i.e. the separation of a chains 48, is dependent on the
required throughput of oleogeneous material through the steriliser and, if the sections 54 are of
excessive lengths, they may be supported centrally to avoid sag, by one or more rows of free-wheeling
rollers arranged to engage the undersides of the sections.
When the oleogeneous material is palm fruit, each conveyor 43 may have the following
characteristics:
The speed of the conveyor is about 5 feet per minute, the drive motors accordingly having a speed
variation between 0 and 20 r.p.m. The length and width of each conveyor are about 25 feet and 6 feet
respectively and the height of the sides 42 is about 1 foot. Each of the sections 54 has a width of about
1 foot and a length of about 6 feet and the perforations have a diameter of 3/8 inch at one inch spacing.
While the exit conveyor 44 is preferably similar to any of the conveyors 43, it may be replaced by one
or more screw conveyors, with perforated plates running in a downwardly inclined cage made of rods
to permit water to circulate therethrough. In order to catch fruit or other material falling from the upper
conveyors 43, the upper part of the bottom screw conveyor is formed with guides made of rods and
inclined inwardly from the sides of the steriliser.
Steam is continuously supplied to the vessel 42, and may also be supplied to the vertical conveyors 13,
14, 18 to maintain the water contained therein at an elevated temperature. The steriliser is generally
supplied with manholes, sight glasses, thermometers, presure gauges and like instrumentation for
observing and controlling the operation. In addition, various baffles and slides are provided within the
steriliser, such as those shown in Figure 2 at 57, to guide the oleogeneous material falling from one
conveyor 43 on to the next lower conveyor.
Reverting to Figure 1, and the system for separating the oil from the liquid expressed in press 71, it
will be seen that that liquid is first fed to the gravity separator 22. The oil-rich fraction from the
separator is fed to separator 23 while the water fraction is directed to separator 24.
The oil fraction from separator 23 is then passed in series through the oil dryers 26, 27.
The water fraction from separator 23 is fed to the separator 25 and oil-containing fractions from both
the separators 24, 25 are recycled to the inlet of separator 23, the water fractions being directed to
waste.
Gravity separators 22, 23 are similar and are is illustrated in Figure 5. The watercontaining oil from
the screw press in the case of separator 22, and from separator 22 in the case of separator 23, enters
through pipe 60 to a solids removal vessel 61; any solids present fall to the bottom of the vessel and are
removed through the bottom pipe 62. The liquid passes through pipe 63 into the interior of vessel 64.
The separation vessel 64 is provided with steam or hot water heating pipes 65, an exit oil pipe 66 at the
top of the vessel, and a bottom discharge pipe 67 for heavier waste constituents, predominantly water.
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The pipe 67 leads to a second vessel 68 having a conical roof in which is located centrally an oil takeoff pipe 70. The inlet pipe 67 has a series of inclined baffle plates 71 which extend into both the vessels
64 and 68 and which are designed to facilitate the freeing of the oil from the water. The water, which
may contain small proportions of oil, leaves vessel 68 through exit pipe 72 and is directed to enter
separator 23 or separator 25. Both oil pipe 66 and water pipe 72 preferably have regulators which are
indicated schematically at 73 and by which the level at which the oil and water are discharged from the
unit can be varied. Oil exit pipe 66 has baffles 74 similar to 67, to release any water carried up with oil.
One of the tank type gravity separators 24, 25 is shown in Figure 6. The supply pipe 76 enters the tank
77 which has a water discharge pipe 78 and an oil discharge pipe80. The latter opens to the interior of
tank 77 above the level of the water discharge pipe 78 and permits the removal of the lighter oil
collected at the top of the tank. As the density of the oil relative to the water may vary, pipe 80 is
adjustable vertically, by means of the mechanism shown in Figure 7. In Figure 7, the pipe 80 is shown
as being telescopic the upper section 80A being carried by two racks 81, which can slide on rollers
carried by a framework 82. The racks 81 are driven by a pair of work wheels 83 mounted on a cross
shaft 84 which can be turned, in order to adjust the position of pipe section 80A, by means of a pulley
85 and chain 86. The regulators 73 are similar.
In the case of each separator 24, 25, the oil through pipe 80 is led to a reservoir 87 provided with a
float switch 88 controlling a pump 90, which, when the oil level gravity separator rises above a given
point, pumps the oil away through recycle pipe 91 to the inlet of separator 23 (Figure 1).
One of the oil driers 26, 27 is shown diagrammatically in Figure 8. The oil is passed through a
labyrinth 100, in contact with steam pipes, which raise the temperature of the oil to 1100C; a
thermostat which responds to the temperature of the steam leaving the labyrinth controls the supply of
steam through the steam pipes; the drier should have at least four passes.
At the temperature within the drier, anywater contained in the oil is vaporised and the oil is then
passed to a steam extractor 101, which has baffle plates 102 and which is connected to a vacuum pump
103.
Steam and any other vapour contained in the oil is removed by the vacuum pump 103 while the
purified oil is passed to either the other dryer 27 or to a buffer tank 104 and thence to storage. Buffer
tank 104 has a float switch 105 controlling a discharge pump 106 which pumps the oil to storage.
WHAT ICLAIM IS:
1. A method of treating oleogeneous material for the extracion of oil in which the material is fed into a
continuously operating steriliser vessel, in which the material is continuously moved through a steam
atmosphere on a succession of vertically spaced conveyors, and from which the material is passed to a
screw press for removing contaned liquid.
2. A method of treating oleogenous material for the extraction of oil, in which the material is fed in a
continuously operating steriliser vessel comprising a vertical succession of sections, which are
removably attached to one another and each of which contains at least one transversely movable
conveyor, the material being continuously moved through a steamatmos- phere, being transported on
each conveyor in turn before falling on the next lower conveyor, and passing the material leaving the
steriliser vessel to a screw press for removing contained liquid.
3. A method of treating oleogeneousmaterial according to claim 2, in which the number of steriliser
sections and the speeds of the conveyors are chosen to give a residence time of the material within the
steriliser vessel appropriate to that material.
4. A method of treating oleogeneous material according to claim 3, in which each conveyor is
independently driven at an adjustable speed.
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5. A method of treating oleogeneous
**WARNING** end of DESC field may overlap start of CLMS **.Data supplied from the esp@cenet
database - Worldwide
Claims:
Claims of GB1474367
**WARNING** start of CLMS field may overlap end of DESC **.
The oil fraction from separator 23 is then passed in series through the oil dryers 26, 27.
The water fraction from separator 23 is fed to the separator 25 and oil-containing fractions from both
the separators 24, 25 are recycled to the inlet of separator 23, the water fractions being directed to
waste.
Gravity separators 22, 23 are similar and are is illustrated in Figure 5. The watercontaining oil from
the screw press in the case of separator 22, and from separator 22 in the case of separator 23, enters
through pipe 60 to a solids removal vessel 61; any solids present fall to the bottom of the vessel and are
removed through the bottom pipe 62. The liquid passes through pipe 63 into the interior of vessel 64.
The separation vessel 64 is provided with steam or hot water heating pipes 65, an exit oil pipe 66 at the
top of the vessel, and a bottom discharge pipe 67 for heavier waste constituents, predominantly water.
The pipe 67 leads to a second vessel 68 having a conical roof in which is located centrally an oil takeoff pipe 70. The inlet pipe 67 has a series of inclined baffle plates 71 which extend into both the vessels
64 and 68 and which are designed to facilitate the freeing of the oil from the water. The water, which
may contain small proportions of oil, leaves vessel 68 through exit pipe 72 and is directed to enter
separator 23 or separator 25. Both oil pipe 66 and water pipe 72 preferably have regulators which are
indicated schematically at 73 and by which the level at which the oil and water are discharged from the
unit can be varied. Oil exit pipe 66 has baffles 74 similar to 67, to release any water carried up with oil.
One of the tank type gravity separators 24, 25 is shown in Figure 6. The supply pipe 76 enters the tank
77 which has a water discharge pipe 78 and an oil discharge pipe80. The latter opens to the interior of
tank 77 above the level of the water discharge pipe 78 and permits the removal of the lighter oil
collected at the top of the tank. As the density of the oil relative to the water may vary, pipe 80 is
adjustable vertically, by means of the mechanism shown in Figure 7. In Figure 7, the pipe 80 is shown
as being telescopic the upper section 80A being carried by two racks 81, which can slide on rollers
carried by a framework 82. The racks 81 are driven by a pair of work wheels 83 mounted on a cross
shaft 84 which can be turned, in order to adjust the position of pipe section 80A, by means of a pulley
85 and chain 86. The regulators 73 are similar.
In the case of each separator 24, 25, the oil through pipe 80 is led to a reservoir 87 provided with a
float switch 88 controlling a pump 90, which, when the oil level gravity separator rises above a given
point, pumps the oil away through recycle pipe 91 to the inlet of separator 23 (Figure 1).
One of the oil driers 26, 27 is shown diagrammatically in Figure 8. The oil is passed through a
labyrinth 100, in contact with steam pipes, which raise the temperature of the oil to 1100C; a
thermostat which responds to the temperature of the steam leaving the labyrinth controls the supply of
steam through the steam pipes; the drier should have at least four passes.
At the temperature within the drier, anywater contained in the oil is vaporised and the oil is then
passed to a steam extractor 101, which has baffle plates 102 and which is connected to a vacuum pump
103.
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Steam and any other vapour contained in the oil is removed by the vacuum pump 103 while the
purified oil is passed to either the other dryer 27 or to a buffer tank 104 and thence to storage. Buffer
tank 104 has a float switch 105 controlling a discharge pump 106 which pumps the oil to storage.
WHAT ICLAIM IS:
1. A method of treating oleogeneous material for the extracion of oil in which the material is fed into a
continuously operating steriliser vessel, in which the material is continuously moved through a steam
atmosphere on a succession of vertically spaced conveyors, and from which the material is passed to a
screw press for removing contaned liquid.
2. A method of treating oleogenous material for the extraction of oil, in which the material is fed in a
continuously operating steriliser vessel comprising a vertical succession of sections, which are
removably attached to one another and each of which contains at least one transversely movable
conveyor, the material being continuously moved through a steamatmos- phere, being transported on
each conveyor in turn before falling on the next lower conveyor, and passing the material leaving the
steriliser vessel to a screw press for removing contained liquid.
3. A method of treating oleogeneousmaterial according to claim 2, in which the number of steriliser
sections and the speeds of the conveyors are chosen to give a residence time of the material within the
steriliser vessel appropriate to that material.
4. A method of treating oleogeneous material according to claim 3, in which each conveyor is
independently driven at an adjustable speed.
5. A method of treating oleogeneous
material according to any one of the preceding claims, in which the material from the steriliser vessel is
comminuted prior to entry into the screw press.
6. A method of treating oleogeneous material according to claim 5, in which the material is
comminuted in a thresher.
7. A method of treating oleogeneous material according to any one of the preceding claims, in which
the liquid pressed from the material in the screw press is subjected to gravity separation to derive
contained oil.
8. A method of treating oleogeneous material according to claim 7, in which there are two gravity
separators arranged in series, the aqueous phase being subsequently treated for the recovery of oil.
9. A method of treating oleogeneous material according to any one of the preceding claims, in which
the solids from the screw press are treated for the extraction of oil.
10. A method of treating oleogeneous material according to claim 9, in which the material is a
vegetable, kernel containing material, the screw press is arranged to avoid breakaged the kernels, and
the kernels are treated for the extraction of kernel oil.
11. A method of treating oleogeneous material according to claim 10, in which the kernel oil is
obtained by solvent extraction.
12. A method of treating oleogeneous material according to any one of the preceding claims, in which,
prior to entry into the steriliser vessel, the material is conveyed through a hot water bath.
13. A method of treating oleogeneous material according to any one of the preceding claims, in which
the steriliser vessel is operated at sub-atmospheric pressure.
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14. A method of treating oleogeneous material according to any one of the preceding claims, in which
the material is a vegetable material.
15. A method of treating oleogeneous material according to claim 14, in which the material contains
kernels.
16. A method of treating oleogeneous material according to claim 15, in which the material is palm
fruit.
17. A method of treating oleogeneous material substantially as herein described with reference to the
accompanying drawings and the drawings accompanying the provisional specification.
18. Oil extracted by the method according to any one of the preceding claims.
19. Apparatus for treating oleogeneous material for the extraction of oil including a screw press, and,
for conditioning the material for pressing in the press, a continuously operable steriliser vessel, in
which the material is continuously moved through a steam atmosphere and which includes a plurality
of continuously operable conveyors located one below another within the vessel and each arranged to
transport material lengthwise of the vessel and then to cause transported material to be transferred to
the next lower conveyor, a continuously operable feed mechanism for feeding the material to the upper,
or uppermost, conveyor, and a continuously operable delivery mechanism for receiving material from
the lower or lowermost conveyor and for removing it from the vessel.
20. Apparatus for treating oleogeneous material for the extraction of oil comprising a steriliser vessel
formed of a vertical succession of sections, which are removably attached to one another and each of
which contains at least one transversely movable conveyor, each conveyor being arranged to transport
material lengthwise of the vessel and then to cause transported material to be transferred to the next
lower conveyor; a continuously operable feed mechanism for feeding the material to the uppermost
conveyor; a screw press; a continously operable delivery mechanism for receiving material from the
lowermost conveyor of the steriliser vessel and delivering it to the screw press; and means for
supplying steam to the steriliser vessel.
21. Apparatus for treating oleogeneous material according to claim 20 in which each section has walls
adapted to mate with the walls of at least one other section.
22. Apparatus for treating oleogeneous material according to claim 20 or claim 21, in which each
conveyor has independent variable-speed drive means.
23. Apparatus for treating oleogeneous material according to any one of claims 20 to 22, in which the
feed mechanism includes a U-shaped conveyor adapted to contain hot water.
24. Apparatus for treating oleogeneous material according to any one of claims 20 to 23, in which the
delivery mechanism includes acomminuting device arranged to receive material from the steriliser
vessel and to feed comminuted material to the press.
25. Apparatus for treating oleogeneous material according to any one of claims 20 to 24, which
includes a gravity separation system for separating oil from liquid from the press.
26. Apparatus for treating oleogeneous material according to any one of claims 20 to 24, which
includes equipment for extracting oil from the solids from the press.
27. Apparatus for treating oleogeneous material for the extraction of oil, substantially as herein
described with reference to the accompanying drawings and the drawings accompanying the
provisional specification.
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เกี่ยวกับ น้ามันปาล์ ม สกัด (Palm oil Extract)
28. Oil extracted by the apparatus of any one of claims 19 to 27.Data supplied from the esp@cenet
database - Worldwide
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เกี่ยวกับ น้ามันปาล์ ม สกัด (Palm oil Extract)
16. GB1485268
- 8/9/1977
THERAPEUTIC PRODUCT EXTRACTED FROM PLANTS
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=GB1485268
Applicant(s):
SERTOG SOC ET RECH TRAVAUX ORG (--)
IP Class 4 Digits: A61K; B01D
IP Class:A61K; B01D; A61K35/78
E Class: A61K35/78
Application Number:
GB19740024640 (19740604)
Priority Number: GB19740024640 (19740604)
Family: GB1485268
Equivalent:
FR2273552; ES438178; BE829459
Abstract:
Abstract of GB1485268
1485268 Plant extracts S.E.R.T.O.G. SOC D'ETUDES DE RECHERCHES DE TRAVAUX
D'ORGANISATION ET DE GESTION 4 June 1975 [4 June 1974] 24640/74 Heading ASB A
pharmaceutical composition, with antiinflammatory, hormonal and muscular reactivation properties,
contains as its active constituent an extract of a plant with an organic solvent, of the Meliaceae family
of the genus Khaya selected from Khaya grandifolia, ivorensis or senegalensis. The extract is prepared
by pre-drying and finely grinding the plant and extracting with an organic solvent selected from
vegetable oils, e.g. palm or ground nut oil, hydrocarbons e.g. hexane chlorinated hydrocarbons e.g.
chloroform or methylene chloride, ethers, alcohols or mixtures thereof.Description:
Description of GB1485268
(54)ThERAPEUTIC PRODUCTEXI7RAMED FROM PlANTS
(71) We, S.E.R.T.O.G.SOCIETE
D'ETUDES, DERECHERCHES DE
TRAVAUX D'ORGANISATION ET DE
GESTION, of 53, Boulevard Victor Hugo, 92200Neuilly S/Seine, France; a Society organised under
the laws of France, do hereby declare the invention, for which we pray that a patent may be granted to
us, and the method by which it is to be performed, to be particularly described in and by the
followingstatement:
The present invention relates to a new therapeutic product extracted from plants, which has remarkable
anti-inflammatory, hormonal, muscular re-activation and conditioning properties, as well as an
exceptional therapeutic activity in the treatment of urino-genital disorders caused by pathological
conditions of the prostate gland.
The therapeutic product according to the present invention is characterised in that its active constituent
is an extract of a plant of the Meliaceae family, of the genus Khaya, selected from plants known under
the names of Khaya grandifolia, Khaya ivorensis, and
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Khaya senegalensis with an organic solvent, which plants are chiefly found in Africa, but are also
found in other regions of the world.
Preferably, the Khaya extract is obtained from the cortex of the plant, but it can equally be obtained
from the wood, the leaves, the fruit or other parts of the plant
Also according to the present invention, there is provided a method of preparing an extract of a plant
of the genus Khaya characterised in that the Khaya plant, which is pre-dried and finely ground, is
extracted with an organic solvent selected from the group which comprises vegetable oils, such as palm
oil or ground nut oil, hydrocarbons such as hexane, chlorinated hydrocarbons such as chloroform or
methylene chloride, ethers, alcohols or mixtures of these solvents.
In accordance with one particular preferred embodiment of the process which is the subject of the
present invention, the plant of the genus Khaya is treated in a first stage with a vegetable oil, the fatty
acids are thereafter saponified and the unsaponified extract further extracted with a hydrocarbon or a
chlorinated hydrocarbon.
In all cases, the extract obtained is put in an appropriate administrative form, after evaporation and
drying, by associating the extract with a therapeutically acceptable carrier.
This therapeutic product can be put into any suitable known form for administration, for example, in
unitary doses, such as tablets, dragees, capsules or microcapsules, for oral administration, and liquid
compositions for parenteral administration.
The invention will be further described, by way of example, with reference to the followingnonlimitative Examples.
EXAMPLE 1.
100 g of powdered cortex of finely groundKhsya grandifolia is pre-dried and is then extracted with
200 ml of chloroform. The pasty extract obtained represents a yield of 0.2% with respect to the weight
of the powdered cortex used as starting material.
After evaporation and drying, the extract obtained is put into an appropriate pharmaceutical form
suitable for administration, in unitary doses, by using known techniques.
EXAMPLE 2.
In an extractor provided with a double heating jacket and a stirrer, there is placed 100 kg of cortex
ofKhaye grandifolia, predried and finely ground, followed by 800 litres of ground nut oil. This is
agitated for 6 hours at a temperature of between 450 C.
and550 C After this time the lipid-rich fraction is extracted in a centrifuge. Subsequently, the fatty
acids are saponified by using potassium hydroxide. The saponified matter is decanted and the
unsaponified mass extracted with 80 litres of hexane. After evaporation and drying, the extract
obtained is put into an appropriate pharmaceutical form.
The Khaya extract obtained in accordance with the process of the present invention possesses
valuable therapeutic properties which are shown by the pharmacological and clinical experiments
which are detailed hereinafter.
The details of the experiments are, of course, given solely by way of example.
PHARMACOLOGICAL STUDY OF THE
TOTAL EXTRACT OF KHAYA
GRANDIFOLIA.
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เกี่ยวกับ น้ามันปาล์ ม สกัด (Palm oil Extract)
With the object of providing an explanation of certain results obtained in human clinology as a result
of the use of Khaya extracts, a pharmacological study has been undertaken on rats.
MATERIAL AND METHOD:
Animals used:
Adult male rats aged more than 20 months,WE STAR of the firm MORINI weighing between 280
and 350 grammes.
Method
3 groups of 20 rats are studied, and treated as follows: at the same time and under the same conditions.
Group I--Control animals
This group receives each day in the week but one, in one oral dose, a 0.1%, by weight, solution of
Tween (Registered Trade Mark) 20.
Group 1l
This group receives a similar solution of
Tween 20 to the control animals but additionally containing 0.725 mg/kg (body weight) of total extract
of Khaya. The animals are treated with one oral dose, six days out of every seven.
Group III
This group receives the same quantity of
Tween 20 but containing 3.625 mg/kg (body weight) of total extract of Khaya, that is to say, five times
the therapeutic dose given to the Group II animals above.
The weight of the animals- is monitored each week. The treatment is effected over a period of 12
weeks. The experiments utilise three groups of rats, amongst which controls have been effected in the
following manner at the end of the experiments. 10 rats from each group were used for examination of
the diureses two days before slaughtering, in 5 rats there is made a determination of the glucose in the
blood, in 5 rats there is effected a bromosulphophthalein test for examination of the hepatic function,
on 10 rats all of the blood is let by the abdominal aorta under an ether anesthetic and the quantities of
total phosphatase acid and the prostatic seric phosphatase are determined.
METHOD OF ANALYSIS OF THE
SERUM.
Glucose is estimated by utilising the Boehringer-Mannheim enzymatic method.
Phosphotase acid is estimated by the Andersch et al method as modified by Fishman et al.
Seric bromosulphophthalein is estimated with the SCLAVO reagent and the diureases are estimated in
accordance with the method of LIPSCHITZ et al.
The organs are weighed, examined histologically and the weight measured relative to 100 grammes of
body weight.
RESULTS 1. Mortality
Only two rats of group II died but this did not appear to be due to the treatment.
In general, the state of the treated animals is very good and noticeably better than that of the test rats.
2. Weight
There is observed an increase in the weight of the animals treated with the Khaya extract, relative to
that of the test rats, whilst the accompanying drawing shows a graph in which the increase in weight
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เกี่ยวกับ น้ามันปาล์ ม สกัด (Palm oil Extract)
with respect to the percentage of the body weight, during the duration of the experiment, that is to say
12 weeks, is shown. The curve I of this graph relates to the control animals, the curve II shows the
increase in weight of rats which have received 0.725 mg/kg/day of Khaya and the curve III shows an
increase in weight of the rats having received 3.625 mg/kg/day of
Khaya.
3. Action ontiw biochemicai parameters of senm
There is observed a noticeable reduction, which is proportional to the dose of extract used, of creatinin,
of creatinin phosphokinase, dehydrogenase lactase and seric creatinin.
Thus, the creatinin phosphokinase and the dehydrogenase lactate are lower by 50% and the seric
creatinin by 21%.
All of the other parameters are not noticeably affected.
4.Nematologic Action.
There is no noticeable difference between the animals treated and the control animals, irrespective of
the dose used.
5. Action on the diuresis
There is no significant difference in the diuresis between the groups of treated rats and the control rats.
On the contrary, there is observed a smaller quantity of blood, which is statistically significant, in the
urine of the rats treated with the dose of 0.725 mg/kg than in the control rats and in the group treated
with 3.625 mg/kg.
6. Action on thehepatic f unctioning
The quantity of bromosulphophthalein excreted is greater in the group of rats treatedwith the dose of
0.725 mg/kg than in theother groups.
There is no variation of the other parameters, viz. glucose, total phosphatase acid andpre static
phosphatase acid in the serum, irrespective of the dose of Khaya extract and the duration of the
experiment.
7. Action on the Organs
There is no notable difference in the percentage weights of the organs of the animals treated and of the
control animals and no apparent adverse effects which can be ascribed to the treatment.
On the contrary, in the treated rats, the prostate glands are more developed and this dilation is more
marked with the strongerdose-3 .625 mg/kg.
With the dose of 0.725 mg/kg the glandular secretion appears greater than with the control rats.
CONCLUSION
First of all, the total extract of Khaya used in the proportions of 0.725 mg/kg and 3.625 mg/kg is
tolerated with no side effects for 12 weeks and causes no apparent toxicity nor dangerous alteration in
the biochemical and haematological parameters.
On the contrary, the total extract shows a favourable action on the growth (weight curve), on the
functioning of the prostate gland, but in particular on the parameters which characterises the muscular
activity and the metabolic energy (creatinin phosphokinase and dehydrogenase lactate), as well as on
function (seric creatinin).
The effect on these functions seems to be proportional to the dose used, because the reduction of the
three parameters is very marked with the dose of 3.625 mg/kg.
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เกี่ยวกับ น้ามันปาล์ ม สกัด (Palm oil Extract)
The animals used were aged rats which frequently showed a reduction in muscular activity, of
metabolic energy and of the renal function. The results obtained showed an effect which is very
different to that which had been studied previously. It relates to an effect of the enzymatic type which
is illustrated by the variations of the levels of creatinin phosphokinase and of dehydrogenase lactate.
Action of the Total Extract of Khaya Grandifolia Administered Per OS on the
Biochemical Parameters over a Period of 12 Weeks
Treatment mg/kg day
EMI4.1
>;SEP; Khaya >;SEP; grandifolia >;SEP; Khaya >;SEP; grandifolia
>;tb; >;SEP; Patameter >;SEP; of >;SEP; serum >;SEP; Tween >;SEP; 20 >;SEP; total >;SEP; extract
>;SEP; total >;SEP; extract
>;tb; >;SEP; 1 >;SEP; /00 >;SEP; 0.725 >;SEP; 3.626
>;tb; protein >;SEP; (total) >;SEP; g% >;SEP; 8.17 >;SEP; # >;SEP; 0.38 >;SEP; 7.39 >;SEP; #
>;SEP; 0.29 >;SEP; 7.54 >;SEP; # >;SEP; 0.27
>;tb; albumin >;SEP; g% >;SEP; 2.53 >;SEP; # >;SEP; 0.10 >;SEP; 2.22 >;SEP; # >;SEP; 0.15 >;SEP;
2.28 >;SEP; # >;SEP; 0.09
>;tb; calcium >;SEP; mg% >;SEP; 9.35 >;SEP; # >;SEP; 0.36 >;SEP; 9.30 >;SEP; # >;SEP; 0.25
>;SEP; 10.04 >;SEP; # >;SEP; 0.23
>;tb; non-organic >;SEP; phosphorus >;SEP; mg% >;SEP; 7.16 >;SEP; # >;SEP; 0.28 >;SEP; 6.67
>;SEP; # >;SEP; 0.34 >;SEP; 6.46 >;SEP; # >;SEP; 0.14
>;tb; cholesterol >;SEP; mg% >;SEP; 77.50 >;SEP; # >;SEP; 2.01 >;SEP; 70.10 >;SEP; # >;SEP; 2.56
>;SEP; 60.00 >;SEP; # >;SEP; 3.78
>;tb; uric >;SEP; acid >;SEP; mg% >;SEP; 1.58 >;SEP; # >;SEP; 0.12 >;SEP; 1.64 >;SEP; # >;SEP;
0.10 >;SEP; 1.33 >;SEP; # >;SEP; 0.10
>;tb; creatinin >;SEP; mg% >;SEP; 0.77 >;SEP; # >;SEP; 0.02 >;SEP; 0.72 >;SEP; # >;SEP; 0.03
>;SEP; 0.61 >;SEP; # >;SEP; 0.02
>;tb; bilirubin >;SEP; (total) >;SEP; mg% >;SEP; 0.38 >;SEP; # >;SEP; 0.03 >;SEP; 0.38 >;SEP; #
>;SEP; 0.05 >;SEP; 0.34 >;SEP; # >;SEP; 0.02
>;tb; alkaline >;SEP; phosphatase >;SEP; micrograms/ml >;SEP; 110.10 >;SEP; # >;SEP; 8.46 >;SEP;
124.10 >;SEP; # >;SEP; 16.60 >;SEP; 108.70 >;SEP; # >;SEP; 8.31
>;tb; creatinin >;SEP; phosphokinase >;SEP; micrograms/ml >;SEP; 1002.00 >;SEP; # >;SEP; 187.96
>;SEP; 640.00 >;SEP; # >;SEP; 115.78 >;SEP; 546.00 >;SEP; # >;SEP; 50.60
>;tb; dehydrogenase >;SEP; lactate >;SEP; micrograms/ml >;SEP; 1076.40 >;SEP; # >;SEP; 101.59
>;SEP; 679,20 >;SEP; # >;SEP; 107.80 >;SEP; 520.00 >;SEP; # >;SEP; 51.98
>;tb; transaminase >;SEP; glutam >;SEP; oxal >;SEP; micrograns/ml >;SEP; 255.90 >;SEP; # >;SEP;
22.14 >;SEP; 233.40 >;SEP; # >;SEP; 14.76 >;SEP; 240.30 >;SEP; # >;SEP; 9.54
>;tb; uric >;SEP; nitrogen >;SEP; mg% >;SEP; 16.05 >;SEP; # >;SEP; 0.44 >;SEP; 15.70 >;SEP; #
>;SEP; 0.73 >;SEP; 15.65 >;SEP; # >;SEP; 0.69
>;tb; glucose >;SEP; mg% >;SEP; 103.90 >;SEP; # >;SEP; 6.15 >;SEP; 112.96 >;SEP; # >;SEP; 5.07
>;SEP; 100.60 >;SEP; # >;SEP; 3.97
>;tb; chloride >;SEP; milli-eauivalents/litre >;SEP; 103.70 >;SEP; # >;SEP; 0.83 >;SEP; 104.60
>;SEP; # >;SEP; 1.04 >;SEP; 105.30 >;SEP; # >;SEP; 0.37
>;tb; phosphatase >;SEP; acid >;SEP; (total) >;SEP; micrograms/ml >;SEP; 14.35 >;SEP; # >;SEP;
0.65 >;SEP; 18.56 >;SEP; # >;SEP; 2.76 >;SEP; 17.42 >;SEP; # >;SEP; 1.36
>;tb; prostatic
>;tb; phosphatase >;SEP; acid >;SEP; micrograns/ml >;SEP; 5.81 >;SEP; # >;SEP; 0.42 >;SEP; 5.68
>;SEP; # >;SEP; 0.48 >;SEP; 5.88 >;SEP; # >;SEP; 0.75
>;tb; Action of the Total Extract of Khaya Grandifolia Adiministered Per OS over a period of 12
weeks on the Biochemical Parameters of the Male Rats
Treatment mg/kg/day
EMI5.1
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เกี่ยวกับ น้ามันปาล์ ม สกัด (Palm oil Extract)
>;SEP; Khaya >;SEP; grandifolia >;SEP; Khyaya >;SEP; grandifolia
>;tb; >;SEP; Parameter >;SEP; Tween >;SEP; 20 >;SEP; total >;SEP; extract >;SEP; total >;SEP;
extract
>;tb; >;SEP; 1 >;SEP; /00 >;SEP; 0.725 >;SEP; 3.625
>;tb; bromosulphophthalein >;SEP; mg >;SEP; % >;SEP; 0.95 >;SEP; # >;SEP; 0.30 >;SEP; (5)
>;SEP; 0.47 >;SEP; # >;SEP; 0.11 >;SEP; (5) >;SEP; 0.68 >;SEP; # >;SEP; 0.17 >;SEP; (4)
>;tb; glucose >;SEP; mg >;SEP; % >;SEP; 95.84 >;SEP; # >;SEP; 4.66 >;SEP; (5) >;SEP; 106.67
>;SEP; # >;SEP; 3.13 >;SEP; (5) >;SEP; 108.20 >;SEP; # >;SEP; 3.18 >;SEP; (5)
>;tb; acid >;SEP; phosphatase >;SEP; (total) >;SEP; micrograms/ml >;SEP; 17.55 >;SEP; # >;SEP;
1.01 >;SEP; (9) >;SEP; 17.61 >;SEP; # >;SEP; 0.90 >;SEP; (7) >;SEP; 16.26 >;SEP; # >;SEP; 0.91
>;SEP; (10)
>;tb; prostatic >;SEP; acid >;SEP; phosphatase >;SEP; micrograms/ml >;SEP; 8.37 >;SEP; # >;SEP;
1.05 >;SEP; (9) >;SEP; 7.28 >;SEP; # >;SEP; 0.51 >;SEP; (7) >;SEP; 7.50 >;SEP; # >;SEP; 0.80
>;SEP; (10)
>;tb; Number of animals in the group shown in brackets g 5 (or mg %) represents the weight of the
parameter in g (of mg) per 100 g body weight Effect of the Total Extract of Khaya Grandifolia on the
Weight of Male Rats
(Treatment over 12 weeks)
Weight of organs in g of mg/100 g boby weight>;/RTI;
EMI6.1
>;tb; >;SEP; No.of >;SEP; Prostate
>;tb; >;SEP; Treatment >;SEP; test >;SEP; heart >;SEP; liver >;SEP; kidneys >;SEP; suprarenals
>;SEP; splsen >;SEP; testlcles >;SEP; gland
>;tb; >;SEP; animal >;SEP; g >;SEP; g >;SEP; g >;SEP; mg >;SEP; g >;SEP; g >;SEP; g
>;tb; Control >;SEP; Animals >;SEP; 1 >;SEP; 0.302 >;SEP; 4.910 >;SEP; 0.623 >;SEP; 12.244
>;SEP; 0.580 >;SEP; 0.887 >;SEP; 0.131
>;tb; Tween >;SEP; 20 >;SEP; 2 >;SEP; 0.259 >;SEP; 3.260 >;SEP; 0.621 >;SEP; 15.469 >;SEP; 0.571
>;SEP; 0.902 >;SEP; 0.191
>;tb; >;SEP; 3 >;SEP; 0.260 >;SEP; 2.918 >;SEP; 0.711 >;SEP; 14.049 >;SEP; 0.500 >;SEP; 0,.896
>;SEP; 0.112
>;tb; >;SEP; 4 >;SEP; 0.418 >;SEP; 3.656 >;SEP; 0.751 >;SEP; 14.237 >;SEP; 0.724 >;SEP; 1.039
>;SEP; 0.174
>;tb; >;SEP; 5 >;SEP; 0.287 >;SEP; 3.074 >;SEP; 0.665 >;SEP; 11.335 >;SEP; 0.600 >;SEP; 0.832
>;SEP; 0.246
>;tb; >;SEP; 1 /00 >;SEP; 6 >;SEP; 0.278 >;SEP; 2.732 >;SEP; 0.582 >;SEP; 14.613 >;SEP; 0.534
>;SEP; 0.846 >;SEP; 0.112
>;tb; >;SEP; 7 >;SEP; 0.247 >;SEP; 2.302 >;SEP; 0.471 >;SEP; 8.695 >;SEP; 0.361 >;SEP; 0.839
>;SEP; 0.083
>;tb; >;SEP; 8 >;SEP; 0.300 >;SEP; 2.739 >;SEP; 0.655 >;SEP; 7.187 >;SEP; 0.327 >;SEP; 1.086
>;SEP; 0.116
>;tb; >;SEP; 9 >;SEP; 0.289 >;SEP; 2.769 >;SEP; 0.530 >;SEP; 9.729 >;SEP; 0.620 >;SEP; 0.840
>;SEP; 0.074
>;tb; >;SEP; 10 >;SEP; 0.296 >;SEP; 2.787 >;SEP; 0.760 >;SEP; 11.525 >;SEP; 0.715 >;SEP; 0.815
>;SEP; 0.971
>;tb; >;SEP; Mean >;SEP; 0.293 >;SEP; 3.115 >;SEP; 0.637 >;SEP; 11.908 >;SEP; 0.553 >;SEP;
0.898 >;SEP; 0.131
>;tb; Khaya >;SEP; grandifoliaq >;SEP; 1 >;SEP; 0.284 >;SEP; 3.051 >;SEP; 0.709 >;SEP; 16.363
>;SEP; 0.371 >;SEP; 1.027 >;SEP; 0.146
>;tb; total >;SEP; extract >;SEP; 2 >;SEP; 0.237 >;SEP; 2.629 >;SEP; 0.683 >;SEP; 6.459 >;SEP;
0.384 >;SEP; 0.279 >;SEP; 0.163
>;tb; 0.725 >;SEP; mg/kg/per >;SEP; os >;SEP; 3 >;SEP; 0.274 >;SEP; 3.184 >;SEP; 0.708 >;SEP;
13.081 >;SEP; 0.600 >;SEP; 0.467 >;SEP; 0.155
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>;tb; in >;SEP; Tween >;SEP; 20 >;SEP; 4 >;SEP; 0.288 >;SEP; 3.043 >;SEP; 0.689 >;SEP; 11.590
>;SEP; 0.460 >;SEP; 0.636 >;SEP; 0.193
>;tb; 1 /00 >;SEP; 5 >;SEP; 0.320 >;SEP; 3.259 >;SEP; 0.726 >;SEP; 11.304 >;SEP; 0.631 >;SEP;
0.801 >;SEP; 0.172
>;tb; >;SEP; 6 >;SEP; 0.250 >;SEP; 3.231 >;SEP; 0.611 >;SEP; 12.990 >;SEP; 0.533 >;SEP; 0.827
>;SEP; 0.180
>;tb; >;SEP; 7 >;SEP; 0.260 >;SEP; 2.340 >;SEP; 0.527 >;SEP; 12.602 >;SEP; 0.403 >;SEP; 0.759
>;SEP; 0.098
>;tb; >;SEP; 8 >;SEP; 0.242 >;SEP; 2.689 >;SEP; 0.554 >;SEP; 9.972 >;SEP; 0.283 >;SEP; 0.786
>;SEP; 0.134
>;tb; Mean >;SEP; 0.269 >;SEP; 2.928 >;SEP; 0.651 >;SEP; 11.795 >;SEP; 0.458 >;SEP; 0.698
>;SEP; 0.155
>;tb; (Continued)
EMI7.1
>;SEP; Prostate
>;tb; >;SEP; No >;SEP; :>;SEP; of >;SEP; heart >;SEP; liver >;SEP; Kidneys >;SEP; suprarenals
>;SEP; spleen >;SEP; testicles >;SEP; gland
>;tb; Treatment >;SEP; test >;SEP; g >;SEP; g >;SEP; g >;SEP; mg >;SEP; g >;SEP; g >;SEP; g
>;tb; >;SEP; animal
>;tb; Khaya >;SEP; grandifolia >;SEP; 1 >;SEP; 0.325 >;SEP; 2.785 >;SEP; 0.733 >;SEP; 10.824
>;SEP; 0.329 >;SEP; 0.679 >;SEP; 0.197
>;tb; >;SEP; total >;SEP; extract >;SEP; 2 >;SEP; 0.269 >;SEP; 2.851 >;SEP; 0.564 >;SEP; 12.533
>;SEP; 0.274 >;SEP; 0.837 >;SEP; 0.191
>;tb; >;SEP; 3.625 >;SEP; mg/kg/per >;SEP; os >;SEP; 3 >;SEP; 0.266 >;SEP; 2.594 >;SEP; 0.544
>;SEP; 8.020 >;SEP; 0.309 >;SEP; 0.827 >;SEP; 0.181
>;tb; >;SEP; in >;SEP; Tween >;SEP; 20 >;SEP; 4 >;SEP; 0.183 >;SEP; 2.412 >;SEP; 0.476 >;SEP;
8.333 >;SEP; 0.595 >;SEP; 0.276 >;SEP; 0.190
>;tb; >;SEP; 1 /00 >;SEP; 5 >;SEP; 0.248 >;SEP; 2.340 >;SEP; 0.588 >;SEP; 7.297 >;SEP; 0.295
>;SEP; 0.855 >;SEP; 0.153
>;tb; >;SEP; 6 >;SEP; 0.293 >;SEP; 3.238 >;SEP; 0.563 >;SEP; 12.051 >;SEP; 0.521 >;SEP; 0.904
>;SEP; 0.203
>;tb; >;SEP; 7 >;SEP; 0.262 >;SEP; 2.641 >;SEP; 0.520 >;SEP; 12.977 >;SEP; 0.503 >;SEP; 0.863
>;SEP; 0.120
>;tb; >;SEP; 8 >;SEP; 0.282 >;SEP; 2.692 >;SEP; 0.593 >;SEP; 16.568 >;SEP; 0.573 >;SEP; 0.876
>;SEP; 0.161
>;tb; >;SEP; 9 >;SEP; 0.280 >;SEP; 2.581 >;SEP; 0.579 >;SEP; 15.312 >;SEP; 0.704 >;SEP; 1.004
>;SEP; 0.142
>;tb; >;SEP; 10 >;SEP; 0.245 >;SEP; 2.512 >;SEP; 0.544 >;SEP; 9.164 >;SEP; 0.259 >;SEP; 0.968
>;SEP; 0.154
>;tb; Mean >;SEP; 0.265 >;SEP; 2.665 >;SEP; 0.570 >;SEP; 11.308 >;SEP; 0.436 >;SEP; 0.809
>;SEP; 0.169
>;tb; Effect of the Total Extract of Khaya Grandifolia Administered Per OS Over
12 Weeks on the Diuresis of the Male Rat
Treatment mg/kg/day
EMI8.1
>;SEP; Tween >;SEP; 20 >;SEP; Khaya >;SEP; grandifolia >;SEP; Khaya >;SEP; grandifolia
>;tb; >;SEP; Parameter >;SEP; 1 >;SEP; /00 >;SEP; total >;SEP; extract >;SEP; total >;SEP; extract
>;tb; >;SEP; 0.725 >;SEP; 3.625
>;tb; urine >;SEP; volume >;SEP; ml/5h >;SEP; 6.07 >;SEP; # >;SEP; 0.69 >;SEP; (10) >;SEP; 7.95
>;SEP; # >;SEP; 0.94 >;SEP; (8) >;SEP; 5.95 >;SEP; # >;SEP; 0.76 >;SEP; (10)
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>;tb; sodium >;SEP; milli-equivalents/5h >;SEP; 0.66 >;SEP; # >;SEP; 0.06 >;SEP; (10) >;SEP; 0.82
>;SEP; # >;SEP; 0.13 >;SEP; (8) >;SEP; 0.63 >;SEP; # >;SEP; 0.07 >;SEP; (10)
>;tb; potassium >;SEP; milli-equivalents/5h >;SEP; 0.22 >;SEP; # >;SEP; 0.04 >;SEP; (10) >;SEP;
0.29 >;SEP; # >;SEP; 0.04 >;SEP; (8) >;SEP; 0.21 >;SEP; # >;SEP; 0.03 >;SEP; (10)
>;tb; chloride >;SEP; (NaCl) >;SEP; milli-equivalents/5h.>;SEP; 0.87 >;SEP; # >;SEP; 0.09 >;SEP;
(10) >;SEP; 1.09 >;SEP; # >;SEP; 0.24 >;SEP; (8) >;SEP; 0.77 >;SEP; # >;SEP; 0.11 >;SEP; (10)
>;tb; blood >;SEP; ml >;SEP; 0.10 >;SEP; # >;SEP; 0.10 >;SEP; (10) >;SEP; 0 >;SEP; (8) >;SEP; 0.30
>;SEP; # >;SEP; 0.21 >;SEP; (10)
>;tb; Albumin >;SEP; g >;SEP; % >;SEP; 0.50 >;SEP; # >;SEP; 0.26 >;SEP; (10) >;SEP; 0.12 >;SEP;
# >;SEP; 0.12 >;SEP; (8) >;SEP; 0.50 >;SEP; # >;SEP; 0.22 >;SEP; (10)
>;tb; cetonic >;SEP; bodies >;SEP; g >;SEP; % >;SEP; 0 >;SEP; (10) >;SEP; 0.12 >;SEP; # >;SEP;
0.12 >;SEP; (8) >;SEP; 0 >;SEP; (10)
>;tb; glucose >;SEP; mg >;SEP; % >;SEP; 0 >;SEP; (10) >;SEP; 0 >;SEP; (8) >;SEP; 0 >;SEP; (10)
>;tb; Urobilin >;SEP; g >;SEP; % >;SEP; 0.10 >;SEP; # >;SEP; 0.10 >;SEP; (10) >;SEP; 0.12 >;SEP; #
>;SEP; 0.12 >;SEP; (8) >;SEP; 0.20 >;SEP; + >;SEP; 0.13 >;SEP; (10)
>;tb; Notes :The number of animals per group is shown in brackets g % (or mg %) represents the
weight of the parameter in g (of mg) per 100 g of body weight.>;/RTI;
Report of clinical tests using the Khaya extract
according to the invention
A clinical test carried out over a period of four weeks on four aged male patients suffering from
rheumatism and on 3 aged male patients suffering from hypertrophy of the prostate gland, showed that
a treatment carried out with the Khaya extract accord- ing to the present invenvion, administered for 3
or 4 weeks, in daily doses corresponding to 100 g of powdered cortex in poxder, which is equivalent to
an approximate daily dose of 2 g/kg body weight administered orally, causes a very considerable
lessening in rheumatic pain, a considerable reduction in the volume of the prostate gland, and a
considerable reduction in the residual urine.Data supplied from the esp@cenet database - Worldwide
Claims:
Claims of GB1485268
WHAT WE CLAIM IS:
1. A plant extract, characterized in that its active constituent is an extract of a plant of the Meliaceae
family, of the genus Khaya, selected from Khaya grandifolia,Rhaya ivorensis, and Khaya senegalensis,
with an organic solvent.
2. A therapeutic composition comprising a
Khaya extract as claimed in claim 1, in association with a therapeutically acceptable carrier, so as to
permit the administration of the said extract by oral or parenteral means.
3. A process for preparing a Khaya extract as claimed in claim 1, characterized in that the plant of the
genus Khaya is pre-dried and finely ground and extracted with an organic solvent selected from the
group which comprises vegetable oils, a hydrocarbon, chlorinated hydrocarbons, ethers, alcohols, and
mixtures of these solvents.
4. A process as claimed in claim 3, characterized in that the plant is extracted with a vegetable oil, the
fatty acids are thereafter saponified and the unsaponified extract is further extracted with a hydrocarbon
or a chlorinated hydrocarbon.
5. A process as claimed in claim 3 or 4, characterized in that the extract of Khaya is obtained from the
cortex, the wood, the leaves or the fruits of the plant.
6. A process as claimed in any one of claims 3 to 5 wherein the vegetable oil is selected from palm oil
or ground nut oil.
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7. A process as claimed in any one of claims 3 to 6 wherein the hydrocarbon is hexane.
8. A plant extract substantially as hereinbefore described.
9. A therapeutic composition substantially as hereinbefore described.
10. A process for preparing aRhaya extract substantially as hereinbefore described with reference to
Examples 1 and 2.
11. A Khaya extract when produced by a process as claimed in any one of claims 3 to 7 or 10.Data
supplied from the esp@cenet database - Worldwide
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17. GB2023120 - 28/12/1979
TREATMENT OF PALM OIL MILL PROCESSING EFFLUENT BY SOLVENT
EXTRACTION
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=GB2023120
Applicant(s):
UNIV MALAYA (--)
IP Class 4 Digits: C02F; C02B; C11B
IP Class:C02F1/26; C02B9/00; C11B13/00
E Class: C02F1/26
Application Number:
GB19790020291 (19790611)
Priority Number: GB19780026675 (19780612)
Family: GB2023120
Abstract:
Abstract of GB2023120
Palm Oil mill processing effluent or sludge is treated by subjecting it to solvent extraction using a
substantially water-imiscible organic solvent. The solvent extract obtained contains palm oil which
may be recovered. The aqueous sludge raffinate obtained is further treated to separate suspended solids
from the aqueous phase. Effluent treated in this way has a greatly improved quality and is safe for
further processing or discharging.Description:
Description of GB2023120
SPECIFICATION
Treatment of palm oil mill processing effluent by solvent extraction
The present invention relates to a method of treating palm oil mill processing effluent or sludge.
More specifically, it relates to a process in which palm oil mill processing effluent or sludge which
usually contains palm oil and other contaminants such as gums, resins and colouring matters, and finely
divided solid particles is pre-treated by solvent extraction followed by further treatment to remove
solids from the water phase whereby the quality of the effluent is successively improved.
The average quality of this effluent is as follows:
pH about 4
BOD (5 days) 20,000 to 30,000 ppm
COD 50,000 to 60,000 ppm
Total solids
content 5 to 10 percent by weight
Suspended solids
content 3 to 7 percent by weight
Oil and Grease ca. 1 percent or more by weight
Such effluent is normally discharged into the drain at a temperature of about50-90 C.
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A medium size mill of 50 ton fruitbuncheslhr could easily discharge an effluent equivalent to a
domestic load of 170,000 people (in BOD).
The processing effluent, commonly known as mill sludge or raw sludge, contains substances resulting
from the milling of oil palm fruits.
This sludge is highly organic carrying relatively high portion of volatile suspended solid. It creates an
undesirable odour and heavy accumulation of viscous pollutant if allowed to move slowly in small
drains around the oil palm plantation. This accumulation of sludge may eventually reach and have an
undesirable effect on larger waterways.
The difficulties which have been encountered in providing an effective treatment of palm oil mill
effluent include:
1) The raw effluent has been shown to be resis
tanttothe usualmethodsofflocculation and
sedimentation.
2) Standard methods of anaerobic or aerobic
sewage treatment to break the emulsion and
thereby assist in the removal of solids are
known to be difficult.
3) Disposal by direct spraying to the land or natu
ral evaporation from open lagoon is
uneconomic and not recommended.
4) Direct settling, flotation, centrifugation or filtra
tion of the solids were not successful and not
recommended. Vacuum filtration studies which
have been carried out have revealed that filtra
tion techniques could not be applied economi
callyto remove the solids.
5) Electro-flotation techniques have also been
tried elsewhere, but no published results are
known.
It has been found that the breaking up of the emulsified solids suspension of the said effluent, in order
to improve separation of suspended solids by, for example, settling, filtration or centrifugation, is
achieved by means of a solvent extraction that removes most of the oil from the emulsion.
The present invention relates to a method of removing the oil and other contaminants present to ease
and to increase the rates of removal of solids and BOD load from the effluent.
Accordingly, the present invention provides a method for the treatment of palm oil mill processing
effluent which method comprises the steps of:
(a) subjecting the palm oil mill processing effluent
to solvent extraction, using a substantially
water-immiscible organic solvent, to give an
extract of the effluent carrying oil and other
contaminants and an aqueous sludge;
(b) recovering solvent and palm oil from the sol
vent extract; and
(c) treating the aqueous sludge to separate sus
pended solids from the aqueous phase.
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In step (a) above the solvent extraction is preferably carried out at a temperature of from200 to80 C,
depending on the prevailing temperature of the incoming effluent and on the solvent used, in order to
ease phase dispersion. Preferably, the step is carried out under superatmospheric pressure.
The ratio of solvent to effluent is preferably 1 :50 to 50:1 by volume, more preferably 10:1 to 1:10.
In step (c) above, the aqueous sludge is treated typically according to one or more processes selected
from:
(1) mixing - and - settling
(2) filtration or centrifugation separation
(3) anaerobic or aerobic bacterial treatment.
The choice of the type of treatment used on the aqueous sludge will depend on the characteristics of
the sludge and the possible use or value of any byproduct derived from such treatments. For instance, if
the presence of additives or foreign chemicals is undesirable in the wet solid (a by-product), a filtration
operation may precede the mixing-and-settling step. A very light sludge containing a low concentration
of suspended solids may be subjected directly to an aerobic or an anaerobic bacterial treatment without
separating the solids present.
The palm oil mill processing effluent or sludge may be collectedandlor diluted in a storage tank,
skimming tank or in an equalizing pond.
The solvents used in the solvent extraction step are organic liquids which are substantially immiscible
with water, such as the derivatives or the members of homologous series of aliphatic hydrocarbons, for
example hexane and heptane and naphtha, and aromatic hydrocarbons such as benzene, and
halogenated hydrocarbons such as trichloroethylene.
The solvent extraction step may be carried out under vigorous agitation in a column or a tank
extraction unit. Preferably, the solvent extraction step is carried out in a pulsed column.
The solvent used for this pre-treatment may contain various concentrations of oil and contaminants.
The spent solvent or the extract carrying higher concentrations of oil and other contaminants are to be
further processed to recover the solvent, the oil and other by-products in a solvent recovery unit (for
extract).
The pre-treated sludge or the raffinate, which is mainly the water phase, flows out of the extraction
unit into another solvent recovery unit (for raffinate) for the recovery of the solvent entrapped between
the solid particles. Dilution and mild heating of the raffinate may be carried out here to ease solvent
separation.
The recovered solvent is preferably recycled and re-used in the extraction unit.
The pre-treatment step (a) of the effluent improves sludge filterability and eases the subsequent
separation of the solids from the water phase.
A preferred system for carrying out the method of the invention is shown schematically in the flow
chart illustrated in Figure 1.
In this flow chart the raw palm oil mill processing effluent is charged to an extraction unit where it is
subjected to solvent extraction. The solvent extract from the extraction unit is lead to a solvent recovery
unit where the solvent is recovered for recycling to the extraction unit and by-products substantially
comprising palm oil are obtained.
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The aqueous sludge or raffinate from the extration unit is lead to a solvent recovery unit after which it
is subjected to aerobic or anaerobic bacterial treatment. Preferably, the bacterial treatment is preceded
by treatment in a mixer-settler unitandlor a filter or centrifuge unit.
Clean effluent obtained after the bacterial treatment may be discharged in the usual manner.
Accumulating the pre-treated sludge in a mixersettler tank encourages solid particles to agglomerate
after which they tend to float Floating of these flocs is speeded up by aerationandlor addition of small
quantities of surface-active chemicalsor additives. The whole flocs may overflow with the water out of
the tank and may be directly filtered or centrifuged to remove most of the solids. In this case, a
relatively clean liquor carrying much less concentration of solids is removed as an underflow.
The pre-treated sludge mixed with/without certain chemicals may also be filtered or centrifuged
directly without going through the settlingor floatation operation.
The liquor or filtrate discharged from any stage of this process may be directly subjected to an aerobic
or anaerobic treatment to further improve the quality of the effluent.
Dilution of process streams are provided at any stage of this process.
By-passing of process streams are also provided to regulate the processing conditions in various units.
A highly preferred embodiment of the method of the present invention will now be described with
reference to the process flow diagram illustrated in
Figure 2.
In this flow diagram the raw sludge is held in tank(1) from where it is pumped into an overhead tank
(2). The raw sludge is then introduced from tank (2) into a pulsed column (3) having grids (4) to mix
up and break the suspension of solids in the raw sludge in contact with asubstantially water-immiscible
organic solvent supplied from a tank (6) to bring about the extraction of the palm oil from the sludge
into the solvent.
The pulsed column (3) is operated under controlled pressure to prevent liquid boiling. The solvent
containing the oil is taken off at the top of the column and lead to a flash column (5). The extract is
flashed in the flash column operated under lower pressure to recover part of the solvent which is
returned to solvent tank (6). The flashed extract passes through condenser (7) and into a further
condenser (8). Part of the solvent together with water is drained into a water-separator (9) which
returns the solvent to the solvent tank (6). The extract vapour not condensed at this stage is led to a
steam distillation unit (7) from which the oil is recovered. The flash column (5), so used, reduces the
load on the distillation unit.
The raffinate from the pulsed column is led via a storage tank (10) into a multistage gravity settling
system(11) with or without a heatingarrangement
Any solvent extract carried over in the raffinate leaving the extraction column may be collected and
recycled back to the extraction column via the heavy extract tank (12). The finalraffinateproduced thus
contains only a trace of oil and may be called deoiled sludge. This is then processed in a filter or
centrifuge (13) to remove the suspended solids as wet solids and give a clean, de-oiled effluent.
Preferably, the separation is carried out using a decanter centrifuge. However, if a filter device is used,
polyelectrolyte or surface-active chemicals may be added to the de-oiled sludge to improve the
efficiency of the solids separation.
The vapour space in the processing tanks or equipmentofthe multistage gravity settling system may be
connected with pipes or ducts to vapour scrubbers or condensers to further recover any solvent vapour
and to improve the general safety of the treatment plant
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The thus de-oiled effluent possesses a quality vastly improved, much better than that of the raw sludge,
and is more amenable to anaerobic or aerobic treatment. The said wet solids may be further processed,
for example, in a dryer to manufacture animal feedstock or composting for soil condition, or anerobic
digestion for methane gas generation.
EXAMPLE 1
A homogeneous sample of palm oil mill processing effluent containing ca. 5% solids and ca.1% palm
oil by weight was divided into two portions, one was treated in a laboratory-scale solvent extraction
unit and the other was not. A laboratory vacuum filter assembly of 12 cm in diameter was used to
separate the solids contained. Standard qualitative filter papers were used and the assembly was
operated under 12 inches of mercury vacuum. The following results were consistently obtained: The
100ml
of treated portion took 15 minutes to filter, whereas the untreated portion took more than 100 minutes.
EXAMPLE2
A second sample of the raw sludge was again
divided into two portions, the first portion was tre
ated in the extraction unit and the second was not
treated. The two portions were centrifuged sepa rately and the centrates, each diluted with tap water
by twice its volume, were subjected to aerobic digestion at 280C in two separate containers
equipped\'vith aeration facilities. Ninety percent reduction in
COD was adopted as the process parameter for comparison purposes: The treated portion took nine
days and the untreated portion took 18 days to reach 90% COD removal.
EXAMPLE3
A pilot plant has beenemployed to process the palm oil mill processing sludge containing about 4 to
10% by weight of solids and about 0.5 to 2% by weight of palm oil giving the following results:
A pulsed column extractor was used to remove the
oil.
Extraction efficiency: over 98% oil removal
Solvent used: hexane (industrial grade)
Solvent/sludge ratio: varied from 10:1 to 1:10
Operating temperature:40 C to 750C
Operating Pressure: 1-1.2 atmospheres
Liquid flow rate of 1 to 14 litres per minute
Pulsing parameters: varied depending on the sol
vent/sludge ratio; frequency was varied from 30 to
120cyclelminute amplitude was varied from 1.25
to 2.5 cm
A bucket or decanter centrifuge was used to remove the solidsfrom the de-oiled sludge. It removed ca.
75% of the suspended solids present
The resulting centrate was collected for analysis.
The wet solids were dried for testing as animal feed or composting. No chemical additives were used
in this test
EXAMPLE 4
An aeration unit consisting of a 1 ft x 1 ft x 4 ft high packed column and a tank digester was used for
conducting a batchwise aerobic treatment of the pentrate obtained from the sludge treatment as
described in Example 3.
The fresh centrate was first diluted prior to the aeration by adding tap water to adjust its COD to
10,000 ppm.
The following operating conditions were main
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tained:
Liquid circulation rate in the column: 43640 l/m2/h
Aeration rate in the column: 40 m3/h
Volume of liquid retained in the tank: 0.1 3m3
The following results were obtained:
Day 0 10 20 25 35
COD, ppm 10,000 4,043 2,095 1,170 690 pH 3.7 7.8 8.3 8.6 8.6
Tap water was added daily to make up for evaporation losses. After 35 days of aeration the resulting
liquor turned to light brown or light tea colour. It could be de-colourized by mixing with charcoal or
activated carbon. The colour quickly disappeared on the addition of chlorine.
EXAMPLE 5
A typical treatment as described in Example 3 where hexane is used as solvent/sludge ratio of 1:1
by volume, raw sludge flowrate of 3 I/minute, pulsing the extraction column at 100 cycles/minute,
1.25 cm amplitude, and maintaining oil concentration in the incoming solvent phase at ca. 3% by
weight for the raw sludge containing ca. 5% solids by weight and ca. 1% oil by weight, the following
additional results are obtained: oil recovery of ca. 85%, hexane in deoiled sludge of ca. 700 ppm by
volume and hexane in oil recovered of ca. 400 ppm by volume, and wet solids of ca. 80% mixture by
weight.Data supplied from the esp@cenet database - Worldwide
Claims:
Claims of GB2023120
CLAIMS
1. A method for the treatment of palm oil mill processing effluent which method comprises the steps
of:
(a) subjecting the palm oil mill processing effluent
to solvent extraction, using a substantially
water-immiscible organic solvent, to give an
extract of the effluent carrying oil and other
contaminants and an aqueous sludge;
(b) recovering solvent and palm oil from the sol
vent extract; and
(c) treating the aqueous sludge to separate sus
pended solids from the aqueous phase.
2. A method as claimed in claim 1, wherein in step (c) the aqueous sludge is treated according to one
or more processes selected from:
(1) mixing - and - settling separation,
(2) filtration or centrifugation separation, and
(3) anaerobic or aerobic bacterial treatment.
3. A method as claimed in either claim 1 or claim 2, wherein the solvent extraction is carried out at a
temperature of from 20 to80 C.
4. A method as claimed in any one of claims 1 to 3, wherein the solvent extraction is carried out at a
pressure of at least atmospheric.
5. A method as claimed in any one of claims 1 to 4, wherein ratio of solvent to effluent is from 1:10 to
10:1.
6. A method as claimed in any one of claims 1 to 5, wherein the solvent used in the solvent extraction
is selected from hexane, heptane, naphtha, benzene, trichloroethylene and mixtures of two or more of
these.
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7. A method as claimed in any one of claims 1 to 6 wherein the recovered solvent is recycled to the
solvent extraction step.
8. A method as claimed in any one of claims 1 to 7, wherein the aqueous sludge is treated to a further
solvent recovery process.
9. A method as claimed in claim 8 wherein the aqueous sludge is subjected to a multistage gravity
settling system.
10. Palm oil whenever recovered from palm oil mill processing effluent by the method claimed in any
one of claims 1to 9.Data supplied from the esp@cenet database - Worldwide
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18. GB644917 - 18/10/1950
IMPROVEMENTS IN OR RELATING TO THE SOLVENT EXTRACTION OF
GLYCERIDES AND OF FATTY ACIDS DERIVED THEREFROM
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=GB644917
Applicant(s):
PITTSBURGH PLATE GLASS CO (--)
IP Class 4 Digits: B01D
IP Class:B01D11/04
E Class: B01D11/04K2; B01D11/04S
Application Number:
GB19470019458 (19470721)
Priority Number: USX644917 (19400513)
Family: GB644917
Abstract:
Abstract of GB644917
The solvent extraction of glycerides, or of fatty acids derived therefrom, with a selective polar solvent
is carried out under an inert gas, for example carbon monoxide, carbon dioxide, nitrogen or a nitrogencontaining gas such as flue gas. In the presence of the inert gas objectionable reactions, which impair
the value of one or more of the components of the material treated and which are due to the action of
atmospheric oxygen, do not take place. Among the >;PICT:0644917/III/1; glycerides that may be
fractionated are linseed oil, marine oils such as menhaden, sardine or whale oils, soya bean oil, perilla
oil, cottonseed oil, corn oil, sunflower oil, peanut oil, olive oil, lard, tallow, palm oil and coconut oil.
The oils may be raw oils, or refined oils, such as alkali-refined oils, and they may also be bodied or
unbodied. Selective polar solvents which may be employed are furfural, furfuryl alcohol, allyl alcohol,
nitroethane, nitromethane, methyl formate, methyl levulinate, propionitrile, ethyl maleate, acetaldehyde,
diacetyl, glycol diacetate, ethyl oxalate, ethylene glycol monomethyl ether acetate and others
mentioned in Specifications 515,468 and 18137/47 (as open to inspection under Sect. 91).
Fractionation may be effected by reason of the higher degree of solubility of the more unsaturated
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components of the glyceride or fatty acid mixture in the selective solvent. Thus drying oils may be
extracted from linseed, soyabean, marine and perilla oils. Alternatively, fractionation may be effected
by reason of the greater solubility of the glycerides of the shorter chain fatty acids in the selective
solvent, particularly in the case of palm and coconut oils. The oils or fatty acids may be deaerated prior
to extraction by heating them and simultaneously subjecting them to vacuum or to blowing with
nitrogen or other inert gas. If the selective solvent employed is one tending to hydrolyse, the inert gas
employed as blanketing agent during the extraction may be preliminarily dried. Extraction may be
carried out as a simple batch operation by mixing the oil and solvent under a blanket of inert gas in a
suitable container, then allowing the resultant fractions to separate into liquid layers and drawing off
the layers into separate containers for removal of the solvent. Alternatively, countercurrent extraction
may be conducted in columns in which all free surfaces of the glycerides or acids are protected by a
blanket of inert gas. In the Figure, glyceride oil or fatty acid from container 21 is introduced via
conduit 23 into column 10. Solvent from container 25 enters column 10 via conduit 28. If desired,
water or other fluid at least partially miscible with the solvent but immiscible with the material to be
refined is introduced into the solvent through line 32a. Raffinate leaves the column via conduit 37 and
proceeds to apparatus for the removal of solvent. Extract is drawn off through conduit 41 which
extends upwardly a sufficient height to admit of hydrostatically balancing of the liquid therein against
the liquid contained in column 10. From the head 43 of conduit 41, the extract proceeds to apparatus
for the removal of solvent. Solvent from both extract and raffinate phases may be recycled for
extraction of additional mixture. A portion of the extract with a small amount of solvent therein may be
returned via conduits 62 and 64 to column 10. Inlets for inert gas are at 32b, 37a, 43a and
59.Description:
Description of GB644917
COMPLETE SPECIFICATION
Improvements in or relating to the Solvent Extraction of
Glycerides and of Fatty Acids Derived therefrom
We, PITTSBURGH PLATE GLASS COM
PANY, a Corporation organised underthe laws of the State of Pennsylvania, United
States of America, of 2200, Grant Building, Pittsburgh, Pennsylvania, United
States of America, do hereby declare thenature of this invention and in what manner thesame is to be
performed, to be particularly described and ascertained in and by the following statement:
The present invention relates to refining of glycerides and free fatty acids derived therefrom, and it has
particular relation to the refinement by the liquid phase extraction with a polar solvent of such
glycerides and acids consisting of components which substantially differ from each other by reason of a
differenceiII degree of unsaturation or activity of unsaturation, or in chain length of the molecule.
One object of the invention is to provide a process of removing a component from glycerides and free
fatty acids of glycerides byextraction with a selective solvent, which process does not produce
obectionable reactionsthat impair the value of one or more of the components of the material treated.
In accordance with the present invention, there is provided a process of separating into components a
mixture consisting of a plurality of glycerides or a plurality of fatty acids derived from said glycerides,
said mixtureineludinz a component which is relativelydifficultly soluble and a component which is
relatively more soluble in a selective polar solvent which comprises extracting the materialby means of
a selective polar solvent under ablanket of inert gas and then separating the mixture into liquid phases,
one comprising the selective polarsolvent saturated - with them ore soluble componentand the other
com- prising the less soluble component saturated with the polar solvent.
In British patentspecification No.
515,468 and copending application No.
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18137/47 (as open to public inspection) there are disclosed processes of separating glycerides and also
free acids of glycerides into components by liquid phase extraction with furfural. furfuryl alcohol and
other active or polar solvents, which include various activating groups such as hydroxyl, carboxyl, nitro,
phosphate and numerous other groups. These active solvents are found to have a substantially higher
affinity for unsaturated glycerides and acids derived from such glycerides than forthe more saturated
or otherwise less activegjycerides or acids.
Correspondingly themore highly unsaturated or actively unsaturatedglyeer- ides and free acids
thereofexhibit asub- stantially greater solubility in the solvents than themore completelysaturated
glycerides and acids or theunsaturateci glycerides which by reason of the arrangement of groups are
less active.
In accordance with the foregoing patent and application, oils and acids consisting of mixtures of more
copletely saturated and less completely saturated or actively unsaturated components are treated with
an active or polar solvent to dissolve out a fractioneu- riched in the more unsaturated or actively
unsaturated components and correspondingly to leave a raffinate of oil or acid which is enriched in the
relatively highly saturatedcomponentse together with a certain amount of the active solvent dissolved
therein. The mixtures can then be separated into liquid phases, one consisting of the solvent and the
fraction rich in unsaturates or active unsaturates and the other consisting of the more saturated or less
actively unsaturated material in which is dissolved a small amount of the solvent. These two liquid
phases may be separated by appropriate means, and by distillation or other suitable treatment, the
solvent may be removea therefrom, leaving the desired fractions of oils or acids.
Although itwas thus possible to separate glyceride oils or the acids derived therefrom into fractions
according to the degree or the molecular arrangement of unsaturation the unsaturated fraction did not
always exhibit the characteristics desired in it, to the degree that might have beenexpected. For
example, where the fraction was to be employed as a paint or varnish vehicle, it was often foundthat
the extracted fraction dried slowly even though its iodine value wasrelatively Ijigh. Pood products
might be discoloured.
It has now been discovered that this peculiar behaviour is apparentlydue to some obscure chemical
reactions within the oil or solvent or possibly between the two. It has further been discovered, that if an
unsaturated glyceride or the free acids therefrom is extracted with a suitable selective polar solvent
such as furfural, while it isblanketed or covered with an inert gas, such as carbon dioxide,flue gas, or
nitrogen. thetendency is substantially eliminated. From this it may, perhaps, be deduced that the
peculiar behaviour of the extracted oil is in someway due to the action of atmosphericoxy- gen which
is bIanlieted out orexcluded by the inert medium covering the oil.
In the application of the principles of the invention various methods ofextract- ing the oil with solvent
may be emploved. For example, extraction may be conducted as a simple batch operation by mixing
the oil and solvent under ablanket of inert gas in a suitable container, then allowing the resultant
fractions toseparate into liquid layers and drawing off the layers into separate containers for removal
of the solvent.Row- ever, thepreferred method involvescountercurrent extraction in columns in which
all free surfaces of the glycerides or acids are protected by ablanket of inert gas. The gas may be
almost anyinert gas, such as carbqn dioxide; how- ever, nitrogen or nitrogencontaining gases, such as
flue gas, are preferred.
A suitable embodiment of apparatus for counter-current extraction isill use trated in the accompanying
drawing in which the single figure is a diagrammatical or schematic view of a suitable embodiment of
apparatus for use inprac tice of the invention.
In the drawing like numerals refer to like parts throughout.
The apparatus as disclosed includes aa extraction tower or column 10 which may be packed with
Raschig rings or Beryl saddles, etc., and may be of substantially any diameter dependent uponthe
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quantity of glycerides or acids to be passed therethrough. The height of the column preferably is
approximately within the range of30 to50 feet.Ho- 'ever, these limits may be substantially exceeded,
if so desired. It also is pro
vided with a cover or jacket 11,which, as shown, may be formed in separatesec- tions, such as12. 13
and14, which may be of substantially any number dependent upon the gradation oftemperate within
the column which it may be desired to maintain. The sections may be supplied with heat
exchangemedium, such as water or the like through inlets 16 and outlets 17. The inlets may be
connected to separate sources of heat exchange medium at different temperatures, or if preferred they
may all be connected to a single source. Also, as shown in the drawings, the outlet con
duit may be connected by a conduit 18
with the inlet conduit of the adjacent section. The various conduits are supplied with valves 19, which
may be opened or closed to admit of thecircula- tion of the heat exchange medium through each
section of the jacket individually or to cause the fluid to flow from the outlet of one section to the inlet
of the adjacent section asmay be desired.
Glycerine oil or free acidsof glyceride oils may be storedin a closed container 21, which, may be
provided with ajacket
22 bv means of which it may be maintainted at any desired temperature. Oil from the container flows
through conduit 23 and is forced by suitable pump24 into an intermediate portion of the column 10,
preferablv at a distance of about 12 feet from the bottom of the column.
Solvent for the extraction map be stored in a container 25 and is fed through
conduit 26 to a pump 27. connected to conduit 28 in a heaterjacket 29,having
at one extremity an inlet 31 for heated fluid such as water and at the opposite extremity anoutlet 32 for
the waste fluid.
In some instances it may be desirable to add water or other fluid at least partially miscible with the
solvent, but immiscible with the material to be refined, in order to reduce miscibilitv thereof in the
solvent. Such addition may be madethrough conduit 32a. The upper extremity of conduit 28 discharges
into tile upper extremity of the column 10; at a short distance from the top thereof. Inert gas may, also,
be supplied to container 25 through conduit 32b.
It will be apparent that by reason of the difference in specific gravity of the solvent and the glyceride
oil or the acids derived therefrom the two liquids will tend to flow counter-currently with respect to
each other. Assuming that the solvent is the heavier component it will descend while the undissolved
oil will rise. Therefore, in a zone 33 extending approximately from the inlet for the solvent down some
distance below the inlet for the glyceride oil or the acids, there will be a mixture of countercurrently
flowing components. Also, the oil will be carried by the solvent certain dis tance below the oil inlet.
In the zone ofcouritercurrent flow of selective solvent and oil or acid it will be apparent that there is
very intimate contact, and the selective solvent gradually estractsa fraction whichis. rich in the more
soluble component, such as the moreunsafurated or activelyunsaturated glycerides and acids, or the
glycerides or acids which are more soluble by reason of differences in chain length inthe moleeule.
The less soluble components of the oil do not dissolve in the solvent, at least not completely but do
tend to take up a certain amount of the solvent. In a zone near or slightly above the inlet for the conduit
28 the less soluble component or raffinate will collect as a body of insoluble glyceride oil, or oil acid,
whichs free of the extractphase andwhich is saturated or substantially saturated with solvent and may
be drawn off through a conduit 37, that leads to suitable apparatus (to be later described) for the
separation of the solvent dissolved Therein.
Inert gas is admittedthrough conduit 37a to blanket the raffinate
The undissolved solvent with the extract phase therein ultimately separates out in the bottom of the
column asa distinct laser or fraction,which may be drawn off through a conduit41, that extends
upwardly a sufficient height to admit of hydrostatically balancing of the liquid therein against the liquid
contained in the extraction column1t0.
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Since the solvent and the oils are of differentspecific gravity, and since under varying conditions there
will be a tendency for the relative amounts thereof in the column 10 to vary somewhat, it is desirable to
provide at the upper extremity of the conduit 41 a section42 which can be elevated or lowered to
accommodate for the variations, thus making it possible to assure that the various strata in the column
10 are approximately at the desired levels. The upper extremity of the adustabIe section49. is provided
with a head 43, in which the pressure may be atmospheric pressure. This head is filled with inert
gasthrough conduit 43a.
The solvent charged with extract dischargesthrough this head to a conduit94 leading to the upper
extremity of a flash vaporizingcolumn 46, provided with a jacket 47 to which steam at a pressure of 20
or 30 pounds per square inch or other heat exchange medium may be admitted through conduit4S and
from which spent medium is dischargedthrough conduit49. The oil is deIivered into column46 s
ashower or spray that falls into a spray trap51 in which the droplets or separated oil, largely freed
from the solvent, are collected. The column 46preferably is maintained under partial vacuum, e.g.
under a pressure of 100 or 300 m.m. Vaporization of solvent in the column is almost instantaneous.
The solvent vapours pass off from the trap through conduit 52 to a condenser 53, which in turn
discharges through conduit 54 and pump56 back to the solvent container25,.
The extract separated from theva.lsor- ized solvent in the trap is discharged through conduit57 to a
surge tank 58, having inlet .59 for inert gas. From the surge tank, the extract or any suitable portion
thereof, is discharged through conduit 61tg stripping apparatus (to be described later) for removal of
the last traces of the solvent contained therein.
A portion of the extract with the small amount of solvent therein isdischarges through conduit 62 to
pump 63, which forces it through conduits 64 back into the column 10 at a point preferably below the
feed oil inlet, butslightlv above thetipper limit of the separated solvent phase in the lower portion of
the container. The concentration of the more soluble component is thus increasedin a zone adjacent to
solvent-extract layer and this results in the separation of more of the less soluble component from the
oil so thatultimately an extract is obtained.which is richer in the more soluble component and poorer
in the less solublecombo nent, than would otherwise be obtained.
Substantially any ratio of the extract.
for example 10 to 90% of the extract may be recycled.
As previously stated the inlet for the recycled oil is slightly above the level of the separated solvent
and preferably it is at such distance below the level of the inlet for the oil that therecycled-olL, as it
passes upwardly through the solvent.
will reach approximately the same composition as the feed oilfrom the container 22. Assuming that
furfural is employed as the selective solvent the distance between the inlets of the feed oil and the
recycled oil may beallproxl- mately12 feet. Tho distance between the inlets for the feed oil and the
solvent may vary over a substantial range,l)ut preferably is about 15 to 35 feet.
If preferred,separation of theextract from the solvent may be effected by addition of water, e.g.8 to
15% ofwater or othernon-solvent. The vnporizer4C may then be eliminated ormay be by- passed
byconduit 65 interconnecting conduit. 44 and conduit 47. Separation of the extract may be effected in
the surge tank 58 by addition of waterthrough conduit65a.
The apparatus for removing the dissolved solventfrom the raffinate includes a vaporizer column 66
into the upper extremity ofwhich the conduit 37 discharges the raffinate as a spray. Thecolumn is
provided with aheating jacket67, which is supplied withsteam or other heated fluid bymeans of
conduit6S andthe spentfluid is discharged fromthe jacket through conduit6(3. The pressure within
the column 66 like that in column 46 is subatmospheric-e.g.,about l()(} to 300 m.m. ofmercury tend
evaporation of the most of the solvent isalmost instantaneous. At its lower extremity the column
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discharges into aconvenional spraytrap 71, ill whichtlle droplets of raffinate from whichmuch ofthe
dissolved solvent has been evaporated are collected.
The solvent freed ofraffimite and ill vapour state is discharged through a conduit 72. to a line 73
leading to a condenser and source of vacuum (not shown).
Theraffinatet separatedfrom thevapours in the trap71 and stillcontaining some solvent, is
dischargedthrough conduit 74 into the upper extremity of a strippingcolumn 76. which column is
provided with a jacket 77 suppliedwith steam or other heated fluid through conduits 78.
having aconnection to a supply line 79.
Where steam is employed the pressure is preferably about50 lbs. per square inch corresponding to
about 280 F. The spent fluid is discharged from the bottom of the jacket through conduitSl.
Column 76 preferablv is packed with an inert material such asR.aschig rings,
Berl saddles or other packing material designedto. check the descent ofthe oil and to cause it to be
spread out info thin films presenting large surfaces. Steam or other distilling medium is introduced at
the bottom of thecolumn through conduit 82 and passes upwardly through the packing in such manner
as intimately to contact with the surface of the oil and thus to carryaway anysolvent dis solved therein.
The steam or other medium passes out of the column more or less completely charged with solvent
through conduit 83 and is discharged into the line 72. The raffinate oil now freed of solvent is
discharged through conduit 84 at thebottom ofthe column and is passed to storage or is passed on for
further treatment. for example. for anadditional extraction in furtherstages of apparatus. Such stages
obviouslymay assume substantially the form of the apparatus hereindisclosed andby such treatment it
is possible to remove an additionalfraction orfractions ofmore soluble component from the raffinate.
The conduit 61 carrying the more soluble orextract components offlie glyceride oil or theacids
thereof,namely the moreunsaturated components. is discharged in a second stripping column 86
substantially corresponding in construction to the column 76 and having a jacket 87 for steam or other
fluid as previously described in connection with the column 76. The column is also packed asindicated
at88 and is supplied with steam or inert gas through conduit 89.
The steam. or gas chargedwith solvent discharges from the upperextremity of the column through
conduit 91, which also discharges into the vapour line 73 and passes on to suitable apparatusfor
separation of thesolvent from the water vapours orgas. The componeilt of the oilwhich initiallv is
dissolved ill the sol- vent and which is liberated in the column 86 is discharged from the bottom of the
latterthrough aconduit 92, is either passed to storage or issubjected tofurther treatment,for example,
to further fractionation in additional stages of apparatus in order more completely be separate out
anysaturated or less solublecomponent. which may becarried therill. In thisway a fractionwhich is
very rich in unsaturates or other component.
which is selectivelysoluble in the sol- vent employed, may be obtained.
In tile practice of the presentino-en- tion substantially any of the selective solvents disclosed in
SpecificationNo.
515,468 and applications No. 18137/47 above referred to may be employed.
Among such solvents are included furfural, above described, furfuryl alcohol.
allyl alcohol, nitroethane, nitromethane, methyl formate. methyl levulinate, propionitrile, ethyl maleate.
acetaldehyde.
diacetyl. glycol diacetate. ethyl oxalate.
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ethylene glycol monomethyl ether acet ate and others. The ratio of solvent to oil may vary over a
broad range extending for example from 1 to 1 all the way to 10 to 1.
Among the glyceride oils that may be fractionated are included bodied or unbodied linseed oil, marine
oils, such as menhaden, sardine and whale oils, soya bean oil, perilla oil, cottonseed oil, corn oil,
sunflower oil, peanut oil, olive oil, lard, tallow and the like. These oils comprise mixtures of glycerides
of varying degrees of saturation and fractionation thereof is effected by the selective solvent by reason
of the higher degree of solubility of the moreunsaturated compoments in the selective solvent The oils
and free fatty acids may bedeaerated prior toextraction, byheating them to 100 C. or thereabout and
simultaneously subjecting them to vacuum or to blowing with nitrogen or other inert gas.
The oils may be raw oils or may bealkali refined, or may be refined by other methods. Theyinlay, also,
be bodied or unbodied.
It has also been found that certain of the oils, such as palm oil andcoconut oil, whichinclnde in their
compositions glycerides of fatty acids of varying chain length can similarly be separated into fractions,
because of the greater solubility of the short chain acid glycerides in the selective solvent. For example,
coconut oil which comprises essentially mixtures ofglycerides of straight chain aliphatic acids of a
chain length from 6 or 8 up to 18 or more may be separated into fractions which are greatly enriched in
specific glycerides.
It is of course obviousthat the appartus and process as herein disclosed is also applicable to the
fractionation of mixtures of relatively saturated and relatively unsaturated fatty acids derived from the
oils herein disclosed.
Almost any inert gas,such as carbon dioxide, carbon monoxide, nitrogen, or a nitrogen-containing gas
such as flue gas may be employed as blanketing agents in the apparatus. Flue gas and nitrogen are of
special value because the solubility in glyceride oils is low.
The gases may be preliminarily dried in orderto prevent hydrolysis of the soIvent in the system. If the
solvent does aot tend to hydrolyze, such drying is not usually necessary. The inert gases not only
prevent objectionable chemical reactions, but they also reduce fire hazards in the system, especially
whereimanis- cible hydrocarbons are present. They also help to reduce objectionable discoloration of
the fractions obtained.
The extracted oils as obtained from linseed soya bean, marine oils, perilla oil and others containing
substantial amounts of glycerides susceptible of air drying are excellently adapted for use as drying oils
in the fabrication of paints and varnishes. By application of the extraction process extracted oil having
gooddrying properties and sufficiently free of objectionable matter, such as free acids,anti-oxidants,
break producing constituents and the like can be obtainedwithout subjecting the oil to severe treatment
with acid or alkali. Inthe fabrication of paints and varnishes the conventional pigments, colours,
thinners and the like are added as with conventional drying oils. For example, titanium oxide, lithopone
and other pig ments may be added inamounts of 5 to90%. Turpentine or any other volatile thinner
may be also added in an amount of 5 to 90%, more or less, based upon weight.
Having now particularly described and ascertained the nature ofoar said invention and in what manner
the same is to be performed, we declare that what weData supplied from the esp@cenet database Worldwide
Claims:
Claims of GB644917
claimis:
1. A process of separating into cOponents a mixture consisting of aplurality of glycerides or a
plurality of fatty acids derived from saidglycerides, said mixture including a component which is
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relativelydifficultly soluble and a component which is relatively more soluble in a selective polar
solvent which comprises extracting the material by means of a selective polar solvent under ablanlret
of inert gas and then separaing the mixture into liquid phases, one comprising the selective polar
solvent saturated with the more soluble component and the other comprising the less solublecomponent
saturated with the polar solvent.
2. A process as defined in claim 1, inwhii'ii the polar solvent and mixture to be separated
intocoinpoiieiits are flowedcountercurrently in acolumn and the liquid phases are collected
respectively at the top and bottom of the column.
3. A process according to either of the preceding claims, which comprisesdraw ing off the liquid
phase containing the selective polar solvent saturated with the more solublecomponent through a
conduit whichextends upwardly asuffi cient height for the liquids therein to balancehydrostatically
the liquids in the column, the material in thecoltinin and in the conduit being under ablanket of inert
gas.
4. A processaccording to claim 1, which comprises separating the two phases removing the selective
polar sol vent therefrom and recycling the polar solvent for extraction of additional mixture.
5. A process according to any of the preceding claims in which said inert gas consists of nitrogen or a
nitrogen-containing gas.
6. A process according to any of thepreceding claims, in which the solvent is furfural.
7. A process according to any of the preceding claims, in which the material treated is soya bean oil,
cottonseed oil, coconut oil or linseed oil.
8. The process of separating a mixture of glycerides or of fatty acids derived therefrom by means of a
polar solvent under a blanket of an inert gas substantially as hereinbefore described.
9. Separated glyceride or fatty acid fractions whenever produced by a process according to any one of
the preceding claims.Data supplied from the esp@cenet database - Worldwide
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19. GB654533 - 20/6/1951
METAL LUBRICATING BASE COMPOSITIONS
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=GB654533
Applicant(s):
BATAAFSCHE PETROLEUM (--)
IP Class 4 Digits: C10M
IP Class:C10M157/10; C10M157/00
E Class: C10M157/10
Application Number:
GB19480019654 (19480722)
Priority Number: USX654533 (19471028)
Family: GB654533
Abstract:
Abstract of GB654533
A lubricating composition comprises from 1-50 per cent by weight, based on the whole composition, of
an associated or polymerized silicon-containing organic compound of the general formula
>;FORM:0654533/IV (a)/1; p in which R is the same or different unsubstituted or substituted
hydrocarbon radical having less than 20 carbon atoms and n is at least 2, and from 5 to 80 per cent by
weight of a reaction product obtained by treating a polymer and/or co-polymer of a hydrocarbon having
an unsaturated aliphatic bond with a sulphurizing agent or an analagous compound suitable for
introducing selenium or tellurium. The radical R of the silicon compound may be alkyl, alkenyl, aralkyl,
alkaryl or heterocyclic, but is preferably a straight chain or cycloaliphatic radical, such as methyl, ethyl,
n-propyl, isopropyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclohexyl, bornyl and
fenchyl; these radicals may be substituted by halogen or alkoxy radicals. Silicones containing different
alkyl radicals may also be used. Preferred silicones are dialkyl silicones such as dimethyl, di-n-propyl,
di-isopropyl, dilauryl and dicetyl silicones, or a mixture of a silicone having short alkyl radicals with
one having long alkyl radicals may be used. The silicon-containing compounds may be prepared in the
usual manner, and association or polymerization may be promoted by carrying out the reaction in the
presence of oxygen with an acidic agent such as hydrochloric acid, sulphuric acid, phosphoric acid,
hydrofluoric acid, boron trifluoride or bromine, at elevated temperature. The hydrocarbon polymer or
copolymer may be obtained from olefinic or acetylenic hydrocarbons such as olefines obtained by
dehalogenation of halogenated paraffins or by cracking of paraffin waxes; other unsaturated
hydrocarbons mentioned are ethylene, propylene, butene-1, butene-2, isobutylene, the amylenes,
hexene-1, 4-methyl-pentene-1, 4,4-dimethyl-pentene-1, 4-methyl-pentene-2, octene-1,decene-1,cetene1, styrene, cyclohexene, 3-methyl-cyclohexene, 1,4, diphenyl butene-2, butadiene-1,3, pentadiene-1,3,
pentadiene-1,4, hexadiene-1,5, hexadiene-1,4, pentadecene-8, heptadecene-1, hexadecene-1, tridecene7, nonadecene-10, 3,9-diethyltridecene-6, dodecene-1, triacontene-14, pentatriacontene-17, olefines
obtained by dehydration of high molecular weight saturated alcohols, acetylene, propyne, butyne-1,
pentyne-2, hexyne-1, cetyne-1, octyl acetylene and phenyl acetylene. Copolymers of olefins such as
isobutylene, 2 - methylbutene - 1, 2 - ethylbutene-1, secondary and tertiary amylenes and hexylenes
with butadiene, isoprene, cyclopentadiene-2,3, dimethylbutadiene-1,3, pentadiene - 1,3, hexadiene - 2,4,
di - isobutenyl, acetylene and vinyl acetylene are also mentioned. Sulphurizing agents and analogous
materials specified are sulphur, sulphur mono-and di-chloride, sodium polysulphides, e.g. sodium tetraand penta-sulphide, sulphur dioxide, hydrogen sulphide, selenide and telluride, ammonium
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hydrosulphide-hydrogen sulphide, phosphorus penta-, tri- and heptasulphides, phosphorus
pentaselenide and phosphorus pentatelluride. The polymerization or copolymerization may be carried
out in the presence of a Friedel-Crafts catalyst, and the product may be sulphurized in the presence of a
catalyst such as 2-mercaptobenzothiazole, tetramethylthiuram, iodine, zinc chloride, zinc oxide and
organic amines such as hexamethylenetetramine. The composition may contain up to 25 per cent by
weight of a non-abrasive mineral filler such as bentonite, pulverized clay, colloidal clay, tungsten
sulphide and disulphide, titanium sulphide, stannic sulphide, molybdenum sulphide and disulphide,
zirconium selenide, titanium telluride, lead iodide, cadmium iodide, silver sulphate and borax. A
preferred composition contains 5-25 per cent of silicon compound, 30-60 per cent of the sulphurized
hydrocarbon polymer and 10-20 per cent of the mineral filler. The composition may be dispersed in a
diluent such as kerosene, gas oil, petroleum naphtha, kerosene sulphur dioxide extract, aromatic
solvents, petroleum ethers and light lubricating oil fractions. Fatty oils such as castor oil, palm oil,
peanut oil and lard oil, synthetic lubricants such as those produced by the polymerization of olefines or
those of the synthetic ester or ether type, may also be added.ALSO:A lubricating composition
comprises from 1-50 per cent by weight, based on the whole composition, of an associated or
polymerized silicon-containing organic compound of the general formula >;FORM:0654533/III/1; or
>;FORM:0654533/III/2; in which R is the same or different unsubstituted or substituted hydrocarbon
radical having less than 20 carbon atoms and n is at least 2, and from 5 to 80 per cent by weight of a
reaction product obtained by treating a polymer and/or copolymer of a hydrocarbon having an
unsaturated aliphatic bond with a sulphurizing agent or an analogous compound suitable for
introducing selenium or tellurium. The radical R of the silicon compound may be alkyl, alkenyl, aralkyl,
alkaryl or heterocyclic, but is preferably a straight chain or cycloaliphatic radical, such as methyl, ethyl,
n-propyl, isopropyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclohexyl, bornyl and
fenchyl; these radicals may be substituted by halogen or alkoxy radicals. Silicones containing different
alkyl radicals may also be used. Preferred silicones are dialkyl silicones such as dimethyl, di-n-propyl,
di-isopropyl, dilauryl and dicetyl silicones, or a mixture of a silicone having short alkyl radicals with
one having long alkyl radicals may be used. The hydrocarbon polymer or copolymer may be obtained
from olefinic or acetylenic hydrocarbons, such as olefines obtained by dehalogenation of halogenated
paraffins or by cracking of paraffin waxes; other unsaturated hydrocarbons mentioned are ethylene,
propylene, butene-1, butene-2, isobutylene, the amylenes, hexene-1, 4-methyl-pentene-1, 4,4-dimethylpentene-1, 4-methyl-pentene-2, octene-1, decene-1, cetene-1, styrene, cyclohexene, 3 - methyl cyclohexene, 1,4-diphenyl butene-2, butadiene-1,3, pentadiene-1,3, pentadiene-1,4, hexadiene-1,5,
hexadiene-1,4, pentadecene-8, heptadecene-1, hexadecene-1, tridecene - 7, nonadecene - 10, 3,9 diethyltridecene-6, dodecene-1, triacontene-14, pentatriacontene-17, olefines obtained by dehydration
of high molecular weight saturated alcohols, acetylene, propyne, butyne - 1, pentyne - 2, hexyne-1,
cetyne-1, octyl acetylene and phenyl acetylene. Copolymers of olefins such as isobutylene, 2methylbutene-1, 2-ethylbutene-1, secondary and tertiary amylenes and hexylenes with butadiene,
isoprene, cyclopentadiene, 2,3-dimethylbutadiene-1,3, pentadiene-1,3, hexadiene-2,4, di-isobutenyl
acetylene and vinyl acetylene are also mentioned. Sulphurizing agents and analogous materials
specified are sulphur, sulphur mono and dichloride, sodium polysulphides, e.g. sodium tetra and
pentasulphide, hydrogen sulphide, selenide and telluride, ammonium hydrosulphide-hydrogen sulphide,
phosphorus penta-, tri- and heptasulphides, phosphorus pentaselenide and phosphorus pentatelluride.
The composition may contain up to 25 per cent by weight of a non-abrasive mineral filler such as
bentonite, pulverized clay, colloidal clay, tungsten sulphide and disulphide, titanium sulphide, stannic
sulphide, molybdenum sulphide and disulphide, zirconium selenide, p titanium telluride, lead iodide,
cadmium iodide, silver sulphate and borax. A preferred composition contains 5-25 per cent of the
silicon compound, 30-60 per cent of the sulphurized hydrocarbon polymer and 10-20 per cent of the
mineral filler. The composition may be dispersed in a diluent such as kerosene, gas oil, petroleum
naphtha, kerosene sulphur dioxide extract, aromatic solvents, petroleum ethers and light lubricating oil
fractions. Fatty oils such as castor oil, palm oil, peanut oil and lard oil, synthetic lubricants such as
those produced by the polymerization of olefines or those of the synthetic ester or ether type may also
be added.Description:
Description of GB654533
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P AN SI
PATENT SPECIFICATION
654,533 Date of Application and filing Complete Specification: July 22, 1948.
No 19654/48.
_ t 2 7 1 Application made in United States of America on Oct 28, 1947.
Complete Specification Published: June 20, 1951.
Index at acceptance:-Classes 2 (v), 0, R 18 c( 4: 6: 8: 9), R 18 (p: t 2), R 24 c( 4: 6: 8: 9: 17); and 91,
Fld(l: 2).
COMPLETE SPECIFICATION
Metal Lubricating Base Compositions We, N V DE BATAATFSCFE PETROLEUM
MAATSCHAPPIM, a Corporation organised under the Laws of The Netherlands, of 3 ( O ', Carel van
Bylandilaan, The Hague, 6 Holland, (Assignees of ROBERT G.
LAR Sn EN, a Citizen of the United States of America, and a resident of the City, of Albany, County
of Alameda, State of California, -United States of America), do hereby declare the nature of this
invention and in what manner the same is to, be performed, to be particularly described and ascertained
in and by the following statement: 16 This invention relates to novel lubricatAng base compositions, particularly suitable for use in those
cases in which metals are subjected to wear or distortion of their surfaces, as well as change in shape
under heat and pressure.
Various lubricating compositions have been used in metal working operations In such arts, for
example, as drawing heading, die-forging, upsetting and forging 26 machine operations, hydraulic,
compression systems of die-forging, forming, rolling, ironing and stamping, it has been the practice to
employ various lubricants to reduce wear aid, friction, prevent welding and metal pick-up on the
forming surfaces, maintain a desired finish of the formed metal surface, and otherwise perform the
function of a, lubricant Metals which can be thus shaped include ferrous and non-ferrous metals, e g
iron, copper, silver, alum-iniumr, magnesium, as well as the alloys of these and like metals.
Heretofore, petroleum oils as well as vegetable oils, such as palm oil and peanut oil, have been used
for such purposes.
However, metal lubricants containing or consisting of such oils inherently possess certain defects
Along with the progressive decomposition of mineral oils and vegetable oils when they are used alone
or with any common additives, (such as friction,-redueinig agents and known antilPioe 2 1 r 5 wear
agents), in severe cases of use, there occurs a charring and even (in some cases) a " flashing '" On
account of defi 50 cient lubrication of local areas between the surfaces of a die and metal being shaped,
welding, furrowing, cutting of lines and scratching of the metal surfaces known as scoring have also
occurred 55 Further, due to faulty lubrication and decomposition of the starting lubricant compositions,
undesirable deposition of constituents and decomposition products of the lubricant composition, has
been 60 frequently noted Good lubrication consists in part in the effective prevention of contact of two
surfaces by means of an oleaginous film; in case of faulty lubrication the metal surfaces are allowed to
65 come together, and under the effect of heat and presure these metal surfaces become welded The
addition of various finely divided materials, commonly called fillers, to, mineral oil and vegetable oil r
O lubricants to prevent marked decomposition of these oils) to prevent scoring, pickup and welding has
generally been found to be unsatisfactory Additionally, the known lubricants have been found un 75
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satisfactory in the die-forging and drawing of magnesium alloys, of aluminium alloys and of
aluminium coated sheets which are advantageously shaped at temperatures above about 400 " F e g,
parti 80 cularly at from about 400,' F to, about 900 F, or at even higher temperatures.
It is therefore an object of the present invention to provide novel lubricating base compositions which
obviate the above 85 and other defects Another object is to, provide new lubricating base compositions
which have superior stability under the conditions of heat and pressure A still further object of this
invention is to 90 provide a metal lubricating base composition which is particularly suitable for use
during the shaping and/or drawing of aluminium alloys, magnesium alloys and 654,533 alumniniunmcoated sheet materials into objects essentially free of undesirable deposits and particularly free of
scoring.
This invention provides a lubricating ibase composition, which fulfils the foregoing objects and is an
excellent metal working lubricant, comprising from 1 to % by weight, based upon the whole
composition, of an associated or polymnerised silicon-containing organic compound which is a silicone
of the general formula:
ora t s or a iiet-i-silicate of the general formula:
OR j si o OR a in which the several R's represent the same or different unsubstituted or substitulted
hydrocarbon radicals having less than 20 carbon atoms and N is a positive integer of at least 2, and
from 5 to 80 % by weight, based upon the whole composition, of a reaction product obtained by
treating a polymer and or co-polymer of a hydrocarbon having an unsaturated ali26 phatic bond with a
suilphurising agent or an analogous compoundl suitable for introducig, selenium or tellurium The
radical R of the above formulhe may be an allvl alkenvl, 3 U aralkyl, alkraryl or heterocyelic radical,
hu', is preferably a straight chain or a cyclo-aliphatic hydrocarbon radical The following are illustrative
examples of such hydrocarbon radicals: methyl ethyl n-propyl, isopropvl, the various h)utyl amyvl
hexyl heptyl, oetvl nonv 1, decyl and higher radicals, as well ac C Ycoloentyl, ecycohexyl; terpeni c
groupssuch as bornvl fenchivl, and the like, and their homologues and analogues These radicals may
also contain sueh substituents as alkoxy or h alogei radicals and similar substituents which do not
interfere with the beneficial use of the co Inpounds.
A preferred class of associated or polyrmerised silicon-containing organie compounds which form a
constituent of the blends of this invention are the normally liquid associated or polymerised dialkyl 5
10 silicones Polymeric dimethyl silicone is particularly effective in the compositions of the invention,
altlhough polymerised din-propyl silicone, di-isopropyl silicone, or high molectular weight silicone
polymers 55 such as dilauryl silicone are also suitable for the purpose of this invention Compounds
containing low molecular weight alkylradicals tend to be more highly polymerised Dicetyl silicone, on
the other 60 hand, appears to form an association of about three monomneric units In some cases it is
advantageous to have present both a polymerised silicone organic compound having short alkyl
radicals such as 65 polymerised dimethyl silicone and also a like compound having long alkyl radicals
such as an associated or polymerised dicetyl silicone.
Silicones may be prepared by hydrolys 70 ing an organo silicone halide, such as the ehloride, bromide
or iodide, and (partially or completely) dehydrating the resulting hydroxy compound The preparation
of polymeric dimethyl silicone is de 76 scribed in JAGS 63 798 ( 1941) Mixtures of such silicone
halides containing different alkyl radicals and/or different halogen radicals may likewise be hydrolysed
lo yield (in the case of silicone 80 halides containing different alkyl radicals) mixed silicones, that is,
compounds wherein the two organic groups are dlissimilar.
As an eximpile dicetyl silicone was pre 85 pared as follows: A solution of 158 gms.
(Wt-50 gms -niol) of cetyl bromide in ether was added to 12 3 gmis ( 0507 gims mol) of inagllesiun
turnings covered by ether containing a trace of iodine, and the 90 mixture was refluxed The resulting
cetyl magnesiumr brormide solution was added to an etheral solution of 42) ms ( O 247, gi mnol) of
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silicon tetrachloride The Grignard aaddition product precipitated out at 95 room temperahure but was
soluble in ether at O f j' C to 35 C It was hydrolysed with cold, dilute sulphuric acid and the ether laver
evaporated to vield 127 gnis of a mixture of' siliconiv aid and dicetvl sili 100 cone The latter sais
senarated by sohltion in hot ( 800 C) methyl etivl ketono from which it preeillitaftdl on coolin".
The Tield vas 93 mnls of dicetyl silicone melting at 57 C to 590 C A se-aond re 105 erystilli Qation
fromii the samne solvent vielded 74 Qms of dicetvl silicone melting at 60 C to O 110 C Tie highest
melting noint obtained bv furthier Durifiration was 630 (C to 65 C An ebullioseopic 110 determination
of thle molecular weight of 654,533 dicetyl silicone in methyl ketone solution indicated a molecular
weight of approximately 1500 ', indicating that the dicetyl silicone was associated or polymerised to the
extent of three monomeric units.
The meta-silicates may be prepared by reacting the alcohol containing the desired hydrocarbon radical
or radicals with silicon tetrachloride and water in the proportions:
2 ROE + Si C 14 + HO-;(RO)2 Si O + 4 l E Cl The ingredients may be maintained anywhere from
room temperature up to about 350 N C or more when refiuxing, or otherwise up to about the boiling
temperature of the alcohol, until the reaction is substantially complete The reaction may be effected
either without the use of a diluent, or in the presence of an inert solvent for the reactants such as water
or dioxane Reaction time is of the order of a few hours to a day.
Association or polymerisation of the silicon compounds may be promoted, if desired, by carrying out
the reaction in the presence of oxygen with an acidic agent such as H O l, HLSO 4, IHPO 4, HF, BF,3
or Br- For example, the degree of polymerisation, of dimethyl silicone was very considerably increased
by refluxing it with a few drops of concentrated hydrochloric acid at 1200 C to 1,380 C for about 16
hours For compounds of greater monomeric molecular weight a temperature in the range of about 175
C to, 2500 C is usually applicable for a, period ranging from a few hours to several days The tern
associated compound " as used herein and in the appended claims is taken to include both the highly
polymerised and the loosely associated compounds.
Silicones in which the two, R's have different values were made by adding mixtures of two or more
organo-magnesium bromides (for example, dodecyl magnesium bromide and eicosyl magnesium
bromide) to the silicon tetrachloride and hydrolysing the product as in the foregoing example.
The silicone organic compound may be used in proportions varying from between 1 and 50 % of the
blend and preferably 5 to 25 % The proportion of silicone compound which is to be used generally
depends upon the other ingredients which constitute the blend, as well as the conditions under which
the lubricant is to, be used.
The other major constituent of the base composition of this invention is a reaction product obtained by
treating a polymer and/or a co-polymer of a hydrocarbon having an unsaturated aliphatic bond with a
sulphurising agent or an 65 analogous compound suitable for introducing selenium or tellurium.
The polymers and co-polymers may be obtained by polymerising or co-polymerising under any wellknown conditions 70 hydrocarbons having an unsaturated aliphatic bond, such as mono and/or
polyolefinic andjor acetylenic hydrocarbons.
The polymers and co-polymers such as polymerised olefins which are reacted 75 with a sulphurising
agent or an analogous, compound suitable for introducing sele.
nium or tellurium to form the sulphurised products or the selenium or tellurium compounds which are
a major constituent 80 of the base compositions of this invention, are of rather high molecular weight,
such, as above 300 and the molecular weight may even lie within the limits of 5000 and 000 or may be
still higher such as 85 100,000 or 500,Q 000.
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The olefins, from which the above defined hydrocarbon polymers may be derived may be obtained
from various sources and by various means Thus, ole 9 ( fins may be ob'tained by de-halogenation of
halogenated paraffins, by cracking of paraffin waxes, or by dehalogenation of alkyl halideds and the
like Also' as olefin starting materials for the production of 95 such polymers, individual olefins or
mixtures of olefins and non-olefinic substances may be used Starting materials may be butylenes,
aniylenes, refinery gases containing normally gaseous olefines and 100 cracked distillates or other
relatively lowboiling hydrocarbon mixtures containing normally liquid olefins and mixtures of
normally liquid olefins containing dissolived therein normally gaseous olefins 105 Polymers resulting
from the treatment of mono-olefins, preferably isomono-olefins such as isobutylene and isoamylene,
and/or co-polymers obtained by the polymerisa tion of hydrocarbon mixtures such 110 as iso-olefins
and normal olefins may be uised The polymerisation of these olefins and their mixtures may be
obtained by use of suitable catalysts siuch as those of the Friedel-Crafts tvpe 115 Examples of
hydrocarbons having an unsaturated aliphatic bond from which may be derived the polymers and/or
copolymers which after treatment with a suiphurising agent or an analogous sele 120 nium or tellurium
compound are used in the composition of this invention are ethylene, propylene, butene-1, butene-21,
isobutylene, the amylenes, hexene-l, 4methyl-penteue-i, 4, 4-dimethvl-nentene 125 1, 4-methyl-pentene
2, octene-J, decene-1, 4 54, 53 3 cetene-1, styrene cyclohexene, 3-methylcvyc(lohexeine, 1,4-diphlenyl
butene-2, butadiene-l,3, pentadiene-1,3, pentadiene-11,4, hexadiene 1,5, hexadiene 1,4; penta6 deceneS, hleptadecene-1, hexadecene-1, tridecene-7, nonadecene-10, 3,9-diethyltridecene-6, dodecene-1,
triacontene-14, pentaftriacontene-17 d, olefins obtained by dehydration of high molecular weight
saturated alcohols, acetylene, propyne, hutyne1, pentyne-2, hexyyne-l, cetyne-1, octyl acetylene and
phenyl acetylene Co-polymers of olefins and other hydrocarbons having an unsaturated aliphatic bond
may also be used Olefins which may be used to form the co-polvmers of this type include isobutylene,
2 methylbutene1, 2 ethylbutene-1, secondary and tertiary am-lenes alnd hexylenes The other
hydrocarbons having an unsaturated aliphatic band may include butadiene, isoprene evelopentadiene,
20,3-dimethylbutadiene1,3, pentadiene-1,3, hexadiene-2,4, the substituted diolefins such as diisohutenyl, and the acetylenes such as acetylene and vinyl acetylene.
The co-polyrnerisation is preferably carried out in the presence of a FriedelCrafts type catalyst and in
the presence of a suitable diluent such as liquefied ethylene or propane.
The polymerisation may be carried out at low temperatures such as below zero degrees centigrade, or
at elevated temperatures such as above 6 () C and 100 ' C and higher.
The above polymeric hydrocarbon products may be treated with a sulphurising agent or analogous
material in an inert solvent and in an atmosphere of air or in an inert atmosphere such as nitrogen,
under wide temperature conditions such as between 100 C and 3000 C and pressures which may be
below or above atmospheric.
The sulphurising agents and analogous materials which are used to treat the polymer may be the
following materials and their mixtures: sulphur, sulphur mono and dichloride, sodium polysulphides, e
g sodium tetra and pentasulphide, hydrogen sulphide, hydrogen selenide, hydrogen telluride,
ammonium hlydrosulphide-HIS, P 255, P 153, P 4157, 56 P 2 Se and P Te 5.
In carrying out the reaction, conditions are so controlled that onlu the sulphur, selenium andl/or
tellurium atoms remain tightly bound to the polymeric compound Thus in cases where, for example P S,
is used as the sulphurising agent, the reaction is carried out at an elevated temperature of above 180 C,
so that any phosphorus entering the reaction finally splits out as sludge and is substantially removed
Asy phosphorus remaining as a component of the sulphurised polymer is present as entrained matter in
amounts not exceeding 0 2 %.
The ablove reactions are greatly aided 70 when carried out in the presence of a catalyst such as 2mereai)tobenzotfliazole; tetramethylthiuram; iodine; zinc chloride; zinc oxide; organic amines e g.
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hexamethylenetetra mine 75 As an example, sulhp Dirised isobutylene polymer was prepared as
follows:
An amount of about 1 gm -mol of an isobutylene polymer having a molecular weight of from about
1,000 to about 80 G 0,000 was dissolved in an inert solvent such as a light liquid hydrocarbon and to
the mixture was added sulphur at between about 125 and 1600 C and the mixture allowed to react for
about 6 to 8 hours 85 under constant agitation and thereafter the product was allowsed to cool and the
solvent removed.
Another desirable reaction product was obtained bv treating a co-polymer of iso 9 o butylenebutadiene with hydrogen sulphide in the r-resence of ammonium hydrosulphide The co-polvmer
dispersed in a hydrocarbon solvent was added to a vessel and saturated with dry ammonia 95 followed
by dry hydrogen sulphide The vessel was allowed to stand for a week witlb infrequent shaking and
occasional heating The reaction mixture was filtered to remove imiurities and the solvent re loo moved
from the filtrate by evaporation.
The polvmers which are particularly preferred are those which have the property of depolymerisino
without formation of tar, coke and the like As the sul 105 phurised polymer depolymerises at elevated
temperatures, the sulphur at this elevated temperature begins to replace the depolyvnerised polymer as
the aetive lubricating agent 110 The proportion of sulphurised hydrocarbon polymer which is used can
vary from 5 to 80 % v y weight and is preferably between 30 and 60 %, by weight The proportion used
generally depends upon the 115 conditions of use as well as the other components which comprise the
base.
The lubricating base composition of the invention may contain up to 25 %, preferably 10 to 20 % by
weio'ht_ based on the 120 total composition, of a non-abrasive mineral filler such as bentonite,
pulverised clay, colloidal clay, tungsten disuluhide, tungsten sulphide, titanium sulphide, stannic
sulphide, molybdenum 125 sulphide and disulphide, zirconium selenide, titanium telluride lend iodide,
cadmium iodide, siirer supihate or borax.
The non-abrasive mineral filler and mixtures thereof may he added to either corm 130 654,533 ponent
of the lubrica tion, i e to the silicoi to the sulphurised oi hydrocarbon polymer may be added to a m
ponents A general composition of this in following component, Organic silicone or meta silicate
polymer Sulphurised hydro16 carbon polymer and/ or co-polymer Non abrasive mineral filler (e g
bentonite or molybdenum disulphide) This base composit lubricant per se or it an inert diluent or c
poration does not lea The invention ti method of working lubricating base com formula is applied to be
worked in the for dispersion in an mie which on evaporation residue Preferred liquid hydrocarbons
nineral seal oil, gas 4 naphtha cuts, miner SO 2 extract, aromati ethers and light lubi The base composir
persed in a si Lital applied on the surf a cated by any known ing, brushing, swab:
the like.
Compositions of tl only superior 1 ubric, superior stability i heat and pressure r tory film between co,
faces, reduce the coc and prevent wear ar die or worked metal more, even at temp( and higher no o;
occurs on the die or face and these surn free from deposits a:
Rants.
The function of m arily to add in spi position on the worl order to impart so M ting base composi ing
and oily properties to the base lubrine or meta-silicate or cant of this invention especially in the 65 c
otherwise treated early stage of application, minor proporor co-polymer, or tions of fatty oils of animal
or vegetable ixture of these corn origin such as castor oil, palm oil, peaformula of the base nut oil, lard
oil, and similar oils as well vention contains the as synthetic lubricants produced for 70 by weight
example, by the polymerisation of olefins or other unsaturated compounds, or synGeneral Preferred
thetic lubricating oils of the ester or Range Range ether type may be added.
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Lubricant compositions of the present 75 invention possess further advantages in 1-510) 5-25 that the
various known additives, for example, the usual anti-wear, friction-reducing viscosity-improving and
stabilisation agents need not necessarily be added 80 5-8,0 30-60 thereto However, these various
materials may be added to, the compositions of this invention.
As an illustrated example of the exceptional suitability of the novel composi 85 Q-25 10-20 tions of
this invention as lubricants, a metal alloy was coated with a blend of ion may be used as a dimethyl
silicone polymer and sulphurmay be dispersed in ised olefin hydrocarbon polymer containarrier which
on eva ing 10 % of molybdenum disulphide and 90 ye a residue then drawn at a temperature of about
ierefore includes a 800 F with practical and satisfactory metals wherein a results Compared with other
lubricants, position of the above only a low drawing force was required the metal surface to and the
metal was clean and had a desired 95 m of a solution or surface finish Good lubrication by the t diluent
or carrier composition was shown by the fact that a does not leave a there was an absence of scoring,
pick-up diluents are light and welding' These results were in consuch as kerosene, tradiction to the
usual ease with previous 100 oil various petroleum lubricants where a sticking or welding to al spirits,
kerosene the die of the object being formed hat c solvents, petroleum made the operation impractical.
icating oil fractions Having now particularly described and Lion or the base dis ascertained the nature
of our said inven 105 De diluent may be tion and in what manner the same is to beData supplied from
the esp@cenet database - Worldwide
Claims:
Claims of GB654533
ce desired to, be lubri performed, we declare that what we claim
means such as sprav is:bing, immersing and his invention are not ants, but also possess under
conditions of lhey form a satisfacntacting moving surefficient of friction, id distortion of the 1 surface
Furthereratures of 700 F.
bjectionable pick-up faces are essentially nd foreign contamithe diluent is prireading the base comked
metal surface In e additional lubricat1 A lubricating base composition comprising from 1 to 50 % by
weight, based 110 upon the whole composition, of an associated or polymerised silicon-containing
organic compound which is a silicone of the general formula:
Si O H 116 or a meta-silicate of the general formula;:.
Is 654,538 OR Si O OR in which the several U's represent the same or dilferent unsubstituted or
substit-Luted hydrocarbon radicals having less than 2 10 carbon atoms and N is a positive integer of at
least 2, and from 5 to 80 % by weight, based upon the whole composition, of a reaction product
obtained by treatinkg a polymer andlor co-polymer of a hydrocarbon having an unsaturated aliphatic
bond with a sulphurising agent or an analogous compound suitable, for introducing selenium or
tellurium.
2 A lubricating base composition as claimed in claim 1 comprising in addition up to 25 % by weight of
a non-abrasive mineral filler, based upun the whole composition.
3 A lubricating base composition as claimed in claim 1 or ?, in which the associated or polymerised
silicon-containin U, organic compound is present in a proportion of between 5 and 25 per cent, by
weight, based upon the whole composition.
4 A lubricating base composition as claimed in any one of the preceding claims, in which the reaction
product obtained hv treating a polymer andlor copolymer of a Ihydrocarbon having an unsaturated
aliphatic bond with a sulphurising ae'cnt or an analogous compound suitable for introducing selenium
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er tellurium is present in a proportion of between 31 and 60 per cent by weight, based upon the whole
composition.
A kluricatino base composition as claimed in any one of the Dreceding elaims 2 to 4, in which the nonabrasive mineral filler is present in a proportion of between 10 and 20 per cent by weight, basen upon
the whole composition.
G A lubricating base composition as elainmed in any one of the preceding claims, containing both a,
silicone having short alkyl radicals and a silicone having long alkyl radicals.
7 A lnuricating base composition as claimed in any one of the preceding claims, containing one or
more dialkyl 50 silicones of the group consisting of dimethvl, di-n-propyl, di-isopropyl, dilaurvl-, dicet 3 l silicone.
8 A lubricating base composition as claimed in any one of the preceding 55 claims containing the
reaction product obtained by treatin a polymer andlor co-polymer of a hydrocarbon havino an
unsaturated aliphatic bond w-ith one of the following materials or mixtures 60 thereof: sulphur, sulphur
mono and dichloride sodiunl polysuipliides, e sodium tetra and pentaslliide sulphur dioxide, hydrogen
saullhile, hydrogen selenide, hydrogen telluride, aniiiloniiunii 65 liyd(rosulphid(e-HIL,,s; P;s PS P 15.
P.Se, and P Te l A lubric o tim ease composition as claimed in any one of the preceding claims
cotltaimn tue reaction product 70 of an olefin polyier wit h a suiphurisiing agent.
11 A lubricating balse composition as claimed in any one of the preceding claims, contaiming the
reaction product 76, of an isob Juttylena olymer with a sulphurisilln aent.
1 i A lugricating base composition as claimed in any one of the precedinclaims, containin,
uiiioliybdennumll disul 80 plimle or bentonite as a non-aurasive mineral filler.
12 A method of working metals wherein a lubricating base comnosition as claimed in a-ny one of the
preveding 86 claims is applied to the inetal surface to be worked in the formi of a solution or dispersion
in an inert diluent or carrier which on evaporation does not leave a residue 90 Dated the 22nd day of
June, 1948.
ELKINXGTON and FIFE, Consultin Clhem ists and Chartered Patent A ejts, Bank Chamlers 329,
High Holborn, London, W C l, Agents for the Applicants.
PUBL Ibnm U u 1 THE PATENT OFFICE, 25, SOUTHAMP ON MWLOIN LONDON W C 2.Data
supplied from the esp@cenet database - Worldwide
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20. GB670764 - 23/4/1952
IMPROVEMENTS IN OR RELATING TO METHODS OF OBTAINING
PRODUCTS DERIVED FROM PALM OIL
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=GB670764
Applicant(s):
INST RECH S POUR LES HUILES DE (--)
E Class: A61K31/595
Application Number:
GB19490026382 (19491014)
Priority Number: FRX670764 (19490210)
Family: GB670764
Abstract:
Abstract of GB670764
Products, particularly a solid vegetable fat and carotene pigments, are obtained from palm oil by
separating the oil into two fractions of which one is solid up to a temperature of 30 DEG C. and the
other containing the carotene pigments is fluid at temperatures above 15 DEG C., alcoholysing the
latter fluid fraction with a low molecular weight alcohol using an alkaline catalyst to obtain esters
thereof, and subjecting the esters either to rapid distillation in a very high vacuum or to saponification
at a temperature below 60 DEG C. The separation may be effected by fractional crystallization at 15-16
DEG C. The alcoholysis of the fluid fraction is preferably effected with methyl alcohol in the presence
of an alkaline hydroxide. Glycerine is removed by decantation and the residue washed with water until
neutral, any excess alcohol being distilled off. The carotene pigments are then extracted from the
mixture of methyl esters. In one method the exters are subjected to rapid high vacuum distillation, e.g.
at 0.001 to 0.0001 mm. of mercury, to leave a residue rich in the carotene pigments. The carotene
concentrate may be used as such or it may be purified by chromatographic treatment with alumina or
magnesia. In an alternative method the esters are saponified with a strong alkali hydroxide at below 60
DEG C. and in a nitrogen atmosphere, the resulting mixture then being evaporated under vacuum. The
soap mixture is then extracted with an organic solvent, such as petroleum ether or chloroform, which
extract is finally distilled to remove the solvent leaving the carotene residue. A liquid vegetable oil,
such as colza, olive or peanut oil may be added to the extract solution before distilling off the solvent
so as to leave the carotene residue in an oily medium. The methyl esters or the soaps thereof may be
used as such or converted to fatty acids. Specification 567,682 is referred to.ALSO:Products,
particularly a solid vegetable fat and carotene pigments, are obtained from palm oil by separating the
oil into two fractions of which one is solid up to a temperature of 30 DEG C. and the other containing
the carotene pigments is fluid at temperatures above 15 DEG C. alcoholyzing the latter fluid fraction
with a low molecular weight alcohol using an alkaline catalyst to obtain esters thereof, and subjecting
the esters either to rapid distillation in a very high vacuum or to saponification at a temperature below
60 DEG C. The separation may be effected by fractional crystallization at 15-16 DEG C. The
alcoholysis of the fluid fraction is preferably effected with methyl alcohol in the presence of an alkaline
hydroxide. Glycerine is removed by decantation and the residue washed with water until neutral, any
excess alcohol being distilled off. The carotene pigments are then extracted from the mixture of methyl
esters. In one method the esters are subjected to rapid high vacuum distillation, e.g. at ,001 to ,0001
mm. of mercury, to leave a residue rich in the carotene pigments. The carotene concentrate may be
used as such or it may be purified by chromatographic treatment with alumina or magnesia. In an
alternative method the esters are saponified with a strong alkali hydroxide at below 60 DEG C. and in a
nitrogen atmosphere, the resulting mixture then being evaporated under vacuum. The soap mixture is
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then extracted with an organic solvent, such as petroleum ether or chloroform, which extract is finally
distilled to remove the solvent leaving the carotene residue. A liquid vegetable oil, such as colza, olive
or peanut oil, may be added to the extract solution before distilling off the solvent so as to leave the
carotene residue in an oily medium. The methyl esters or the soaps thereof may be used as such or
converted to fatty acids. Specification 567,682 is referred to.Description:
Description of GB670764
COMPLETE SPECIFICATION.
Improvements in or relating to methods of obtaining products
derived from palm oil
We, INSTITUT DERECMERCHES POUR LES
HUILES DE PALME ET OLEAGINEUX, a body corporate duly organised according to the
French laws, of 11, square Petrarque, Paris, in the Seine Department, France, do hereby declare the
nature of this invention and in what manner the same is to be performed, to be particularly described
and ascertained in and by the followingstatement:
This inventionrefers-to a process for obtaining carotene by starting with palm-oil.
It is known to separate palm-oil into two fractions, viz. a solid fraction and a liquid fraction., Such
separation is effected at the ordinary temperature as, for instance, by crystalhsation followed by
pressing, filtration orcentrifuging. 'i'he solid fraction represents abouti of the initial weight of the
palm-oil, and has little colour, but it still contains an appreciable quantity of carotenoids. The liquid
fraction is of a highly blood-red colour and is very rich in carotene. For instance, upon fractionating an
oil which at the start contains1. 2% by weight of carotene, the aforesaid liquid fraction contains1.8%
by weight of carotene.
It is likewise known to obtain carotene starting from palm-oil, by subjecting the palm-oil which has
not been fractioned to alcoholysis with alcohol of a low molecular weight. For instance, British Patent
Specification No. 567,682 describes a process for the alcoholysis of entire palm-oil followed by
distillation, e.g. for example, in a vacuum of0.02-0.5 mm. of mercury, the time and temperature being
regulated throughout; in general, temperatures of less than130 C. are safe for a period which may be
15 to 20 hours, or of150"C. for a short period such as 2 hours. Now, it has been found that, in that way,
carotene loses a large portion of its biological value, on account of the formation ofstereo-is๓me้์rs
the -activity of which is 40%-50% of the activity of the caroteness present in palm-oil.
According to the invention, a process for preparing carotene and carotene products from palm-oil
comprises separating the oil into two fractions of which the one fraction is solid up to a temperature
of30"C. and the other is fluid at temperatures above15 C., subjecting the last-mentioned fraction,
which contains glycerides and is enriched with carotene pigments, to alkaline alcoholysis with an
alcohol of low molecular weight to form esters of said alcohol, and subjecting the said esters either to
rapid distillation in a very high vacuum, or to saponification at a temperature below60 C. Thus, the
esters formed by the alcoholysis are either distilled in a very high vacuum, at a temperature below110
C. during a period sufficiently short to avoid a change in the structure of
the carotene, or are saponified with a strong alkali and extracted by means of an organic solvent.
With the above process, the losses of carotene by stereo-isomerisation are avoided, because the
duration of the treatment is short, and the temperature is lower, as compared with the known processes.
In fact, on the one hand, only the enriched liquid fraction is treated, representing about one-third of the
initial palm-oil and, on the other hand, too high a temperature during distillation or saponification, is
avoided.
The distillation is effected in a vacuum brought up to at least 0.001 mm. of mercury.
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Preferably, the distillation is carried out in a vacuum of from 0.001 mm. to 0.0001 mm. of mercury, at a
temperature of-aboutlQ0 C.
Molecular distillation is very suitable for that purpose.
Likewise, the saponification of the esters takes place at a low temperature and during a greatly reduced
period. This saponification may be effected by mixing the esters, either with a caustic alkali in powder,
or with a concentrated lye or with an alcoholic solution of alkali. The temperature of the operation must
not exceed60 C., and the operation should be carried out in a nitrogen atmosphere. The soap is dried
by evaporation in a vacuum and extracted by an organic solvent, such as petroleum ether or a
chlorinated derivative which dissolves carotene. By evaporating the solvent, a residue is obtained
formed by the part of the palm-oil, which cannot be saponified. The extraction is greatly facilitated by
the high concentration of carotene and the absence of glycerol in the soap.
To the extract solution obtained there mayhi added acontreolled amount, e.g. of a liquid vegetable oil
such as colza-, olive- or peanut oil, the solvent then being driven off on a hot water bath. An oily
carotene preparation remains which is particularly suitable for alimentary or therapeutic purposes.
The raw soap is decomposed in the hot by means of a dilute acid and a layer of fatty acids separates
and is collected.
Example1.-100 kgs. of raw palm-oil having an acid value of 10% are neutralized with sodium
hydroxide About 80 kgs. of neutral oil are obtained which are subjected to fractional crystallization at
about15 C.
By filter-pressing there are obtained 50 kgs. of a solid fat which is light in colour and besides 30 kgs. of
a liquid red oil.
To 30 kgs. of the red oil there are added 7 to 10 kgs. of concentrated methyl alcohol containing1%
to3% of alkali hydroxide.
The mixture is agitated for 3 hours at surrounding temperature. About 2 kgs. ofhigh - percentage
glycerine separates out which is removed by decanting.
The methanolysis product is washed repeatedly with water until neutral and then rapidly distilled
under a vacuum of about 0.001 mm. of mercury. The methyl esters distil normally and about 29 kgs. of
the same are obtained; about 0.5 kg. of a strongly coloured residue remains which contains about 6% to
10% by weight of carotene as ascertained with Beckmann's spectro-photometer.
The carotene concentrate thus obtained may be used as such or may be purified by chromatographic
treatment with alumina or magnesia, preferably following asaponifica- tion step with alcoholic
potassium hydroxide.
The methyl esters may be saponified in the conventional manner or converted directly to the
corresponding fatty acids either by pressure hydrolysis or by means of Twitchell's reagent.
Example2.-30 kgs. of the red-coloured esters obtained as stated above are admixed with 14 kgs.
of36"by. soda lye, the operation being carried out in a nitrogen atmosphere and care being taken that
the temperature remains below60"C. The said temperature is maintained for 3 hours while agitating
mechanically and the whole product is dried by evaporation in a vacuum under continued agitation.
The soap is then extracted with about 50 litres of petroleum ether or chloroform until same is bleached
as much as possible, after which 1 to 2 kgs. of colza-, or olive-, or peanut oil are added to the extract
solution.
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The petroleum ether is distilled off and an oily carotene-containing residue is obtained in which the
carotene-content is about3% by weight, more or less depending on the percentage of the same in the
initial palm-oil.Data supplied from the esp@cenet database - Worldwide
Claims:
Claims of GB670764
Having now particularly described and ascertained the nature of our said invention and in what manner
the same is to be performed, we declare that what we claim is:
1. A process for preparing carotene and carotene products from palm-oil, comprising separating the oil
into two fractions of which the one fraction is solid up to a temperature of30 C. and the other is fluid at
temperatures above15 C., subjecting the last-mentioned fraction, which contains glycerides and is
enriched with carotene pigments, to alkaline alcoholysis with an alcohol of low molecular weight to
form esters of the said alcohol, and subjecting the said esters either to rapid distillation in a very high
vacuum, or to saponification at a temperature below60 C.
2. Process according to claim 1 wherein the distillation is carried out in a vacuum of from 0.001 mm.
to 0.0001 mm. of mercury, at a temperature of about100 'C.
3. Process according to claim 1, wherein a molecular distillation is resorted to.
4. Process according to claim 1, wherein the saponification is effected in nitrogen at a temperature
below60"C. and the product then dried by evaporation under vacuum, the soaps then being extracted
by a solvent and the carotene solution, separated from the soap by any mechanical method, being
evaporated, so as to leave a residue of carotene concentrate.
5. Process according to claim 1 or 4, wherein the carotene solution obtained is diluted in a liquid
vegetable oil, and thesolvent - - --Data supplied from the esp@cenet database - Worldwide
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21. GB671816 - 14/5/1952
METAL WORKING LUBRICANT
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=GB671816
Applicant(s):
BATAAFSCHE PETROLEUM (--)
E Class: C10M1/08
Application Number:
GB19480018293 (19480707)
Priority Number: US19470767860 (19470809)
Family: GB671816
Equivalent:
US2590451
Abstract:
Abstract of GB671816
A metal-fabricating lubricant, for use in such operations as the rolling, drawing and forging of metals,
comprises a major proportion of a substantially non-aromatic waxy hydrocarbon and 20-40 per cent by
weight of a liquid hydrocarbon boiling within the range 300-700 DEG F. The non-aromatic waxy
hydrocarbon may be of petroleum origin or may be prepared by polymerisation of olefins or
dehydration of long-chain fatty alcohols. The liquid hydrocarbon may be gas oil, mineral seal oil,
kerosene, undecane or dodecane. A list of optional ingredients which may be present in the lubricant is
given. This list is subdivided into the following headings:-Animal, vegetable and marine oils; fatty
acids; esters of carboxylic acids with mono- and poly-hydric alcohols; esters of inorganic acids;
phosphatidic materials; sulphur-containing extreme pressure materials such as dibenzyl disulphide,
sulphurized fatty oils and sulphurized fatty acids; halogenated extreme pressure organic materials;
naturally occurring and synthetic waxes. In the examples, lubricants are described consisting of gas oil
and (a) non-aromatic short residue petroleum (b) non-aromatic microcrystalline slop wax, or (c) nonaromatic Pennsylvania cylinder stock slop wax. For comparison purposes a lubricant is described
consisting of palm oil and non-aromatic microcrystalline slop wax. Specifications 565,333 and 569,520
are referred to. The Specification as open to inspection under Sect. 91 refers to a metal-fabricating
lubricant comprising a major proportion of a substantially non-aromatic waxy hydrocarbon and up to
40 per cent by weight of a light liquid hydrocarbon boiling below the lubricating oil range. Examples
of suitable light liquid p hydrocarbons include petroleum naphtha cuts, mineral spirits, kerosene SO2
extract, petroleum ether, and paraffinic hydrocarbons such as normal hexane, dimethyl pentane, octane
and isooctane. This subject-matter does not appear in the Specification as accepted.Description:
Description of GB671816
PATENT SPECIFICATION
671 Date of Application and filing Complete Specification: July 7, 1948.
No. 18293/48.
Application made in United States of America on Aug. 9, 1947.
Complete Specification Published: May 14, 1952.
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Index at acceptance:-Class 91, Fldl.
COMPLETE SPECIFICATION
Metal Working Lubricant We, N.V. DE BATAAFSCHE PETROLEUM MAATSCHAPPIJ, a Body
Corporate organised under the laws of The Netherlands, of 30 Carel van Bylandtlaan, The Hague,
Holland (Assignees of GEORGE L. PERRY, a citizen of the United States of America and resident of
the City of Berkeley, County of Alameda, State of California, United States of America), do hereby
declare the nature of this invention and in what manner the same is to be performed, to be particularly
described and ascertained in and by the following statement:This invention relates to novel lubricants.
More particularly this invention is concerned with metal working or metal fabrication lubricants for
use in such operations as the rolling, drawing and forging of metals.
Problems encountered in lubricating metals under conditions referred to in the previous paragraph are
particularly complex because of the various factors encountered such as high temperatures, excess
pressure, emulsification, presence of foreign bodies or contaminants and work speeds. To lubricate
effectively under these adverse conditions the lubricant must act primarily as a coolant and lubricant.
In the field of rolling lubricants, palm oil was considered most efficient and suitable.
However, palm oil has serious drawbacks in that it is difficult to remove from a metal surface thereby
requiring the use of cleaners which greatly increases operating cost. Also it has a tendency to stain
surfaces which on annealing mars the surface and exerts a detrimental effect when such metals are to
be subsequently tinned, alloyed and the like.
In addition metal surfaces which become too heavily coated with palm oil cause excessive slippage of
the rolls thereby decreasing rolling efficiency. Palm oil is also very costly and scarce and a cheap and
effective substitute for palm oil as a metal working lubricant is greatly desired.
To meet the requirements demanded of a good metal fabricating lubricant such as a [Price 2s. 8d. 1
roll lubricant, it must have high absorption properties (low surface tension) to adhere or wet metal
surfaces even in the presence of 50 water. Also enough reduction -of friction coefficient must be
realised to keep the mill from overheating.
Essential properties of such lubricants are: film strength, ability to reduce friction, 55 ability to wet
metals in presence of water, ability to produce a good lustre on metal surface worked, ease of removal
and nonstaining and de-emulsifying properties, i.e., separating from water and contaminants. 60 Film
Strength When lubricated metal surfaces are forced to slide past each other under high pressures there
is a tendency for surface asperities to penetrate the lubricant film and adhere; 65 this in turn permits the
transfer of metal from one surface to another. This phenomenon known in metal working operation as "
pick-up " of the worked metal by the die or roll may become very pronounced at 70 elevated
temperatures. Although high temperatures may be a result of high friction and may lead to " pick-up ",
it is generally agreed that the ability of a lubricant to prevent adhesion of metal surfaces is a 75
property distinct from and not necessarily related to ability of the lubricant to reduce friction between
sliding surfaces which do not adhere. For this reason the ability of a lubricant to form surface films
which 80 prevent actual metal to metal contact and adhesion is very essential.
Reduction of Friction Roll lubricants must possess the ability to reduce friction between the rolls and
the 85 work sheet in order to reduce power consumption, prevent overheating and minimise the force
which must be applied to the rolls.
The property of a lubricant to reduce friction is referred as " oiliness " and depends upon 90 the sheer
strength of the film formed on a metal surface and to the rheological behaviour ?rice 4s Md r,. Gd.
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9816 ---a7 -,1) 671,816 of thin films of oil when subjected to high pressures.
Wetability and Adhesion Since roll lubricants are usually used in conjunction with water as a coolant,
they must possess the property of displacing water from metal surfaces and resist the washing action of
large quantities of water applied to the rolls and work sheet. Often washing water is applied in the form
of a high pressure spray so that the ability of the lubricant to adhere to metal surfaces is of paramount
importance.
Lustre The appearance of the surface of rolled stock referred to in practice as " lustre " is markedly
influenced by the character of the roll lubricant. To accomplish this, lubricants used for this purpose
should be non-staining and prevent microscopic tears on the worked metal surface.
Ease of Removal and Non-staining A serious drawback of palm oil is the difficulty of removing it from
rolled metal sheets. Generally electrolytic cleaners are required to remove the palm oil for if it is left on
the metal surface and the metal is thereafter annealed the metal surface becomes stained. Roll
lubricants should therefore possess the property of being easily removed when desired and also not
stain the surface with which it is in contact, regardless of the temperature.
Corrosion Resistant Efficient roll lubricants in addition to being able to withstand high temperature and
pressure must be non-corrosive during the rolling process and preferably act as a corrosion inhibitor
after the rolling process, particularly in cases where the rolled metal is stored for long intervals before
being further worked, It is an object of this invention to provide an improved roll lubricant substantially
superior to palm oil. It is another object of this invention to provide a lubricant for metal working
which is stable and noncorrosive. Still another object of this invention is to provide a tacky metal
working lubricant having the property of resisting being displaced by water sprayed under pressure.
Furthermore it is an object of this invention to provide a metal working lubricant which is non-staining
and which can easily be removed from lubricated surfaces.
Specification No. 565,333 describes a composition for lubricating metal surfaces which in the absence
of a lubricant would move in contact with each other at temperatures above about 400 F. by applying
to said contacting surfaces a lubricant comprising a major proportion of a mineral seal oil to which
there is added a sufficient quantity of an aliphatic hydrocarbon polymer (which 65 may be a plastic
solid iso-olefin polymer) for the solution to have a viscosity of at least seconds Saybolt Universal at
1000 F.
Specification No. 569,520, describes as an aid to the process of cold drawing, cold 70 pressing and
cold extruding of metals, first immersing in or swabbing or spraying the metal with a composition
comprising a lubricant (which may consist of animal, vegetable, mineral or synthetic waxes) dissolved
in a volatile solvent such as trichlorethylene (B.P. 1890 F.) and exposing to atmospheric temperature so
as to allow the solvent, to evaporate and leave a film of lubricant on the metal. 80 It has now been
discovered that a metal fabricating lubricating composition, such as a roll lubricant, can be prepared,
which possesses all the above desired properties and which in many respects is far superior to 85 palm
oil or roll lubricants containing as the main constituent palm oil and its derivatives, by forming a blend
of a major proportion of a substantially non-aromatic waxy hydrocarbon and of from 20-40% by
weight of a 90 liquid hydrocarbon boiling within the range of between 300 and 7Q00 F. such as gas oil.
The proportion of the non-aromatic waxy hydrocarbon in the metal fabricating lubricating
compositions of this invention lies 95 preferably between 60 and 80% by weight.
The preferred proportions of the liquid hydrocarbon, which has a boiling range of between 300 and
7000 F. and preferably below 6000 F., lie between 20 and 30% by weight of the 100 composition. The
waxy hydrocarbon base when diluted with a minor proportion of a light hydrocarbon such as gas oil
should have a buttery consistency at low temperatures but under conditions of use should possess 105
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the ability of spreading through water and on to the sheet being lubricated without congealing and
without marring the surface.
Agents having the property of imparting extreme pressure properties to the blend, or 110 of stabilising
the blend against oxidation, or deterioration, or of rendering the blend noncorrosive, may be added in
minor proportions to the blend. Agents which reduce the coefficient of friction of the compositions of
115 this invention, such as the polyalkylene glycols and polyalkylene glycol esters of monocarboxylic
esters may also be added to the blend.
The main components of roll lubricants Qf 12Q this invention, namely, a waxy hydrocarbon or a
hydrocarbon of wax consistency, may be derived from petroleum fractions such as petroleum distillates
or residues, or may be 671,816 produced synthetically by polymerisation of olefinic materials by the
Fischer-Tropsch process or by dehydration of long chain aliphatic alcohols. Preferred waxy hydroS
carbons are those which have a minimum flash point of around about 5000 F. and which do not
vaporise at elevated temperatures such as encountered in rolling of metals under high pressures and
temperatures.
Waxy hydrocarbons may be recovered from suitable petroleum crudes such as Pennsylvania crudes,
East Texas crudes, Mid-Continent crudes and the like by deasphaltising the oil, preferably after
removal of the lower boiling constituents, and thereafter removing the wax from the asphalt free oil by
any known suitable means. The asphalt may be separated from the oil either by distillation or solvent
extraction although solvent extraction is preferred. In this process a solvent is selected in which the oil
is relatively soluble but in which the asphaltic materials are relatively insoluble. Among such solvents
are the light liquid hydrocarbons such as ethane, propane, butane, as well as naphtha and gasoline.
Such solvents extract the oil and wax leaving behind the asphaltic materials as residue. Wax may be
removed from the asphalt-free solution by chilling the solution, and then separating the precipitated
wax by settling, filtering or centrifuging. The waxy material thus produced is sometimes referred to as
a whole wax. Waxy hydrocarbons may also be recovered from suitable petroleum crudes by processes
which involve the fractionation of the crude by distillation. Examples of waxy hydrocarbons recovered
by such processes are slack wax and petrolatum stock. In subsequent processing of these waxy
materials (i.e., the whole wax, slack wax and petrolatum stock mentioned above) there may be obtained
various waxes such as slop waxes, scale waxes, paraffin waxes, plate, malcrystalline and needle waxes,
microcrystalline waxes. The whole wax, the petrolatum stock, the slack wax and the various waxes
which may be obtained therefrom as the result of subsequent processing, are all examples of waxy
hydrocarbons which may be used as one of the component parts of compositions of this invention,
provided the waxes are non-aromatic.
De-waxing or separation of the above waxy constituents from the oil may be accomplished by
selective solvent treatment using liquefied normally gaseous hydrocarbonssuch as propane, butane, and
other organic liquids such as alcohols, ethers, esters, ketones, aldehydes, acids and/or their mixtures,
including methyl, ethyl, propyl, butyl, amyl alcohols; methyl or ethyl or methyl ethyl ether; acetone,
diethyl, methyl ethyl, or methyl isobutyl ketones. Chlorinated hydrocarbons such as carbon
tetrachloride or trichloroethylene and mixtures of chlorinated and non-chlorinated hydrocarbons as
mentioned above may be used.
The first step in obtaining waxy constituents from petroleum crudes such as MidContinent crude may
be to treat the oil, preferably after removal of the lower boiling constituents, with about six volumes of
liquid propane so as to remove the asphalt. The propane from the propane-oil solution is 75 vaporised
so that the ratio of propane to oil is reduced to approximately 2 to 1. The solution may then be chilled
to about - 400 F. or lower causing separation of the wax from the oil. The wax can be removed 80 by
filtration and the propane separated from the de-asphalted and dewaxed oil and waxy material by
distillation. A most desirable wax fraction may also be obtained by treating a heavy fraction of
Pennsylvania waxy 85 oil stock suitable for the production of steam cylinder oil with methyl ethyl
ketone so as to obtain two fractions, one being dewaxed oil and the other fraction being what is known
as whole wax. This whole wax is 9o also treated with methyl ethyl ketone from which again two
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separate fractions are obtained, one fraction being partially deoiled micro-crystalline residue wax
which contains about 5 to 6% of oil and has a 95 melting point of about 1300 F. and the other fraction,
having a melting point of about 65 F. Both the partially de-oiled microcrystalline residue wax
containing about 5 to 6% of oil and having a melting point of 100 about 130 F. and the other fraction
having a melting point of about 65' F. are suitable for rolling lubricants when blended with minor
proportions (20-40% by weight of the whole composition), sufficient to inhibit 105 congealing of the
wax on the rolls and nips, of a liquid hydrocarbon boiling within the range of between 300 and 7000 F.
such as gas oil.
Waxy materials can also be recovered from 110 petroleum distillates or residuum lubricating fractions
and these wax fractions can be split further into special wax cuts having desired characteristics by use
of selective solvents.
This is based on a difference in solubility of 115 different waxy fractions in a given solvent.
Thus when using a methyl ethyl ketone type solvent the aromatic constituents can be removed by
cooling the mixture down to between about - 40 to - 600 C. The aromatics remain substantially soluble
in the solvent as the temperature is lowered while the straight chain waxes and isoparaffins become
substantially insoluble in the solvent.
The straight chain waxes can be separated 125 from the isoparaffins by extraction and fractional
crystallisation. Depending upon the distillate cut used waxes of from 12 to 671,816 about 36 carbon
atoms per molecule and higher can be obtained.
Petroleum wax materials which are particularly suitable have the following properties:
Viscosity at 2100 F.
S.U.S.
Flash 0 F..'.
Fire 0 F.
to Melting Point 0 F.
Mol. Wt.
Amount of oil %. . Amount of aromatic % Wax content..
Broad- Range . 62-134 . 490-560 . 560-640 . 25-143 (25-70 preferred) 600 or higher Not more than
40% 0-2% 60-100% (65-80 preferred) Specifically preferred waxes such as slop waxes have the
following properties:Ref. Index, 300 C. 1.4796-1.4887 Per cent Solid Wax 43-80% Per cent Liquids..
20-57% Melting Point 25-70 C.
(25-40 C. preferred) Instead of obtaining natural waxes from petroleum in the manner indicated above,
waxes can be produced synthetically by polymerisation of olefins under pressure or dehydrating long chain fatty alcohols such as octadecyl alcohol. Thus waxes can be prepared by catalytically dehydrating
octadecyl alcohol at between about 375 to 4500 F.
to yield a mixture or mixtures of monomers and dimers of C18 and C,6 olefins. If desired these
fractions may be separated from each other by atmospheric steam distillation at 550 to 5900 F. and
moisture removed from the waxy fractions by any desired suitable means.
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The diluent for the waxy base of this invention is a liquid hydrocarbon boiling within the range of
between 300 and 7000 F.
and preferably a hydrocarbon having a boiling point within the gas oil range. The amount of diluent
used should not amount to less than 20% and should not exceed 40% of the blend and preferably
should be kept in the range of 20 to 30%. If less than 20% of a diluent is used congealing takes place
and above 40% the blend becomes too fluid and is easily washed away from the rollers, resulting in
poor lubrication and appearance of the worked metal due to tearing action exerted on the worked metal
by the rollers.
Although light petroleum hydrocarbon fractions of the gas oil boiling range are preferred as the
diluent for the waxy hydrocarbon base; other liquid hydrocarbons boiling within the range of between
300 and 7000F. such as mineral seal oil, kerosene, undecane and dodecane may be used.
A preferred light hydrocarbon liquid has the following properties:
Flash 0 F....... 260 Viscosity at 1000 F. S.U.S. 46.5 Boiling range F..... 490-700 A blend of a waxy
hydrocarbon and light petroleum hydrocarbon of this invention suitable as a rolling lubricant may have
the following properties for a blend of 20% gas oil and 80% slop wax. 70 Flash0 F...
Fire 0 F...
Viscosity at 2100 F. S.U.S.
320 350 57.6 V.I... ... 142 Melting Point O F... 92 75 These blends of waxy hydrocarbon and liquid
hydrocarbon boiling within the range of 300 and 7000 F. may be, if desired, fortified with improving
agents such as minor amounts of: 80 A. High molecular weight fatty acids derived from animal,
vegetable, marine oils, e.g.
1. Animal oil Tallow Lard Bone oil 2. Vegetable oils Castor oil Cashew oil Peanut oil Cocoanut oil
Jojoba seed oil Olive oil Olive kernel oil Palm oil Palm kernel oil 3. Marine oils Codfish oil Codliver
oil Dogfish oil Dolphin body oil Dolphin fish oil Herring oil Japanese sardine oil Porpoise body and
jaw oils Neat's foot oil 85= Wool fat Horse foot oil Corn oil Cottonseed oil Kapok oil Rapeseed oil
Ravison oil Sesame oil Sunflower oil Teaseed oil Salmon oil Sardine and 100 sardine liver oils Seal oil
Shark and shark liver oils Sperm whale body 105 and head oils Whale oil Menhaden oil B. Naturally
occurring fatty acids of high molecular weights 1. Saturated Capric Undecylic Lauric Myristic Palmitic
2. Unsaturated Oleic Linoleic Erucic Stearic Arachidic Lignoceric Cerotic Montanic acids Linolenic
Brassidic Elaidic 671,816 3. Substituted fatty acids Ricinoleic Hydroxystearic Ricinelaidic acids C.
Esters of any of the above acids with mono and polyhydric alcohols and other types of esters, e.g.
1. Glycerol mono-oleate, methyl dichlorostearate, diglycol stearate, di-2-ethyl hexyl-azelate, diglycol
laurate, ndecyl hydrogen phthalate or succinate, octadecyl stearate, polyalkylene glycol esters of monocarboxylic acids.
2. Esters of inorganic acids, e.g. tricresyl phosphate and phosphatidic materials such as cephalin and
lecithin.
D. Sulphur-containing materials imparting extreme pressure properties to the compositions of this
invention, e.g.
Dibenzyl disulphide Sulphurised sperm oil Sulphurised fatty oils such as sulphurised cotton-seed oil
Sulphurised fatty acids as listed under part B E. Halogen-containing materials imparting extreme
pressure properties to the compositions of this invention, e.g.
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Chlorinated paraffin waxes Chlorinated fatty acids and esters Chlorinated aromatic compounds
Chlorinated organic compounds containing sulphur F. Natural occurring and synthetic waxes Montan
wax Castor oil distillate Carnauba wax Ozokerite Beeswax Polyalkylene glyc ols, Spermaceti. e.g.
polyethylene glycol The above improving agents may be excluded from the rolling lubricant of this
invention or added to the roll lubricants in 40 very minor proportions generally not exceeding 10% of
the total composition. Smaller proportions of improving agents, such as 1-2%, are generally preferred.
To illustrate more clearly the present 45 invention, the following examples are presented:
TEST I Steel metal strips of standard size (25" x 5") and gauge (.0102") were rolled on a rolling 50 mill
under an idling gauge pressure of about 50,000 pounds. The mill was run at a controlled speed, cooling
water being applied also at a controlled rate and the lubricant tested applied at a temperature of about
55 to 2400 F. The temperature of the rolls at the exit side of the roll nips was held between about 150
and 175 F. The total rolling pressure was measured with a constrained capsule-type pressure gauge
placed 60 between the screw down and the bearing chock. The efficiency of each roll lubricant tested
was determined from the ratio of total rolling pressure in pounds x Extension in inches 65 on the metal
being worked. This ratio is a good comparative criterion of the coefficient of friction developed by the
lubricant on the worked surface.
atai Ttl Ratio Rl Roll Lubricants lresure pressure Extension te Roll Remarks on Lubricant RlLucdn)
(pounds) (inches) ature Extension 1. Mineral lubricating 50,000 78.0 x 103 3.0 260.0 155 Unsuited for
rolling oil Easily washed away 2. Gas oil.. 50,000 157.0 155 Same as 1 3. Commercial 50,000
33.8x103 5.6 121.0 155 Difficult to remove, Nigerian Palm oil stains metals and has some congealing
tendencies 4. 80% non-aromatic 50,000 82.0xO10 11.1 77.0 155 Tends to only Short Residue slightly
congeal, Petrolatum and but does not stain 20% gas oil metal and is easily removed 5. 80% nonaromatic 50,000 82.0 x 103 8.2 89.3 155 No tendency to conmicro - crystalline geal, does not stain slop
wax and 20% metal and is easily gas oil removed 67-1,816 TEST II Another method of determining
the efficiency of roll lubricant is by the lustre test which is a measure of the degree of freedom from
surface tearing during rolling of metals.
The device used consists essentially of a light source from which light is directed on to an area of a
rolled sheet at 450, and the amount of light reflected at 45 is measured with a G.E. photo-electric light
meter. The numbers recorded are foot-candles redfected light Where the theoretical perfect reflectorwould give a reading of approximately 75 foot-candles.
A black plate before being rolled has a reading of approximately 58 foot-candles.
LUSTRE OF METAL PLATE AFTER BEING ROLLED WITH VARIOUS LUBRICANTS % Lustre
Lubricant Lustre (using Composition Reading 58 footcandles as 100%) 1. None (black plate not rolled)
-. 58 100% 2. 60% non-aromatic P ennsylvania Cylinder Stock slop wax 40% gas oil 3. 80% nonaromatic micro-crystalline slop wax 20% gas oil 4. 75% non-aromatic micro-crystalline slop wax 25%
palm oil 77.6% 34 58.6% 19 32.7% TEST IIII One of the most important properties of a good rolling
oil in addition to its -noncongealing properties and the ability of imparting lustre, i.e., its ability to
prevent the tearing of the metal during rolling, is its ability of being easily removed without leaving on
the metal surface lacquer-like stains on annealing.
To determine the lacquer staining properties of roll lubricants the following procedure was followed.
A drop of lubricant was placed on a panel of ftilly deoxidised black plate and inserted in a-small tube
furnace at 2000 F.
with an atmosphere of dry, oxygen-free nitrogen. The temperature was then raised to 12250 F. and
held for 20 minutes. The furnace was then cooled to 2000 F. and the annealed panel removed and
examined for stains caused by the lubricant.
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Lubricant Remarks 1. Palm oil.... Entire panel covered with lacquer and several spots of flaky
carbonaoeous material noted 2. Mineral lubricating Oil Entire panel -coveted with lacquer and 65
several spots of flaky carbonaceous material noted 3. 80% of non-aromatic Slight stain and no microcrystalline catbonateous-materslop wax + 20% ial formed on panel.
gas oil The gas oil employed in Tests I-to III was a gas oil fraction derived from a West Texas crude.
The gas oil fraction had the following 75 properties Flash point, Cleveland open cup F... 300
Viscosity at 1000 F. S.U.S.
Boiling range (ASTM Dist,) 42.7 80 Initial 0 F....... 544 10%........ 566 50%....... 574 90%...... 590 E.P...
--.... 616 85 The non-aromatic micro-crystalline slop wax -employed in Tests I to III had the following
properties:
Flash point, -Cleveland open cup, 0 F...... 520 90 Fire point, Cleveland open cup, 0 F......;.. 600
Viscosity at 1000 F. S.-U.'S. 570 Viscosity at 1300 F. S.U.S... 288.5 Viscosity at -210 F. S.U.S... 85.1
95 Viscosity Index.. .. 133 Melting point, 'F... 102.2 Carbon residue, Conradson.. 0.01 Wax
content, %.. .. 65.2 Specific dispersion -. -. 0. -6 -13 100 Aniline point -..... 134.8 Average -molectilar
weight. . 65 Content of aromatics, %.. 0 Content of naphthenes, %.. 6 Content of paYaffins, %. . 4 105
Specific gravity.. .. 0.8495 The non-aromatic Penfisylvania Cylinder Stock slop wak employed in Test
II had the following properties:
Filash point, F........545 -110 iFire point, 0 F..-... '15 Carbon residue, Conracson.. 0:25 Viscosity at
2100 F., S.U.S... 85.8 Melting point, F.... 152 Wax content, %.. .. 97.6 115 Rolling lubricants of this
invention are wdll adapted as rust inhibitors after thexrolled sheet has been worked.
The roll lubricant of this invention may be applied to the rolls of a sheet metal rolling 120 mill by-any
suitable means such as spraying, dripping or the like. It -may -be applied on the sheet metal prior to,
duinng or after rolling. Preferably the lubricant is warmed to about a temperature of 150 to f75 F., 125
before applying it -to the rolls so as to aid in 671,8167 spreading the lubricant more evenly on the rolls
and work piece.
In addition to being an excellent roll lubricant, compositions of this invention may be used as drawing
lubricants, forging and die lubricants and in various other processes where drawing and working of
metals requires lubrication.
HAVING NOW particularly described and ascertained the nature of our said invention and in what
manner the same is to be per-Data supplied from the esp@cenet database - Worldwide
Claims:
Claims of GB671816
formed, we declare that what we claim is:1. A metal fabricating lubricating composition comprising a blend of a major proportion of a
substantially non-aromatic waxy hydrocarbon and of from 20-40% by weight of a liquid hydrocarbon
boiling within the range of between 300 and 700 F.
2. A metal fabricating lubricating composition as claimed in claim 1 which contains the light liquid
hydrocarbon in a proportion of between 20 and 30% by weight.
3. A metal fabricating lubricating composition as claimed in claim 1 or 2 comprising micro-crystalline
wax, paraffin wax, slop wax or petrolatum stock as the substantially non-aromatic waxy hydrocarbon.
4. A metal fabricating lubricating composition as claimed in any one of the preceding claims
comprising a gas oil as the light 30 liquid hydrocarbon.
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5. A metal fabricating lubricating composition as claimed in any one of the preceding claims
comprising a minor proportion of an extreme pressure agent. 35 6. A metal fabricating lubricating
composition as claimed in any one of the preceding claims comprising a minor proportion of one of the
improving agents hereinbefore specified, such as a sulphurised fatty oil, a 40 chlorinated paraffin wax,
a chlorinated fatty acid or ester, a polyalkylene glycol ester of a monocarboxylic acid.
Dated the 7th day of July, 1948.
ELKINGTON & FIFE, Consulting Chemists and Chartered Patent Agents, Bank Chambers, 329, High
Holborn, London, W.C.1.
Agents for the Applicants.
Redhill: Printed for Her Majesty's Stationery Office, by Love & Malcomson Ltd.-1952.
Published at The Patent Office, 25, Southampton Buildings, London, W.C.2, from which copies may
be obtained.Data supplied from the esp@cenet database - Worldwide
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22. GB682797 - 19/11/1952
METHOD OF FRACTIONATING FATTY OILS
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=GB682797
Applicant(s):
SEPARATOR AB (--); SVENSKA OLJESLAGERI AB (--)
IP Class 4 Digits: C11B; C11C
IP Class:C11B7/00; C11C3/10; C11C3/00
E Class: C11B7/00B; C11C3/10
Application Number:
GB19500009225 (19500414)
Priority Number: SEX682797 (19490425)
Family: GB682797
Abstract:
Abstract of GB682797
Fatty oils are separated into fractions of relatively saturated and relatively unsaturated homogeneous
triglycerides by simultaneous inter-esterification and extractoin with a selective solvent at such a
temperature that two liquid phases are formed. Inter-esterification (the effect of which is to increase the
proportion of homogeneous triglycerides in the oil and reduce the proportion of mixed triglycerides)
may be effected by treating the oil with a suitable catalyst, e.g. a polyhydric alcohol such as ethylene
glycol, propylene glycol, glycerol, pentaerythritol, mannitol or sorbitol, or a polyhydric alcohol and an
alkali, e.g. sodium hydroxide, or an oxide or hydroxide of tin, cadmium or lead, or an alkali alcoholate,
e.g. lithium, sodium or potassium ethylate. The selective extraction may be carried out (1) with a
solvent which dissolves most of the oil at the operative temperature but separates selectively as a liquid
phase the saturated triglycerides present or produced in the oil, or (2) with a solvent which has only a
low solvent power at the operative temperature and dissolves only the unsaturated triglycerides. In case
(1), the process may be effected at a gradually falling temperature, with continuous or periodic removal
of the raffinate, whereby first the saturated triglycerides and then triglycerides of fatty acids with only
one double bond are caused to separate from the mixture. Suitable solvents for use in this way are
ethylene glycol monomethyl or monoethyl ether and nitroethane. In case (2), the process may be
effected at successively increasing temperatures to extract in turn the most unsaturated triglycerides
and then triglycerides of an increasing degree of saturation. Suitable solvents for use in this way are
nitromethane, acetonitrile and trimethyl phosphate. In an example, a solution of sodium methylate in
methanol is added to a mixture of soya oil and ethylene glycol monomethyl ether, and the mixture is
allowed to stand for 2 hours at 50 DEG C. A layer of saturated triglycerides separates and is removed,
and the residual mixture is cooled to 45 DEG C and allowed to stand for 4 hours, whereupon a layer of
less saturated triglycerides separates and is removed. The process is repeated at 35 DEG C and 25 DEG
C, the separated layers being removed in each case. In another example, a raffinate obtained from
herring oil by extraction with furfural is treated with sodium methylate and extracted with acetonitrile,
the extraction being repeated three times with intermediate agitation for two hours. Other oils which
may be treated are cotton-seed, peanut, olive, palm, sunflower, sesame, rapeseed, poppy-seed, linseed,
perilla, Chinese-wood, whale, sardine, shark and fish-liver oils and dehydrated castor oil.Description:
Description of GB682797
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PATENT SPECIFICATION
682,797 Date of Application and filing Complete Specification: April 14, 1950.
No. 9225/50.
/ \,.a r k J Application made In Sweden on April 25, 1949.
Complete Specification Published: Nov. 19, 1952.
Index at acceptance:-Class 91, C(2al: 3a7).
COREPLETE SPEOIFIQCAT(ION Method of Fractionating Fatty Oils We, AKTIEBOLAGET
SEPARATOR, a Swedish Company, of 8, lFlemminggaten, Stockholm, Sweden, and SVENSKA
OLJESLAGERI ATIBBOLAGET, a Swedish Cornpany, of Goteborg, Sweden, do hereby declare the
invention, for which we pray that.a patent may be granted to us, and the method by which it is to be
performed, to be particularly described in and by the following statement: It is known that vegetable or animal oils consisting of natural glycerides of saturated and unsaturated
fatty acids can be fractionated by treatment with selective solvents. The desired object is to separate
glyceride fractions with a high content of unsaturated fatty acids from glycerides containing mainly
saturated fatty acids. This separation can be effected by treatment with certain solvents, such as furfural,
acetone, acetoacetic ester, nitro ethane and others with which the oil is not quite miscible at the
operating temperature. The mixture is then divided into two layers, one containing oil with some
solvent dissolved in it (the raffinate phase) and one consisting of solvent with some oil dissolved in it
(the extract phase). After separating the phases and evaporating the solvent, a raffinate and an extract
are obtained with different properties, their properties differing also from those,of the initial oil. When
using solvents of the aforementioned type. a raffinate is obtained having a lower iodine number than
that of the initial oil, and is a concentrate of the saturated glycerides, while the extract h as a higher
iodine number than the initial oil and is a concentratp of the more unsaturated glvcerides.
The technical importance of the extraction method depends on the separated saturated and unsaturated
glycerides having quite different fields of application, the produets thus refined commanding
considerably higher prices on the market than the initial oil.
r I The saturated triglycerides are used mainly in the food industry while the unsaturated glycerides are
used as drying 50 oils in the paint and lacquer industry.
The object of treating fatty oils with selective solvents is to separate as completely as possible
saturated and unsaturated glycerides. The yield and properties 55 of the products obtained are
determined partly by the selectivity and dissolving power of the solvent, partly by the extraction
process and partly by the chemical character of the initial oil. It is evident 60 that an oil with a
relatively high content of unsaturated fatty acids must be used if a good yield of siccative oils is to be
obtained. Thus, a yield of about 60%' extract (of iodine number 150) can be oh- 6.5 tained by countercurrent extraction of soya bean oil (iodine number 135) with furfural, and up, to, 55%l extract (iodine
number 240) by extraction of sardine oil (iodine number 190) with the same sol- 7? vent, whereas
furfural extraction of coconut oil does not give any appregiable amount of extract with high iodine
number. The difference in the extraction result depends on the different fatty acid 75 constitution of the
fats, Soya bean oil contains about 30'% of oleic acid and 50%' linoleic acid, while the sardine oil
contains in addition to oleic acid and linoleioc acid a considerable amount of unsatur- 8(j ated fatty
acids with three or more conjugated double bonds per molecule. Coconut oil, however, consists
practically exelusively of saturated triglycerides.
Natural oils are, however, comp)licated 85 mixtures of triglycerides containing to a large extent
different fatty acids in the same molecule. Hilditch (The Chemical Constitution of Natural Fats) has
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pointed out that the fatty acids in natural glvcerides show a tendency to be as evenly or widely
distributed as possibl:e, among all the glycerol or triglyceride molecules. The main part of a given fatty
acid which occurs in a relatively small quantity is therefore found in glycerides containing only one
molecule of such acid, whereas the two other hydroxyl groups, of the glycerol are esterified with other
fatty arid molecules. For this reason the extraction gives mixed glycerides which contain not only
unsaturated but also saturated fatty acids. In like manner, that portion of the oil being relatively
saturated after the extraction (the raffinate) contains unsaturated fatty acids which cannot be removed
by extraction, as the unsaturated fatty acids are bound to glycerol molecules which are simultaneously
esterified with saturated fatty acids.
It is known that a more complete separation of saturated and unsaturated fatty acoid esters can be
obtained if the extrac"O tion process is combined with an interesterification of such a type that the
natural mixed fatty acid glycerides are transmuted, entirely or partly, into glycerides with only one acid
radical in the same molecule.
The inter-esterification is preferably carried out in the presence of catalysts in order to obtai a higher
rate of reaction.
The molecular interchange can be carried out at different temperatures depending upon the desired
state of equilibrium and the activity of the catalyst. When using polyhydric alc.ohols. such as.ethylene
glycol, propylene glycol, glycerol, pentaerythritol, mannitol or sorbitol, as catalysts, the isomerisation
should take place at a relatively high temperature in order to obtain a reasonable rate of reaction. Under
such reactive conditions., however, especially when treating produ ts containing fatty acids of high
iodine number, undesirable reactions may ensue, such as polymerization or oxidation. In the presence
of..alkali, e.g. sodium hydroxide, and some of the aforesaid polyhydrio alcohols, the requisite reaction
temperature may bee considerably reduced.
Other catalysts, such as oxides or hydroxides of tin, cadmium, lead and other metals, are.also very
effective. Combinations of the monohydrio alcohols.with the alkali. metals, e.g. lithium, sodium or
potassium ethyjate, are active at relatively, low temperatures, i.e about 2.0100 C. It may often be
important to pr.otet thle retaction mixture against undesirable supplementary. reactions by carrying out
the inter-esterification in a neutral solvent or in an inert gas atmosphere.
Extraction of the inter-esterified mixture with a selective soliv.ent, if desired, after inactivation. of the
catalyst, often gives at suitable temperatures as is known, a better_ yield or a higher iodine 63 number
than the extraction of the untreated oil.
When carried out in a homogeneous phase the inter-esterification will result in an equilibrium where
the different fatty acids are evenly distributed among the trifglyceride molecules. Subsequently the
yield of glycerides with only one kind of fatty acid combined with the glycerol molecule will be very
small. A controlled inter-esterification may, however, be 75 effected in such a way that the equilibrium.
is disturbed 1by continuous removal of certain of the products formed. In this way the yield of
uniform glycerides may be considerably improved. - 80 According to a prior proposal, the
interesterification may for instance, take place at such a temperature that certain highmelting
components are crystallized out of the oil mixture. Thus, triglycerides containing only saturated
fatty.acids are] usually relatively diffi.ult to dissolve in the oil mixture and are separated from it by
cooling. This giyes.rise to, a shifting of the equilibrium between the liquid 90 phase glycerides, and the
inter-esterification in the homogeneous phase can continue while a new formation of saturated
triglycerides takes place. The process may go on as long as saturated fatty acids are 95 components of
the glycerides,'liquid at the reaction temperature, but the process may be interrupted when the desired
transmutation has been obtained. By adding some suitable solvent, such as. hexane, 100 gasoline, lower
alcohols or mixtures of these, it is possible to further reduce the solubility of the solid, saturated
triglycerides, whereby a more compete separation of these components is obtainable. This manner in
which the inter- esterification process is conducted in the prior proposal has certain disadvantages.
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The process must be carried out at a low temperature at which certain components, 110 i.e. the most
saturated glycerides, crystallize, the equilibrii-m iof the liquid homogeneous phase at the same time
being displaced, but at such.Iqow temperatures the reacetion velocity is low. Also, the process 115 is
suitable only for separating off saturated - glycerides. _ It is not suitable for removal of small quantities
of glycerides having a high iodine number. Additionally the dividing of the initial material must be 120
carried out by two separate Operating steps, namely, inter-esterification and - a subsequent filtration.
It has now been found, according to the present.invention that a very suitable way. 1265 of cenducting and controlling the process of molecular rearrangement consists in carrying,out -the interesterijicatio6n and extraction with a selective solvent simul taneously. 130 682, 7 97 682,797 3 5When
carrying out the process according to the present invention the interesterification is carried out in the
presence of a selective solvent and at a temperature at which the components in the initial material as
well as the reaction products atire in the liquid state. In the presence of a catalyst the inter-esterification
proceeds and homogeneous triglycerides are formed as reaction products. The selective solvent and the
reaction temperature are so chosen that two liquid phases are formed either from the beginning or as
the reaction proceeds. Having different solubilities the different triglycerides are distributed between
the two layers according to their solubility and concentration.
One of the layers contains the bulk of the initial material. From this layer homogeneous triglycerides
will be separated out during the inter-esterification which may consequently be conducted in the
desired direction. The other liquid layer contains from the beginning only small amounts of material
hut as the process proceeds greater amounts of homogeneous triglycerides are concentrated in this layer.
By choosing a solvent with high selectivity but with a relatively low solvent power for the triglycerides,
the reaction can be carried out at a high temperature in which case the reaction velocity is great. In
comparison with the elder inter-esterification methods the time of reaction can thus be considerably
reduced.
The dividing of the initial material in fractions with the desired properties is carried out in one
operation and at temperatures at which both phases are in the liquid state. This is a great advantage
from a technical point of view as it is much more easy to separate two liquid phases than one liquid and
one solid phase.
The operating conditions may be chosen according to the properties of the initial oil and the desired
products, so that either triglycerides of a mainly saturated character or unsaturated triglycerides are
separated out of the reaction mixture, as will be explained in the following.
In the first case, a solvent is chosen which, at, the reaction temperature, dissolves most of the oil but
which separates selectively as a second liquid phase the saturated fatty acid Glycerides present in the
oil or formed during the reaction. The raffinate then obtained is continuously removed during the
reaction, and an extract freed from saturated fatty acids is obtained. The remaining extract contains a
mixture of unsaturated fatty acids. whileh are further fractionated by reducing the temperature until the
triglycerides containing only fatty acid radicals with one double bond are selectively separated out as a
special liquid phase. The process may be carried out by gradual temperature reductions with stepwise
removal of the most saturated triglycerides. By a suitable choice of reaction time, temperature 70
gradient and solvent, the initial oil is thus split up into a series of fractions consisting of homogeneous
triglycerides which in one and the same molecule contain only one.and the same fatty acid radical. Ex.
75 amples of solvents which may be used in the process described above are ethylene glycol monoethyl
ether, ethylene glycol monomethyl ether and nitro ethane.
The combined inter-esterification and 8( selective extraction can also be performed in such a way that
the triglycerides with a high content of unsaturated fatty acids present in the natural!oil or formed at the
inter-esterification are extracted from the 85 reaction mixture. The extraction is carried outf with a
solvent which has a low solvent power at the reaction temperature and thus dissolves only the
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unsaturated triglycerides, leaving the mixed and/or 90 saturated glycerides in the liquid reantion
mixture. Suitable solvents are then used, e.g. nitro methane, aceto-nitrile or trimethyl-phosphate, and
by successively increasing the reaction temperature, the triglycerides of an increasing degree of
saturation are extracted and the initial oil is divided into fractions of homogeneous glycerides.
The extraction may be carried out in atloo 100 least two steps by a multiple contact process or as a
counter-Durrent contact process, a temperature gradient being maintained between the steps.
The method of the present invention 105 may be used to great advantage in the fractionation of fatty
oils of vegetable, aninal and marine origin. Examples of oils which may be treated according to the
invention are cotton seed oil, peanut oil, 110 olive oil, palm oil, sunflower oil, sesame oil, rape seed oil,
poppy seed oil, linseed oil, soya bean oil, perilla oil, Chinese wood oil, whale oil, cardine oil, herring
oil, shark oil, various fish liver oils, and dehydrated castor oil.
The products obtained may be used for various purposes, e.g. as raw material for margarine
production, as cooking and salad oils, as shortening agents in the fat 120 industry, as siccative oils in
the paint and varnish industries, for the manufacture of wetting agents, as well as for cosmetics, and
pharmaceutical and medicinal products. 125 EXAMPLESS.
1. To a mixture of equal parts of soya oil (iodine number 131) and methyl cellosolve (glycol
monometlhyl ether -,OCH., CH2OC0H) is added such a quantity of a 130 682,797 solution of sodium
methylate in methanol that the quantity of sodium methylate in the mixture will be 0.5;% of the
quantity of soya oil. The mixtire was homogeneous at 50 C. After 2 hours rest at this temperature, a
layer containing substantially saturated glycerides and a minor quantity of solvent had separated. After
this layer had been drawn off, the temperature was reduced to 45 C., and.aftex further 4 hours rest at
this latter temperatuire a new layer of relatively saturated glycerides had separated. After separation of
the phases the mixture was cooled to 35' C., where the newly formed layer was drawn 15 off after 6
hours. Finally, the temperature of the mixture was reduced to 25 C., and a newly formed layer was
drawn off after 6 hours. The phases drawn off were treated by distilling off the s-'vent,_and 20 then the
iodine numbers of- the fractions obtained were determined. The results are given in the following table.
TAsIr:8.
Simultaneous inter-esterification - a.nd 25 selective extraction of soya oil -in the presence of methyl
cellosolve. The iodine number of the initial oil is 131. Reaction Temperature, C.
Reactio Time, Ho 2 4 6 Quantity glyceride obtained after n separation, in 1urs % of the initial oil 7
ReAt 53 Iodine number of the fat fraction obtained 38 71 98 164 2. 0.5% sodium methylate and 200%'
aceto-nitrile were added to a raffinate obtained from herring oil (iodine number 137.0) by countercurrent extraction with furfural. The mixture was agitated vigorously at 24 C. during two hours. After
this period the agitation was interrupted, and the aceto-nitrile layer containing the unsaturated
glycerides formed by the inter-esterification was drawn off. Then further 200% aceto-nitrile were
added and the agitation- was continued still two hours, before the aceto-nitrile was drawn off. The
same treatment was repeated two times.
All the four aceto-nitrile extracts were combined and the actalyst neutralized with diluted acetic acid,
whereupon the solvent was distilled off and the iodine number and quantity of the residue determined.
A parallel test was at the same time carried out by extracting the starting oil with the same quantities of
aceto-nitrile and during the same periods of time but without the presence of a catalyst. By
simultaneous inter-esterification and extraction 29.7%' extract (iodine number 168.4) was obtained. By
repeated extraction of the starting oil without the presence of a catalyst, only 9.7%' extract (iodine
numher 158.2) was obtained.Data supplied from the esp@cenet database - Worldwide
Claims:
Claims of GB682797
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What we claim is:1. A method of fractionating fatty oils during simultaneous inter-esteriofication of them, characterised
in that the interesterification is acoomplished in the 75 presence of a selective solvent and at such a
temperature, that two liquid phases are formed, fractions consisting of homogeneous triglycerides
being separated from the other triglycerides contained in 80 the starting oil.
2. A method of fractionating fatty oils according to claim 1, ciaracterised in that the reaction
temperature is gradually increased or decreased while the process is 85 progressing.
3. A method of fractionating fatty oils according to claim 2, chaxacterised in that either that phase,
containing relatively saturated triglycerides, or the solvent 90 phase is continuously separated from the
reaction mixture.
4. Method of fractionating fatty oils according to any of the preceding claims, character'ised in that
the extraction is carried mout in at least two steps by a multiple contact process or as a counter current
contact process.
5. Method of fractionating fatty oils according to claim 4, characterised in that 100 a temperature
gradient is maintained between the steps.
6. The method of extractive fractionation of fatty oils substantially as herein described - 105 A. A.
THORNTON & CO., Chartered Patent Agents, Napier House, 24-27, High Holborn, London, W.C.1,
For the Applicants.
Leamington Spa: Printed for Her Majesty's Stationery Office, by the Courier Press.-1952.
Published at The Patent Office, 25, Southampton Buildings, London, W.C.2, from which copies may
be obtained, 682,797Data supplied from the esp@cenet database - Worldwide
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23. GB685681 - 7/1/1953
IMPROVEMENTS IN OR RELATING TO THE FRACTIONATION OF FREE
FATTY ACIDS
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=GB685681
Applicant(s):
PITTSBURGH PLATE GLASS CO (--)
IP Class 4 Digits: C11C
IP Class:C11C1/00
E Class: C11C1/00D
Application Number:
GB19470030209 (19471113)
Priority Number: USX685681 (19400517)
Family: GB685681
Abstract:
Abstract of GB685681
A relatively unsaturated fraction is separated from a mixture of free fatty acids substantially free from
oxidized fatty acids by introducing the mixed fatty acids into a vertical column at a point between the
ends thereof, introducing a polar solvent substantially immiscible with a non-polar petroleum
hydrocarbon solvent of lower specific gravity used in the process into the column at a point above that
at which the acids are introduced, introducing the hydrocarbon solvent into the column at a point below
that at which the acids are introduced, maintaining a temperature within the column at which the
components of the mixture remain in the liquid state but below that at which the hydrocarbon solvent
phase and the polar solvent phase are completely miscible, and withdrawing a relatively less
unsaturated raffinate and a relatively more unsaturated polar solvent extract from opposite ends of the
column. The non-polar solvent may be a paraffinic hydrocarbon such as iso-octane and the polar
solvent may be furfural. A list of other polar solvents which may be used is given. The mixed fatty
acids fractionated may be those of marine oils, such as menhaden, sardine, whale or cod oil, or those of
linseed, tung, soya bean, cottonseed, perilla, and palm oil, or of fats such as lard and tallow. The
volume ratio of polar to non-polar solvent may range from about 4 : 1 up to 10 or more of the latter to
one of the former. The volume ratio of the fatty acid mixture to that of the solvent mixture may range
from 1 : 1 up to 12 parts of the solvent mixture to one part of acids. The extraction column and the feed
conduit for the fatty acid mixture may be furnished with jackets through which temperature control
media are circulated. Specification 658,967 is referred to.Description:
Description of GB685681
PATENT SPECIFICATION
685,68 1 Date of Application and filing Complete Specification: Nov. 13, 1947.
4. No. 30209/47.
Application made in United States of America on May 17, 1940.
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Complete Specification Published: Jan. 7, 1953
Under Rule 17A of the Patents Rules 1939-1947, the proviso to Section 91 (4) ___wtw of the Patents
& Designs Acts, 1907 to1946, became operative on Nov. 13, 1947.
Index at acceptance:-Class 91, B(2a: 4).
COMPLETE SPECIFICATION
Improvements in or relating to the Fractionation of Free Fatty Acids We, PITTSBURGH PLATi
GLASS CO1iPANY, a corporation organised under the laws of the State of Pennsylvania, United
States of America, of 2200, Grant Build6 ing, Pittsburgh, Pennsylvania, United States of America, do
hereby declare the nature of this invention and in what manner the same is to be performed, to be
particularly described and ascertained in and by the following statement:The present invention relates to a method of separating mixtures of free fatty acids into fractions, each
of which is relatively enriched in certain comf) ponents of the mixture and correspondingly
impoverished in other components, and it has particular relation to the fractionation of such mixtures
by liquid phase extraction with a polar solvent which is a more powerful solvent for certain
components of the mixtures of acids than for others.
One object of the invention is to provide a process of solvent extraction for frac26 tionation of
mixtures of free fatty acids, by means of which it is possible to fractionate mixtures with polar solvents
possessing such degree of miscibility with all components of the acid mixture as to ao render it difficult
to make a liquid phase fractionation by ordinary methods.
In our British Patent Specification No.
658,967 there is disclosed a process of extracting a relatively unsaturated fraction from a mixture of
free fatty acids free from oxidised fatty acids comprising such unsaturated fatty acid in admixture with
less unsaturated fatty acid, which process comprises contacting the mixture at room temperature with a
two phase solvent system comprising a hydrocarbon solvent and a polar solvent immiscible therewith,
separating the immiscible solvents while the two phases are in the liquid state and eliminating the
solvents from the fatty 46 acids dissolved therein.
The present invention provides a process of separating a relatively unsaturated fraction from a mixture
of free fatty acids substantially free from oxidized fatty 60 acids and containing acids of relatively high
unsaturation and acids which are relatively more saturated which comprises introducing the mixed fatty
acids into a vertical column at a point between the 65 ends thereof, introducing a polar solvent of
higher specific gravity than and substantially immiscible with a non-polar petroleum hydrocarbon
solvent used in the process into the column at a point above 60 that at which the acids are introduced,
introducing the hydrocarbon solvent into the column at a point below the point at which the acids are
introduced, maintaining a temperature within the column at 65 which the components of the mixture
remain in the liquid state but below that at which the hydrocarbon solvent phase and the polar solvent
phase are completely miscible, and withdrawing a raffinate and 70 polar solvent extract from opposite
ends of the column.
The more unsaturated components of the mixture of acids are more strongly attracted to the polar
solvent than are the 75 less unsaturated components which tend to concentrate in the non-polar
petroleum hydrocarbon solvent so that there is considerable degree of separation of the components of
the mixture. As the non-polar B0 petroleum hydrocarbon solvents used are substantially immiscible
with the polar solvent at the temperatures employed and are of substantially lower specific gravity than
the polar solvents separation into 85 phases is rapid and relatively complete.
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When a non-polar petroleum hydrocarbon and a polar solvent of higher 685,081 specific gravity and
substantially immiscible therewith are conjointly contacted in counter-current flow as described above
with a mixture of free fatty acids differing in their degree of unsaturation, such as are derivable by
saponification from various glyceride oils including linseed oil, tung oil, soya bean oil, cottonseed oil,
perilla oil and palm oil marine oils, such as menhaden, sardine, whale and cod oil and fats such as lard
and tallow, it is possible to separate the mixture of free fatty acids into relatively saturated and
relatively unsaturated components.
The following constitute specific examples of polar solvents which may be used in the treatment in
various ratios, for example 1 to I volume ratio with an immiscible petroleum hydrocarbon solvent, such
as iso-octane, and applied to the liquid phase separation of the free acids at room temperature.
TABLE A.
HYDROXYL Methyl alcohol Ethylene glycol Propylene glycol Glycerine HYDROXYL, ESTER.
beta-lHydroxy ethyl acetate Methyl lactate Ethyl lactate Diacetin HYDROXYL, CARBONYL Methyl
butanolone Acetyl methyl carbinol HYDROXYL, ETHER f-methoxy ethanol Diethylene glycol
Triethylene glycol Diethylene glycol monoethyl eth 2-hydroxy methyl-i, 3-dioxo-lan CARBOXYL
Formic acid Acetic acid HYDROXYL, DOUBLE BONDS Phenol Benzyl alcohol HYDROxYL,
TRIPLE BONDS Dimethyl ethynyl carbinol HYDROXYL, HALOGEN Ethylene chlorhydrin
Propylene chlorhydrin 6 beta, gamma-dibromo propyl ali HIDROXYL, OTHER beta-hydroxy
propionitrile beta-ethoxy ethyl lactate beta-ethoxy ethyl glycolate Furfuryl alcohol Eugenol
Salicylaldehyde (aldehyde, bond) 2-nitro-1-butanol 2-nitro-2-methyl-3-hexanol ACID ANHYDRIDE
Acetic ESTER Ethylene glycol diformate Triacetin Glycol diacetate Ethyl acetyl glycolate Ethylidine
diacetate Methyl mnialonate Ethyl oxalate Methyl oxalate ESTER, CARBONYL Methyl levulinate
Ethyl levulinate Methyl acetoacetate Ethyl acetoacetate ESTER, ETHER fi-methoxyethyvl formate -rmethoxyethyl adipate di(P-methoxyethyl) succinate ESTER, IMIDO Ethyl n-methyl carbamlate
ESTER, DOUBLE BoND Ethyl maleate ESTER-DoUlLE BOND-ETHER Methyl furoate Furfuryl
acetate ESTER, HALOGEN Methyl chloroacetate beta-chloroethyl acetate Acetochlorhydrin ESTER,
CYANIDE Miethyl cyanoacetate AMINO (on IMINo) Diethylene triamine Triethylene tetramine
AMINO (OR Iro DOUIBLE BONDS Aniline Toluidine NITRILEer Propionitrile e SULPHATE
Dimethyl sulphate ALDEHYDE Methoxy acetaldehyde Furfural Cinnamaldehyde Benzaldehyde -m nitrobenzaldehyde CARBONYL Acetonyl acetone CARBOTNYL, ETHER, DOUBLE BONDS
Furfural acetone cohol CARBONYL, DOrBLE BONDS Benzalacetone CARBONYL, A31IDO
Formamide Acetamide CARBONYL, CHLORO 1-ehlor butanone-2 double ETHER Dimethioxy
tetraglycol volume ratios. For example, in ratios from 1 to 1 up to a ratio of 10 or 12 parts of the
solvent mixture to 1 part of acids.
The degree of fractionation desired in any particular mixture of acids will depend upon the
characteristics desired in the fractions. In some cases a small degree of fractionation is sufficient. In
other cases relatively marked differences between one or more components, and the 35 original acid
mixture may be desired.
Mixtures of free fatty acids differing in their degree of unsaturation may be subjected to, a multiple
stage extraction. Such extraction is substantially analogous to 40 back washing the free fatty acids in
countercurrent flow to a polar and a non-polar hydrocarbon solvent. The) following flow diagram
illustrates the treatment of a mixture of soya bean acids 45 using furfural and a non-polar petroleum
naphtha as the selective solvents in repeated stages. The figures given with each stage indicate the
iodine values (I.V.) of each fraction obtained at the several 50 stages.
URAL ETHER, CHLORO beta, beta'-dichloro diethyl ether Chloroethoxychlorethyl ether ETHE1R,
IMINO Morpholine ETHER, NITRO o-nitro anisole o-nitro phenotole ETHER, CARBONATE lt betamethoxy ethyl carbonate NITRiO Nitromethane Nitrobenzene THIOCYANATE Methyl thiocyanate
PiHO SPHATE Trimethyl phosphate Triethyl phosphate The volume ratio of polar solvent to non-polar
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hydrocarbon may vary over a range of from about 4 to 1 up to 10 or more of the latter to one of the
former.
The substantially immiscible mixtures of polar solvent and hydrocarbon may be applied to the free
fatty acids in varying ExTRRCT RAFFtNA'rI E xtrat.- If _l.V. = 13s Extract= furf-urall phase.
In conducting the extraction the free fatty acids of soya bean oil were dissolved in petroleum naphtha
to obtain a 50% solution by volume, of free fatty acids.
This solution was extracted by agitating with furfural which had previously been saturated with
petroleum naphtha at room temperature (approximately 23 C.) The volume ratio of furfural to fatty
acid solution was 1 to 1. The petroleum naphtha. phase was re-extracted with furfural saturated with
naphtha at each stage keeping the volume ratio of furfural Rafinate=petroleum naphtha phase.
toe, fatty acid solution in the relation of 1 to 2.
The furfural phase was similarly contacted with an additional equal volume of petroleum naphtha.at
each stage and 7() separation repeated.
Such apparatus and process are illustrated diagrammatically in the accompanying drawing in which an
extraction column 10 is provided with jacket sections 11,-having inlets 12 and outlets 13 for
temperature control medium.
A non-polar hydrocarbon diluent such 685,681 as petroleum naphtha is introduced into the column a
short distance above the lower extremity -through conduit 14, and a free fatty acid mixture, such as
soya bean oil acids, cotton seed acids, or others of like nature, is fed to an intermediate portion of the
column at a substantial distance above the inlet 14 through conduit 16. The latter may be encased in a
heating jacket 17 having inlet 18 and outlet 19 for a heating fluid. Polar solvents such as furfural or one
of the other solvents herein disclosed may be introduced into the column a short distance 1.5 from the
upper extremity thereof through conduit 20.
It is to be observed that the raffinate phase comprising the more highly saturated fatty acids dissolved
in the hydrocarbon solvent collects as a layer 23 in the upper extremity of the column while the extract
comprising the polar solvent saturated with more unsaturated acids collects as a distinct liquid layer 24
in the lower portion of the column. Between these! two layers there is an extensive zone 26 filled with
countercurrently flowing mixtures which may be described as being composed of a polar solvent phase,
nonpolar hydrocarbon solvent phase and undissolved liquid free fatty acids. Extract is drawn off at the
lower extremity through conduit 27 and the petroleum naphtha. phase (non-polar hydrocarbon) is
drawn out at the upper extremity through conduit 28.Data supplied from the esp@cenet database Worldwide
Claims:
Claims of GB685681
What we claim is1. A process of separating a relatively unsaturated fraction from a mixture of free fatty acids
substantially free from oxidized fatty acids and containing acids of relatively high unsaturation and
acids which are relatively more saturated which comprises introducing the mixed fatty acids into a
vertical column at a point between the ends thereof, introducing a. polar solvent substantially
immiscible with a non-polar petroleum hydrocarbon solvent of lower specific gravity used in the
process into the column at a point above that at which the acids are introduced, introducing the
hydrocarbon solvent into the column at a point below the point at which the acids are introduced,
maintaining a temperature within the column at which the components of the mixture remain in the
liquid state but below that at which the the hydrocarbon solvent phase and the polar solvent phase are
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completely 60 miscible, and withdrawing a raffinate and a polar solvent extract from opposite ends of
the column.
2. A process according claim 1 in which the polar solvent is one specified in 65 Table A herein.
3. A process according to either of the preceding claims, in which the non-polar petroleum
hydrocarbon solvent is a paraffinic hydrocarbon. 70 4. A process according to claim 3, in which the
hydrocarbon is iso-oetane.
5. A process according to any of the preceding claims, in which the polar solvent is furfural. 75 6. A
process according to any one of the preceding claims, in which the mixed free fatty acids are those of
marine oils, soya bean oil, linseed oil, perilla oil, tung oil, cottonseed oil, lard or tallow. 80 7. The
process of separating a relatively unsaturated fraction from a mixture of free fatty acids free from
oxidised fatty acids into fractions of varying degrees of unsaturation substantially as 85 hereinbefore
described.
8. Free fatty acid fractions of varying degrees of unsaturation whenever prepared by a process
according to any one of the preceding claims. 90 Dated the, 13th day of November, 1947.
For: PITTSBURGH PLATE GLASS COMPANY, Stevens, Langner, Parry & Rollinson, Chartered
Patent Agents, 5, to 9, Quality Court, Chancery Lane, London, W.C.2, and at 120, East 41st Street,
New York, 17, N.Y., UTnited States of America.
Leamington Spa: Printed for Her Majesty's Stationery Office, by the Courier Press.-1953.
Published at The Patent Office, 25, Southampton Buildings, London, W.C.2, from which copies may
be obtained.
685,681Data supplied from the esp@cenet database - Worldwide
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24. GB700400 - 2/12/1953
METHOD OF PRODUCING HIGH-VALUE CAROTENE-CONTAINING PALM
OIL FROM PALM-TREE WASTE PRODUCTS
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=GB700400
Applicant(s):
INST RECH S POUR LES HUILES DE (--)
E Class: A61K31/595
Application Number:
GB19510027150 (19511120)
Priority Number: FRX700400 (19510928)
Family: GB700400
Abstract:
Abstract of GB700400
Palm oil of high carotene content is extracted from the kernel-free residue obtained from the usual
extraction methods of the palm fruit, which kernel-free oil-cake residue is known as "palm fibres," by
extraction with a solvent for both the oil and carotene. Hydrocarbons, such as petroleum spirit, and
chlorinated solvents, such as trichlorethylene, are specified. The "palm fibres" are preferably
preliminarily dried under conditions not detrimental to the carotene content thereof and also crushed to
provide the maximum degree of fineness. The solvent is distilled from the extract, with or without
steam, to give a carotene enriched palm oil.Description:
Description of GB700400
COMPLETE SPECIFICATION
Method of Producing High-Value Carotene-Containing Palm Oil
from Palm-Tree Waste Products
We, INSTITUT DE RECHERCHES POUR LES
HUILES DE PALME ET OLEAGINEUX, a Body
Corporate duly organised according to the
French Laws, of 11, 12, 13, Square
P้้trarque, Paris (Seine), France, do herebydeclare the invention, for which we pray that a patent may
be granted to us, and the method by which it is to be performed, to beparticularlydescribed in and by
the followingstatement :
Palm oil extracted in the conventional manner by squeezing,centrifugai separation, or any other
process, contains a considerable amount of carotene averaging about 1 per thousand. Ordinary
extractive methods leave a residualoil-cake wherefrompallm kernals are separated.
TheLernel-free oil-c ekes constitute what is commonly called "palm fibres" and although this residue
still contains about10 per cent of palm oil no other use has hitherto been found for it except as a fuel in
oil-plant boilers or as a fertilizer in the plantations. Besides, its low density militates against such
applications.
It was during systematical tests carried out in order to dry these fibres that the surprising discovery
was made that the residual oildbtained therefrom contains a much higher percentage of carotene than
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the corresponding oil produced by the conventional pressure method. On the other hand, these oils
differ only in their carotene contents.
This is only ascribable to the fact that the carotene is not evenly distributed in the fresh palm pulp. In
fact, the thin cutinized or epicarp coating that surrounds the fruitnotoriously has apoor oilproduc- ing
structure yet its carotene content is extremely high. During the squeezing of the fruits the oil runs out
without carrying along the epicarp caortene, thereby leaving the latter in the oil cake.Prefer- ably after
the squeezing process the epicarp cells are capable of giving off this carotene to solvents such as
petroleum spirit, chlorinated solvents, and, as a rule, any solvents suitable forcarotenoids and lipids.
Thus, by processing milled palm fibres with a solvent of this type not only is residual oil extracted
from the oil-cake but also carotene from the epicarps.By eliminating the solvent the carotene is left in
the recovered oil and the latter,bering an over-carotenized substance, may be considered as a highvalue raw-material for preparingcarotenized concentrates. It is also suitable, when purified, for use as a
natural colouring matter for fats and other food products.
According to the invention, a process for obtaining palm oil particularly strong in carotene consists of
extracting palm oil in known manner from the pulp of the fruit of the oil palm, separating the
stones,consisting of thekernals of the fruit and the hard shells surrounding thesekernels, from the
fibres, and extracting these fibres with a solvent suitable forcarotenoids and lipids.
It has been found that by drying and squeezing the fibres before, the extraction step the latter was
considerably facilitated, making it possible to produce a powder having an apparent density of the
orderof .5 which in relation to the original fibres represents a reduction of from 3 to5 times their
volume and permits of extracting with smaller apparatus, and with less volume of solvent than usual.
The dried and solvent-free fibres may be used either as a fertilizer (they are easilyspread both because
they are in powder condition and occupy a reduced space) or as a fuel in boilers of any types adapted to
use fuels in pulverulent form, or, after being caked to briquettes, in ordinary boilers. The ash residue
may be used as a fertilizer forrestoring to the ground a fraction of the mineral elements removed
therefrom by the crop.
EXAMPLE
Fresh palm fibres are dried in a hot-gas drier of the type used in themaking of lucerne meal, the drying
temperature and time being adjusted to values not detri mental to the carotene content of the fibres.
Complete dryness is not sought in this step but only a reduction of the moisture content to about 10% in
order to facilitate the consecutive squeezing and extraction steps.
The squeezing step is carried out in a manner adapted to provide the maximum degree of fineness in
view of the extraction step and the milled fibres are treated batchwise or continuously with a solvent,
for example trichlorethylene in fixed or >;RTI rotary extractors.Data supplied from the esp@cenet
database - Worldwide
Claims:
Claims of GB700400
The palm-oil and carotene-containing solvent is distilled off from the mixture, this step being
terminated in racuo, with or without steam for carrying over the solvent. The residue is an avercarotenized palm-oil having a carotene content of >;RTI about 5 per thousand whereas the oil vielded
by the conventional pressure method titrates only 1.1 p. 1000 of carotene. The solvent retained by the
extracted fibres is recovered either in the extractor or in an adjacent apparatus,
What we claim is:1. A process for obtaining palm-oil paticularly strong in carotene consisting in extracting palm-oil in
known manner from the pulp of the fruit of the oil palm, separating the stones, consisting of the kernals
of the fruit and the hard shells surrounding these kernals, from the fibres, and extracting these fibres
with a solvent suitable for carotenoids and lipids.
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2. A process for obtaining palm-oil particularly in carotene, as claimed in claim 1, wherein the
treatment of the fibres to obtain the residual oil consists in extracting the fibres with a solvent suitable
for carotendoids and lipids, after a drying step and a squeezing step carried out under conditions not
detrimental to the carotene content of the fibres.
3. A process for obtaining palm-oil particularly strong in carotene, as claimed in claim 1. wherein the
treatment of the>;/RTI; fibres is carried out as herein described in the Example.Data supplied from the
esp@cenet database - Worldwide
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25. GB707385 - 14/4/1954
IMPROVEMENTS IN OR RELATING TO THE SOLVENT EXTRACTION OF
FATTY OIL, FAT AND WAX FROMSOLID MATTER OF ANIMAL OR
VEGETABLE ORIGIN, AND APPARATUS THEREFOR
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=GB707385
Applicant(s):
TIGER OATS AND NAT MILLING COM (--)
IP Class 4 Digits: C11B
IP Class:C11B1/10; C11B1/00
E Class: C11B1/10B
Application Number:
GB19500022722 (19500915)
Priority Number: ZAX707385 (19490921)
Family: GB707385
Abstract:
Abstract of GB707385
>;PICT:0707385/III/1; Fats, fatty oils and waxes are extracted from solid particles of vegetable and
animal (including fish and marine animal) materials with the aid of an organic solvent, employing a
solvent to solute ratio by volume not substantially greater than 1.5 : 1, to produce a miscella of at least
40 per cent. solute content by volume. In calculating the solvent to solute ratio, that portion of the
solvent which is retained by the exhausted solids upon separation of the miscella is excluded.
Vegetable and animal materials mentioned are maize, maize germ, cottonseed, soyabean, sesame seed,
rapeseed, coconut meat, linseed, groundnuts, sunflower seed, palm kernel, copra and oil cakes
therefrom, whale, fish and/or parts therefrom, suet, hides and bones. Organic solvents mentioned are
solvent naphtha, petroleum naphtha, n-hexane, n-heptane, mixed octanes, trichlorethylene, ethylene
dichloride, methyl chloride, carbon disulphide, acetone, ethyl ether or mixtures thereof. If insufficient
fibrous material is present to facilitate separation of the miscella from the residue, this fibrous material
may be added, for example in the form of bran, husks, chaff, straw, or asbestos. The process may be
carried out in the apparatus shown in the drawing, wherein the material to be extracted is taken from
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storage bin 1 and reduced to a suitable size by means of rollers 3. The comminuted material passes
through line 5 to loading device 7, from which it passes into the basket of the centrifugal solvent
extractor 8. Fresh solvent is contained in tank 9, while miscellae of decreasing concentration are
contained in tanks 10, 10a, 10b and 10c. Solvent or miscellae pass from these tanks to the extractor 8
through lines 11, 11a, 11b, 11c and 12, and miscellae are returned to the tanks through pump 16 and
line 17. Extracted meal is removed from the centrifuge basket and passed via duct 24 to bin 25 and then
via duct 26 to drier 27, the vapours from which pass to a solvent recovery system. In operation,
concentrated miscella from tank 10 is passed to extractor 8 and recycled to tank, this circulation being
continued as long as economic. The same procedure is adopted in turn with miscellae from tanks 10a,
10b and 10c and finally with pure solvent from tank 9. When the extraction is complete, miscella from
tank 10 is passed via line 23 to the solvent recovery system for separation of extract and solvent, while
the contents of tank 10a are transferred to tank 10. Similarly, miscella is passed from tank 10b into tank
10a, from tank 10c into tank 10b and from tank 9 into 10c, while fresh solvent is passed into tank 9.
The system is then ready to commence a new extraction. Instead of a five-stage extraction, employing
the five tanks 10, 10a, 10b, 10c, 9, the extraction may be conducted in any desired number of stages. In
the examples, (1) and (4) corn germ meal is extracted with n-hexane or trichlorethylene in five stages,
(2) and (3) soyabean or cottonseed meal is extracted with n-hexane in four stages, and (5) corn germ
meal is extracted with n-hexane in seven stages.Description:
Description of GB707385
PATENT SPECIFICATION
Date of Application and filing Complete Specification: Sept 15, 1950.
707,385 No 22722/50.
Application made in South Africa on Sept 21, 1949.
Complete Specification Published: Apri, 14, 1954.
Index at acceptance:-Class 91, C 1 (A 3:F).
CO-MPLETE SPECIFICATION'
Improvements in or relating to the Solvent Extraction of Fatty Oil, Fat and Wax from Solid Matter of
Animal or Vegetable Origin, and Apparatus therefor We, TIGER OATS AND NATIONAL MILLING
COMPANY, LIMITED, a Corporation organised under the Laws of the Union of South Africa, of 106,
Carr Street, Newtown, Johannesburg, Transvaal Province, Union of South Africa, do hereby declare
the invention, for which we pray that a patent may be granted to us, and the method by which it is to be
performed to be particularly described in and by the following statement: The present invention relates to a new and improved process for the extraction of fatty oils, fats and
waxes from solids which are capable of extraction and which are of biological origin, i e vegetable or
animal origin (animal being used in its widest sense to include fish and marine animals), by means of
an organic solvent for the said matter, and to apparatus for carrying out the said new process.
Up to the present it has been conventional, in so far as we are aware to treat such solids with a solvent
in an extractor, in which the solid is at rest or agitated in a bath of solvent or in which the solvent is
caused to percolate through one or more beds or layers of solid capable of extraction Where suitable,
such solids may be first subjected to an expeller treatment The miscellae obtained in practice according
to previous methods, are usually rather dilute and in order to recover the extracted matter and the
solvent therefrom thev are first concentrated in a series of pre-evaporators, usually operated at
atmospheric pressure and indirectly heated by steam coils, and the rest of the solvent is then removed
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from the concentrate in an evaporator and a stripper operated under reduced pressure and with direct
injection of steam.
The present invention comprises a process for the extraction by means of an organic solvent of at least
one of the group consistine of fatty oil fat and wax from particles of solid matter of biological origin
lPrice 2/81 as herein defined, characterized in that the solvent to solute ratio by volume as herein
defined is low (i e, not substantially greater than 1 5 to 1) to produce a miscella of at 50 least 40 per
cent solute content by volume.
We have now found that the extraction of fatty oils, fats and waxes, from solids which are capable of
extraction and which are of biological origin as above defined by 55 means of an organic solvent is
greatly improved by operating in accordance with the invention, in which a solvent to solute ratio by
volume of not substantially greater than 1.5 to I is employed, excluding from such 60 ratio that solvent
which is retained by the exhausted solids upon separation of miscella therefrom to produce a miscella
of at least per cent solute content by volume.
Preferably, centrifugal force is applied 65 throughout the duration of the extraction for passage of the
solvent liquid (including miscella) through the solids e g, the extraction may be carried out while the
solids are in the form of a bed inside a revolving per 70 forated basket However, broadly speaking, the
bed of solids may be disposed in any other manner which includes a stationary bed, and, if desired, any
means known in the art may be employed to assist the flow 75 of the solvent liquid through the bed or
to separate the solvent from the bed.
Solvent extraction in accordance with the present invention, may have one or more of the following
advantages, as against pre 80 vious methods:
(a) A more concentrated miscella is obtained direct Thus a miscella obtained direct in the solvent
extraction of soy bean meal, according to previous methods, con 85 tains only between approximately
14 and 22 per cent of fatty oil by volume (between approximately 19 and 28 per cent of fatty oil by
weight when using hexane as solvent).
whereas in the process according to the pre 90 sent invention a concentrated miscella is obtained
direct which is withal more suit707,355 able for stripping, and which usually contains approximately
40 to 50 per cent or more of fatty oil by volume (about 50 to 60 per cent or more of fatty oil by weight
when a using hexane as solvent).
The advantages obtainable with a more concentrated miscella are:
(i) That the miscella can be stripped direct, e g, in a tower type of evaporator, or after only little preevaporation treatment Consequently no or only a small investment for pre-evaporators is required.
(ii) That owing to the reduction of the extent of the pre-evaporator treatment or its elimination, the
extracted matter undergoes less heat-treatment and therefore suffers no deterioration or less than
hitherto This is important as regards its colour and/or keeping qualities.
(iii) An economy in energy for the removal of solvent from the miscella is attained.
(b) A smaller solvent-fatty oil ratio is required and in consequence solvent losses and the costs for
solvent recovery are reduced For example in an efficient soy bean solvent extraction plant, as hitherto
employed the solvent-fatty oil ratio is approximately 4:1 by volunme When working according to the
present invention, the solvent-fatty oil ratio is about 1 5:1 by volume but may be lower, whilst the
degree of extraction is the same or higher.
(c) The miscella is frequently more thoroughly removed from the extracted solid.
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Thus a soy bean meal, which has been extracted, in accordance with the present invention, may
contain only about 5 to 15 per cent by weight of solvent for recovery, and rarely more than 15 per cent,
whereas according to the methods previously practised, it frequently contains about 30 to 35 per cent of
solvent for recovery.
Therefore by the present invention, the recovery of solvent from the residue is simplified, as fewer or
simpler driers are required, and the corresponding outlay is reduced.
(d) Extractable matter can be extracted from solids of a type which could not be extracted
economically according to previous solvent extraction methods for example.
from South African maize germ meal.
(e) If a higher degree of extraction is desired than that normally attained in certain conventional
solvent extraction processes.
this can easily be arranged according to the present invention by simply givine one or more additional
solvent treatments in the centrifuge without increase of the solventfatty oil ratio To attain comparable
results, according to these conventional ( 65 methods, inter alia the solxent-fatty oil ratio must be great
11 increased, or the entire process must be repeated.
(f) Pretreatment of the initial solids is in certain cases eliminated or simplified.
(il For example in certain conventional 70 plants flaking is regarded as a more or less essential
pretreatment According to the present invention, flaking has shown no appreciable advantage in the
case of ground expeller oil 75 cakes inter alia although in certain cases such as with cotton seed flaking
or pulverizing is advantageous.
(ii) In certain conventional plants, conditioning of the initial material as re o 80 gards moisture content
for example, in soy bean extraction has been found most important In accordance with the present
invention, conditioning as regards moisture content can fre 85 quently be dispensed with if desired.
As shown above many of the problems besetting experts in solvent extraction, according to the
methods and means hitherto employed have been overcome by the O go present invention.
Extraction in accordance with the invention is preferably carried out in a basket centrifuge.
Usually the solvent or miscella is sprayed 95 on to the solid to be extracted in the centrifuge It may be
desirable previously to moisten the solid with solvent or miscella, or to mix it therewith for transport
into the centrifuge Again the solid may be mixed o 100 with the requisite amount of solvent or miscella
from the beginning and centrifuged.
Advantageously the organic solvent or miscella is pumped around in a closed circuit for extraction of
the solid in the centri 105 fuge.
It will usually be desirable to subject a given charge of solid to successive extractions with miscellae
from earlier extractions.
having successively decreasing concentra 110 tions and finally with clean solvent Separate containers
may be provided for fresh solvent and for separately collected miscellae of various concentrations from
various stages of extraction 115 A preferred method is to charge a single centrifuge or a battery of
centrifuges with fresh solid to be extracted, and to treat it successively with different miscellac, each
being more dilute than that preceding it until 120 finally clean solvent is passed thr 1 ough the solid to
be extracted The nmiscella employed for the initial treatment of fresh solid conveniently may be the
most concentrated.
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or next most concentrated mniscella from an 125 earlier operation on solid matierial fr lomll the same
or a similar source Cocks are provided to switch over to the supplies of miscellae of different
concentration and of clean solxent Other cocks are provided adapted 130 707,385 to switch over the
effluent from tile centrifuges to ducts leading to the containers for miscellae of corresponding
concentration.
The time of switch-over of the cocks for the eilluent is preferably correlated to the time of switch-over
of the corresponding cocks for the feed of miscella The control of the cocks may be effected
automatically.
A-ain a series of centrifuges may be employed in the first of which fresh solid is extracted with the
most concentrated miscella or next most concentrated miscella from an earlier operation, whereas in
the last tilhe most impoverished residue is treated with fresh solvent and so on through the series
according to the counter-current principle.
Miscella is used for extraction until a concentrated miscella is obtained preferably suitable for direct
stripping This concentrated miscellae may contain 40 to 50 per cent by volume or more of fatty oil.
The size and speed of the centrifuge and therewith the amount of centrifugal force employed, are
selected according to circumstances The amount of centrifugal force should be sufficient to leave only
a small amount of miscella say between 10 and 20 per cent by weight or even between 5 and per cent
or less, in the residue.
The process is particularly adapted for the solvent extraction of fatty oils and or fats, hereinafter
referred to as " oleaginous matter" from vegetable matter containing the same, such as maize (corn),
maize germ.
mieiie (maize) germ meal, cotton seed, soya bean, sesame seed, rape seed cocoanut meat.
linseed, ground nuts, sunflower seed, palm kernel, copra and oil cakes therefrom or from animal
matter such as whale fish and or parts thereof, suet, hides, or bones from land animals.
Any organic solvents with the desired extraction properties and having a boilinc range allowing of
their easy recovery mav be employed Examples of these are solvent naphtha petroleum naphtha nhexane.
n-heptane, mixed octanes, tri-chlorethvlene, ethylene dichloride methyl chloride carbon disulphide
acetone and ethyl ether, or mixtures thereof.
If desired provision may be made for raising the temperature of the material in the centrifuge e g by
injecting steam or hot solvent vapor e g that produced during solvent recovery into the centrifuge, or by
indirectly heating as with steam, andior by preheating the solid and/or solvent prior to its introduction
into the centrifuge.
If the solid is not in a form suitable for extraction, it is comminuted or subjected to some other
preparatory treatment e g grinding or in some cases flaking which treatment may or may not include
preliminarv cooking.
It is preferred that sufficient fibrous material of a character which will facilitate separation of miscella
from residue be present If this is not naturally present in the solid to be extracted, such fibrous material
mayv be admixed therewith, if desired e g in the 70 form of bran husks chaff straw or asbestos If
desired two concentric centrifuge baskets may be provided and the said fibrous material filled into the
space therebetween to form a jacket of filter material 75 Alternatively a filter cloth or filter paper may
be arranged to line the centrifuge baskets.
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An interesting application of the invention in practice is the extraction of maize oil 80 from mielie
(maize) germ meal This meal is a by-product of milling of maize for the production of samp (hulled
Indian corn), and usually contains about 10 to 14 per cent of fatty oil by weight, say about 12 per 85
cent on an average It was hitherto not considered economic to extract fatty oil from this material, as the
material is too poor in fatty oil and too inconvenient to process according to conventional methods 90
because of the high content of fines For the production of maize oil, maize germs as pure as possible
were hitherto taken as the initial material.
It was therefore surprising that by treat 95 ing mielie (maize) germ meal, containing 13.3 per cent by
weight of fatty oil in various batches in basket centrifuges with miscellae obtained in previous
extractions of step-wise decreasing concentration of ex 100 tracted fatty oil dissolved in n-hexane and
finally with clean n-hexane, on an average with an over-all of 30 to 35 per cent by weight of n-hexane
calculated on mielie germ meal about 12 5 per cent by weight of maize 105 oil was extracted Further a
residue containing only 0 8 per cent by weight of fatty oil (based on the weight of the original meal)
and substantially all of the original protein, admirably suitable as an animal feed e g, 110 as a pig feed
was obtained.
The residue contained on an average approximately 20 per cent by weight of solvent (based on the
weight of the residue).
which was recoverable with little expendi 115 ture of heat The miscella obtained direct by extraction
contained approximately 50 per cent by volume of maize oil from which the solvent was recoverable
direct in a stripper without having recourse to evaporators 120 Like results are obtained with soy bean
meal.
The following numbered examples are by way of illustration and not of limitation.
since the general principles are applicable 125 to the various solids to be extracted and solvents
employed in the process.
EXAMPLE I pounds of corn germ meal are treated in a five-stage extraction with normal hexane 130
707,385 as follows: The corn germ meal is placed in a perforated centrifuge basket operating at a
centrifugal force of 1 500 times gravity.
and is sprayed with 3 5 pounds of miscelia having a concentration ot 33 per cent oil by weight in
normal hexane said miscella being that obtained in the second stage treatment of a previous similar
extraction of corn germ meal from the same source The original corn germ meal contained 12 per cent
by weight i e, 1 2 pounds of oil The treatment in this first stage is continued by recycling of miscella if
necessary, through the meal in the centrifuge basket, until the concentration of oil in the miscella is
raised to at least 50 per cent by weight or 42 3 per cent by volume After final separation of this
concentrated miscella from the corn germ meal, the meal is similarly contacted in a second stage
treatment with 3 pounds of miscella this miscella being that obtained from the third stage treatment of
said previous extraction, and having an oil concentration of 19 4 per cent by weight This second stage
treatment is continued, if necessary, until the concentration of the oil in the miscella is raised to 33 per
cent by weight.
After final separation of the latter miscella from the corn germ meal the meal is similarly contacted in
a third stage treatment with 2 7 pounds of miscella, this miscella being that obtained from the fourth
stage treatment of said previous extraction and having an oil concentration of 9 6 per cent by weight
This third stage treatment is continued, if necessary until the oil concentration of the miscella is raised
to 19 4 per cent by weight After final separation of the latter miscella from the corn germ meal, the
meal is similarly contacted in a fourth stage treatment with 2 4 pounds of miscella, this miscella being
that obtained from the fifth stage treatment of said previous extraction and having an oil concentration
of 3 4 per cent by weight This fourth stage treatment is continued, if necessary, until the oil
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concentration of the miscella is raised to 9 6 per cent by weight After final separation of the latter
miscella from the corn germ meal, the meal is similarly contacted in a fifth stage treatment with 2 23
pounds of fresh normal hexane and this fifth stage treatment is continued, if necessary, until a miscella
having an oil concentration of 3 4 per cent by weight is obtained.
As above pointed out the above-mentioned fresh meal fed to the process contained 1 2 pounds of oil In
this illustrative example thile meal after the first stage treatment still contains 1 2 pounds of oil, and
also contains 1 2 pounds of hexane The meal after the second state treatment contains 63 pounds of oil
and 1 3 pounds of hexane The fmeal after the third stage treatment contains 3 pounds of oil and 1 25
pounds of hexane The meal alter tie fourth stage treatment contains 12 pounds of oil and 1 15 pounds
ot iexane The final exhausted meal from the fifth stage treatment contains only O 037 pounds of oil and
701.06 pounds of hexane.
The foregoing illustrative extraction is the result of feeding 10 pounds of fresh meal to the first stage
and 2 23 pounds of fresh normal hexane to the fifth stage and advanc 75 ing by one stage each the
respective miscellae of a similar previous extraction with the miscella from the first stage of said
previous extraction going to solvent recovery.
Of the 2 23 pounds of fresh hexane fed to SO the fifth stage the equivalent of 1 06 pounds of this
hexane is left in the spent meal leaving 1 17 pounds of hexane (neglecting unavoidable losses) which
hexane finally leaves the process in the highest concentrated mis 85 cella as the result of the fourth
subsequent extraction Thus the solvent to oil ratio is 1.17 to 1 2 by weight or substantially 1:1 bv
weight The volume ratio of solvent to oil is approximately 1 33 to 1 90 EXAMPLE II pounds of soya
bean meal are treated in a four-stage extraction with normal hexane as follows: The soya bean meal is
placed in a perforated centrifuge basket op 95 erating at a centrifugal force of 1 500 times gravity and
is sprayed with 4 6 pounds of miscella having a concentration of 28 per cent oil by weight in normal
hexane said miscella being that obtained in the second 100 stage treatment of a previous similar
extraction of sova bean meal from the same source.
The original soya bean meal contained 20 per cent by weight i e 2 0 pounds of oil.
The treatment in this first stage is continued 105 by recycling of miscella if necessary, through the
meal in the centrifuge basket, until the concentration of oil in the miscella is raised to at least 50 per
cent by weight or 42 3 per cent by volume After final 110 separation of this concentrated miscella from
the soya bean meal the meal is similarly contacted in a second stage treatment with 4 pounds of
miscella this miscella being that obtained from the third stage treatment of 115 said previous extraction
and having an oil concentration of 14 per cent by weight This second stage treatment is continued if
neces.
sarv until the concentration of the oil in the miscella is raised to 28 per cent by weight 120 After final
separation of the latter miscella from the soya bean meal the meal is similarlv contacted in a third stage
treatment with 3 7 pounds of miscella this miscella being that obtained from the fourth stage 125
treatment of said previous extraction and having an oil concentration of 5 per cent bv weight This third
stage treatment is continu Led if necessary until the oil concentration of the miscella is raised to 14 per
130 stage treatment of said previous extraction.
and having an oil concentration of 11 9 per cent by weight This second stage treatment is continued, if
necessary until the concentration of the oil in the miscella is 7 () raised to 23 5 per cent by weight After
final separation of the latter miscella from the cotton seed meal, the meal is similarly contacted in a
third stage treatment with 5.5 pounds of miscella, this miscella being 75 that obtained from the fourth
stage treatment of said previous extraction, and having an oil concentration of 4 per cent by weight.
This third stage treatment is continued, if necessary until the oil concentration of the 80 miscella is
raised to 11 9 per cent by weight.
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After final separation of the latter miscella frcm the cotton seed meal, the meal is similarly contacted
in a fourth stage treatment with 5 0 pounds of fresh normal hexane, and 85 this fourth stage treatment is
continued, if necessary, until a miscella having an oil concentration of 4 per cent by weight is obtained.
As above pointed out, the above-men 90 tioned fresh meal fed to the process contained 3 0 pounds of
oil In this illustrative example, the meal after the first stage treatment contains 1 4 pounds of oil, and
also contains 1 4 pounds of hexane The meal 95 after the second stage treatment contains 73 pounds of
cil and 2 1 pounds of hexane.
The meal after the third stage treatment contains 25 pounds of oil and 1 9 pounds of hexane The final
exhausted meal from the 100 fourth stage treatment contains only 0 08 pounds of oil and 2 0 pounds of
hexane.
The foregoing illustrative extraction is the result of feeding 10 pounds of fresh meal to the first stage,
and 5 0 pounds of fresh nor 105 mal hexane to the fourth stage, and advancing by one stage each the
respective miscellae of a similar previous extraction with the miscella from the first stage of said
previous extraction going to solvent recovery 110 Of the 5 0 pounds of fresh hexane fed to the fourth
stage the equivalent of 2 0 pounds of this hexane is left in the spent meal leaving 3.0 pounds of hexane
(neglecting unavoidable losses) which hexane finally leaves the 115 system in the highest concentrated
miscella as the result of the third subsequent extraction Thus the solvent to oil ratio is 3 0 to 3.0 by
weight or I: I by weight The volume ratio of solvent to oil is approximately 1 38 120 to 1.
The following example illustrates the use of a heavy solvent The particular solvent employed, namely
trichlorethvlene has a specific gravity of 1 46, whereas n-hexane 125 which may be considered to be
illustrative of a light solvent, has a specific gravity of 0.66.
EXAMPLE IV pounds of corn germ meal are treated 130 cent by weight After final separation of the
latter miscella from the soya bean meal, the meal is similarly contacted in a fourth stage treatment with
3 34 pounds of fresh normal hexane and this fourth stage treatment is continued, if necessary, until a
miscella having an oil concentration of 5 per cent by weight is obtained.
As above pointed out, the above-mentioned fresh meal fed to the process contained 2 pounds of oil In
this illustrative example the meal after the first stage treatment contains 1 4 pounds of oil, and also
contains 1 4 pounds of hexane The meal after the second stage treatment contains 59 pounds of oil and
1 5 pounds of hexane The meal after the third stage treatment contains 24 pounds of oil and 1 5 pounds
of hexane.
The final exhausted meal from the fourth stage treatment contains only 0 07 pounds of oil, and 1 37
pounds of hexane.
The foregoing illustrative extraction is the result of feeding 10 pounds of fresh meal to the first stage
and 3 34 pounds of fresh normal hexane to the fourth stage, and advancing by one stage each the
respective miscellae of a similar previous extraction, with the miscella from the first stage of said
previous extraction going to solvent recovery.
Of the 3 34 pounds of fresh hexane fed to the fourth stage the equivalent of 1 37 pounds of this
hexane is left in the spent meal, leaving 1 97 pounds of hexane (neglecting unavoidable losses) which
hexane finally leaves the system in the highest concentrated miscella as the result of the third
subsequent extraction Thus the solvent to oil ratio is 1 97 to 2 0 by weight, or substantially I: L by
weight The volume ratio of solvent to oil is approximately 1 37 to 1.
EXAMPLE III pounds of cotton seed meal are treated in a four-stfige extraction with normal hexane as
follows: The cotton seed meal is placed in a perforated centrifuge basket operating at a centrifugal
force of 1,500 times gravity and is sprayed with 5 7 pounds of miscella having a concentration of 23 5
per cent oil by weight in normal hexane, said miscella being that obtained in the second stage treatment
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of a previous similar extraction of cotton seed meal from the same source The original cotton seed meal
contained 30 per cent by weight, i e, 3 0 pounds of oil The treatment in this first stage is continued by
recycling of miscella, if necessary throughi the meal in the centrifuge basket until the concentration of
oil in the miscella is raised to at least 50 per cent by weight or 423 per cent by volume.
After final separation of this concentrated miscella from the cotton seed meal the meal is similarly
contacted in a second staeac treatment witlh 5 7 pounds of miscella, this miscella bein that obtained
from the third 7 U," 3 '5 in a fie-staue extraction with trichlorethylene as follows: The corn germ meal
is piaced in a perforated centrifuge basket operating at a centrifugal force of 1500 times gravity, and is
sprayed with 7 6 pounds of miscella having a concentration of 21 4 per cent oil by weight in
trichlorethylene.
said miscella behingl that obtained in the second stage treatment of a previous similar extraction of
corn germ meal from the same source The original corn germ meal contained 12 per cent by weight i e
1 2 pounds, of oil The treatment in this first stage is continued by recycling of miscella if necessary,
through the meal in the centrifuge basket until the concentration of oil in the miscella is raised to at
least 32 per cent by weight or 42 8 per cent by volume After final separation of this concentrated
miscella flom thie corn germ meal, the meal is similarly contacted in a second stage treatment with 6 5
pounds of miscella, this miscella being that obtained from the third stage treatment of said previous
extraction, and having an oil concentration of 13 0 per cent by weight This second stage treatment is
continued, if necessary, until the concentration of the oil in the miscella is raised to 21.4 per cent by
weight After final separation of the latter miscella from the corn germ meal, the meal is similarly
contacted in a third stage treatment with 5 8 pounds of miscella this miscella being that obtained from
the fourth stage treatment of said previcus extraction, and having an oil concentration of 6 7 per cent by
weight This third stage treatment is continued, if necessary until the oil concentration of the miscella is
raised to i 3 0 per cent by weight.
After final separation of the latter miscella from the corn germ meal, the meal is similarly contacted in
a fourth stage treatment with 5 2 pounds of miscella, this miscella being that obtained from the fifth
stage treatment of said previous extraction and having an oil concentration of 2 7 per cent by weight
This fourth stage treatment is continued if necessary until the oil concentration of the miscella is raised
to 6 7 per cent by weight After final separation of the latter miscella from the corn germ meal, the meal
is similarly contacted in a fifth stage treatment with 4 8 pounds of fresh trichlorethylene and this fifth
stage treatment is continued if necessary until a miscella having an oil concentration of 2 7 per cent by
weight is obtained.As above pointed out the above-mentioned fresh meal fed to the process coni tained 1 2 pounds of oil In this illustrative example the meal
after the first stage treatment contains 1 7 pounds of oil, and also contains 3 6 pounds of
trichlorethylene The meal after the second stage treatment contains 9 pounds of oil and 3 2 pounds of
trichloretih Lvlen fhe meal after the third 'age treatment contains 44 pounds of oil and 3 0 pounds of
trichlorethylene The meal after the fourth stage treatment contains 19 pounds oif oil and 2 6 pounds of
70 trichlorethylene The final exhausted meal from the fifth stage treatment contains only 0.06 pounds
of oil and 2 4 pounds of trichloreth N lene.
The foregoing illustrative extraction is the 75 result of feeding 10 pounds of fresh meal to the first
stage, and 4 8 pounds of fresh trichlorethylene to the fifth stage and advancing by one stage each the
respective miscellae of a similar previous extraction with the mis So O cella from the first stage of said
previous extraction going to solvent recoverx Of the 4.8 pounds of fresh trichlorethylene fed to the fifth
stage, the equivalent ot 2 4 pounds of this trichlorethvlene is left in the spent 85 meal leaving 2 4
pounds of trichlorethylene (neglecting unavoidable losses) which trichlorethylene finally leaves the
systemn in the highest concentrated mniscella as the result of the fourth subsequent extraction Thus 90
the solvent to oil ratio is 2 4 to 1 2 by weight, or substantially 2:1 by weight The volume ratio of
solvent to oil is approximately 1 26 to 1.
The following example illustrates the use 95 of vacuum filtration.
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EXAMPL E V pounds of corn germ meal are treated in a seven-state extractien with normal hexane as
follows: The cern germ meal is dis 10)U posed in a bed in a vacuum filter and is sprayed with 5 pounds
of miscella having a concentration of 37 per cent oil by weight in normal hexane said miscella being
that obtained in the second stage treatment of a 105 previous similar extraction of corn germ meal from
the same source The original corn germ meal contained 13 per cent bv weight i e 1 3 pounds of oil A
vacuum of 500 inm of mercury is applied to the 110 underside of the bed of meal on the filter and the
miscella sucked through The treatment in this first stage yields a miscella having a concentration of oil
of 50 per cent by weight or 42 3 per cent by volume After 115 final separation of this concentrated
miscella from the corn germ meal the meal is similarly contacted under vacuum in a second stage
treatment with 4 6 pounds of nmiscella this miscella being that obtained 120 from the third stage
treatment of said previous extraction, and haxing an oil concentration of 26 3 per cent by weight This
second stage treatment X ields a miscella having a concentration of 37 per cent by weight 125 of oil
After tinal separation of the latter miscella from the corn germ meal, the menal is similarly contacted
under vacuum in a third stage treatment with 4 3 pounds of mniscella this miscella being that obtained
1 O from i'e fourth stage treaticnt o' said pr C tioa _oiicti L Ions and particular batches of LIIC atcl s L
vious extraction, and having an oil concen meal from particular sources ani generally tration of 17 5
per cent by weight This illustrate the practice of thile inxention The third stage treatment yields a
misceila hay extraction of solids from various animal or in>; an oil concentration ot 26 3 per cent by
vegetable sources under various conditions 70 weight After final separation of the latter according to
the stepwise operation of the miscella from the corn germ meal thile meal invention requires onr the
part of the operais similarly contacted under vacuum in a tor a determnination of the per cent of
solfourth state treatment with 4 2 pounds of vent retained by the particular solids under misceila this
miscella being that obtained the particulatr employed conditions of sorar 75 from the ifth stage
treatment of said pre ation of exhausted solids in the las T stage of vious extraction and having an oil
concentra the process or under sinlulated conditions.
tion of 10 8 per cent by weight This fourth so that a solvent to solute ratio bx volume stage treatment
yields a misceila having an as hereinbefore defined of not re:l \ exoil concentration of 17 5 per cent by
weight ceeding 1 5 to 1 may be chosen since this 80 After final separation of the latter miscella ratio as
above pointed out excludes that from the corn germ meal the meal is simi solvent W O hich is retained
by the exhausted larly contacted under vacuum in a fifth stage meal after separation of miscella
therefrom.
treatment with 4 0 pounds of miscella this To obtain a final mniscella of at least 40 per miscella being
that obtained from thile sixth cent solute content by volume it is merely 85 stage treatment of said
previous extraction necessary to choose at least the minimum and having an oil concentration of 5 7 per
requisite number of stages of treatment for cent by weight This fifth stage treatment this purpose all of
which will be well underyields a miscella having an oil concentra stood by persons skilled in the art.
tion of 10 8 per cent bv weight After final The expression "solids " when herein em 90 separation of
the latter miscella from the pioned includes pulps.
corn germ meal the meal is similarly con The nature of the invention and how it tacted under vacuum
in a sixth stage treat may be carried out in practice w-ill be furment with 3 9 pounds of miscella this
mis ther illustrated by way of example with recella being that obtained from the seventh ferenee to the
accompanying flow-sheet 95 stage treatment of said previous extraction, which illustrates by way of
example the layand having an oil concentration of 2 per cent out of a plant in accordance with the
invenby weight This sixth stage treatment yields tion It should be understood that the ina rniscella
having an oil concentration of vention is not limited to the examnples given.
5 7 per cent by weight After final separa Referring to the flow-sheet solid material 100 tion of the
latter miscella from the corn germ canable of extraction is contained in the meal, the meal is similarly
contacted under storage bin or hopper I N Material requiring vacuum in a seventh stage with 3 9
pounds comnminution such as beans kernels or nuts.
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of fresh normal hexane This seventh stage is rassed from the storaae bin 1 by xlax of treatment yields
a misceila having an oil the duct 2 to cracking rollers 3 whicha reduce 105 concentration of 2 per cent
by weight Thile it to a suitable size If the solid material is final exhausted meal from the seventh stage
already in a form suitable for extraction as treatment contains only O 085 pounds of oil in the case of
certain meals it is passed and 3 62 pounds of hexane through by-pass 4 to pipe 5 leadlng direct Thile
foregoing illustrative extraction is the to the extraction units The comminuted 110 result of feeding 10
pounds of fresh meal to material from the cracking rollers 3 is in the first stage and 3 9 pounds of fresh
nor view of the flexibility of the present new mal hexane to the seventh stage and ad process with
regard to the initial ma:erial.
vancing by one stage each the respective usually directly suitable for centrifugal solmiscellae of a
similar previous extraction, vent extraction in accordance with the ne 115 with the niscella from the
first stage of said sent invention and is therefore passedi previous extraction Poing to solvent re through
duct 6 to pipe 5 leading to tne excovery Of the 3 9 pounds of fresh hexane traction unit Where
necessary suitable fed to the seventh stage the equivalent of units for pretreatment of the mazeri- fromn
2 62 pounds of this hexane is left in the spent rollers 3 may be provided as for example a 120 meal,
leaving 1 28 pounds of hexane dehulline unit a conditioner and fl,king rol(neglecting unavoidable
losses) which hexane ler- not shown on the flow-sheet The solid finally leaves the system in the hichest
con material to be extracted passes from pire 5 centrated miscella as the result of the sixth into the
loading device 7 from xihichl, it subsequent extraction Thus the solvent to passes into the basket of the
centrifugal sol 125 oil ratio is 1 28 to 1 3 by weight, or sub vent extractor S which latter is preferably
slantially 1:1 by weight The volume ratio constructed gas-tight to avoid loss of solof solvent to oil is
approximately 1 36 to 1 vent Fresh solvent is contained in the solIt will be understood that the
foregoing vent tank 0, whereas concentrated miscella examples are based upon particular opera is
contained in tank 10 The tanks 10 I Oa 130 707,Vq 5 707,385 lo O b and 10 c contain nilscella in
decreasing order of concentration tronm hich the various misccllae can be taken off b thile pipes 11 Ila
11117 and Hlc respectixely which are controlled by thile respectixe takles 13 13 a, 13 b and 13 c to thie
soilent injector in the centrifugal extractor S i hich injector usuall\ has the form of a srpra.
In starting the operation concentrated miscella from tank 10 I is passed through pipe 11 and valve 13
(t hich is now open while valves 1 a 13 b l 3 C and 14 are kept closed) to the solvent injector in thile
extractor 8.
where it passes through the solid in the basket and extracts extractable matter e a oil therefrom.
Any centrifugal force suitable to the circumstances may be emnployed Good results have for example
been obtained with centrifu al torces between about 600 g and 1.500 g.
The miscella thus obtained passes from the centrifuge through pipe 15 and is pumped by means of
pump io and pipe 17 to thile manifold 18 from which the valve controlled connections l O 19 a 19 b 19
c and 20 lead to the tanks 10 10 a lob, 10 c and 9 respectively At this stage the valve connection 19 is
open whereas the valve controlled connections I 9 a to 20 are closed.
When the requisite amount of concentrated miscella has been circulated through the centrifuge until
further extraction at this concentration is no longer considered economical valves 13 and 19 are closed
and valves 13 a and 19 a are opened thus admitting a miscella of lesser concentration from tank 10 a to
the centrifuge S and the circulatin, svstem.
This is repeated by successively circulating miscellae of lesser concentration through the solid
undergoine extraction in centrifuge S until finally clean soltent from tank 9 is circulated via pipre 12
valve 14, centrifuge 8 line 15 pump 16 pipe 17, manifold 18 and val Ne-controlled connection 20.
Finally valve 14 is closed and the centrifuge run until miscella is expelled as far as possible usually
down to a content of 10 per cent or even q per cent or less With solvents of lower density e g n-hexane
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the solvent to oil weliht ratio (ratio by weight of solvent to oil content of feed solids) employed is
usually 1:1 or less.
With solvents of higher denstv e trichlorethylene the solvent to oil weight ratio employed is usually
somexwhat higher eg.
2:1 How exer in any case the solvent to solute ratio by volume is not substantially greater than 1 5:1
and is usually less e g 1.4:1 or less.
The control of the valves may be automatic.
The miscella in tank 10 is now so concentrated that it is rassed o:reoo b; way of pipe 2 S to tile
exaporatar tower 37.
Extracted meal is removed from the centrifuec Basket by a knife or other suitable means and passed
tia duct 24 into the extracted meal bin 25 and thence for the re 70 coverv of the solvent contained
therein by duct 26 to the meal drier 27 which mav be of ant suitable construction and operation.
For example meal drier 27 may be steam jacketted and live steam may be injected 75 through pipe 2 S
for passage through the drier 27 counter-currently to the meal which is conx eed therethrough by
screw-conve ors '2 o and finally discharged at 29 a.
Solvent vapors and steam issue from the 80 drier at 50 and 31 and are passed through pipe 32 to the
condenser 33 whence the condensed liquids are passed through pipe 34 into the water and solvent
separation tank 35 wherein water and solvent are sep 85 arated by layer formation Thence the
recovered solvent mav be fed to fresh solvent tank 9 by means of pump 36 and pipe 22.
Any other means of solvent separation may be employed such as distillation par 90 ticularlv Ehen the
solvent has an appreciable solubility in water.
As shown concentrated miscella is passed by means of pipe 23 into the top of the falling film
evaporator tower 37 in which it is 95 passed in counter-current to live steam introduced at the bottom
of the tower from pipe 38 The miscella issuing from the bottom of tower 37 is passed by pipe 39 to the
top of the vacuum stripping column 40 into the 100 bottom of which live steam is introduced from pipe
41 The bottom of column 40 may be steam-jacketted.
The extract e fatty oil which has thus been completely freed from solvent is with 105 drawn from the
bottom of the column 40 to storage through pipe 43.
Solvent vapor and steam are withdrawn from the tep of columns 37 and 40 through pipes 44 and 45
respectively into pipe 46 110 to condenser 47.
The vacuum producing equipment is indicated at 48 and may be of any type desired such as a wet
vacuum pump The solvent and water thus condensed are passed 115 by way of pipe 40 to the water and
solvent separation tank 35 As previously pointed out any other means for the separation of water and
solvent such as distillation may be employed Likewise any other means 120 for the recovery of solvent
from the miscella and or from the meal may be employed without departing from the spirit of the
invention.
l Heat exchange and other equipment may 125 be installed in the solvent recovery plant.
as required or desired.
After the draining of miscella from tank the miscella in tank 10,t is transferred to tank 10 such as by a
pump (not shown) 130 7 it 7, 3 5 This is followed by the transfer of the miscella in tank 10 b to tank 10
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a then by the transfer of the miscella in tank 10 c to tank O 10 b, and then by the transfer of the
miscella in tank 9 to tank 10 c such as by suitable pumps (not shown) Fresh solvent is then introduced
from supply pipe 21 and pipe 22 into tank 9 A fresh charge of solid material to be extracted is placed in
centrifuge 8.
whereupon the above-described cycle of operations is repeated.
Alternatively after the draining of miscella from tank 10 and the placing of a fresh charge of solid
material to be extracted in the centrifuge 8 the miscella in tank 10 a is passed to tank 10 through
centrifuge 8 by opening valves 13 a and 19.
whereupon if it is desired to continue the extraction at this stage, valve 13 a is closed and valve 13
opened so that the miscella in tank 10 may be passed as many times as desired through the charge in
the revolving centrifuge 8 and back to tank 10 in the manner already described.
After the extraction at this stage is carried on to the extent desired, valves 13 and 19 are closed and
valves 13 b and 19 a are opened, whereupon the miscella in tank 10 b is passed through centrifuge 8 to
tank 10 a.
When this has been completed valve 13/ is closed, and if it is desired to continue the extraction at this
stage, valve 13 a is opened.
and the miscella now in tank 10 a is passed as many times as desired through centrifuge 8, and back to
tank O la in the manner already described.
After the extraction at this latter stage is carried on to the extent desired, valves 13 a and 19 a are
closed and valves 13 c and 19 b are opened, so as to pass the miscella from tank 10 c to tank 10 b via
centrifuge 8, and the charge contained therein When this has been completed valve 13 c is closed, and
if it is desired to continue the extraction at this stage valve 13 b is opened and the miscella now in tank
10 b is passed as many times as desired through centrifuge 8 and back to tank O lb, in the manner
already described.
After the extraction at this latter stage is carried on to the extent desired valves 13/, and 19 b are
closed and valves 14 and 19 c are opened whereupon the miscella in tank 9 is passed to tank 10 c
through centrifuge 8 When this transfer of miscella has been completed valve 14 is closed and if
desired.
extraction at this stage may be continued by opening valve 13 c so as to pass as many times as desired
the miscella now in tank 10 c thlrough centrifuge 8 and back to tank c in the manner already described.
When extraction at this latter stage has been carried on to the extent desired valves 13 c and 1 Oc are
closed and fresh solvent is charged to tank 4 from solvent supply line 21 Valves 14 and 20 are now
opened to effect the last stage of the extraction by passing as many times as desired the solx ent in tank
9 through centrifuge S and back to tank 9 to produce miscella of the 70 lowest concentration in the
process.
Atter this has been completed the miscelia is drained from tank 10, and passed to solvent recovery as
already described Likewise the exhausted charge in centrifuge S is 75 removed and passed to solvent
recovery as already described.
Thereupon with the placing of a fresh charge in centrifuge 8, the above cycle of operations are
repeated So Likewise any other number of stages of extraction may be employed, such as 2 3 4.
6 7 8 or more, as desired without departing from the spirit of the invention.
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While we have particularly described our 85 invention for purposes of illustration in connection with
a single centrifuge it will be obvious to persons skilled in the art that any desired number of centrifuges
may be emploxed following the principle of succes go 90 sively extracting with miscella of
progressively decreasing oil concentration and with ratios of solvent to solute concentration in the
original charge as described and whether any individual charge of solids re 95 mains in a single
centrifuge throughout the extraction or progresses from centrifuge to centrifuge in any desired manner
during the extraction or otherwise However we preter to operate in a manner such that any o 100
original charge of solids to a centrifuge remains in that centrifuge throughout the extraction.
While hereinabove we have referred to mixing the solid to be extracted with sol 105 vent for transport
into the centrifuge e g in the form of a pumpable slurry we prefer when following the principle of
successivelv extracting with miscella of progressivelv decreasing fatty oil concentration I 10 (and
finally with fresh solvent) to transport the fresh charge of solid to be extracted into the centrifuge in the
form of a mixture (e g a slurry) with miscella of highest fatty oil content produced in practising the
process 115 Thus miscella from tank 10 may be used for this purpose prior to passing it to the
evaporator towver 37 or to other solvent recoverv processing provided that its volume is permitted to
build up in tank 10 as the 120 result of successive extractions in order to provide sufficient liquid for
this purpose.
The miscella is then separated from the charged mass by centrifuging and may be returned to tank 10
by opening valve 19 A 125 portion only of the contents of tank 10 e o_ equivalent in volume to the
final miscella produced during a single extraction may then be sent to solvent recovery as above
described in order to maintain in tank 10 130 707,385 sulticient liquid for subsequent slurrsing
purposes On tile other hand and if desired.
this portion may be withdrawn from tank prior to such slurrying procedure provided sufficient
miscella is left in tank 10 to accomplish the desired purpose It will be understood that the miscella
employed for slurrying purposes may be kept in a tank separate from tank 10 and returned thereto upon
separation from the charged mass, in which case, if desired, the final miscella from tank 10 may be
transferred to such separate tank, and the portion of concentrated miscella going to solvent recovery
may be removed from such separate tank.
Tanks 10 10 a 10 b, 10 c and 9, or their equivalent and irrespective of number, may be of any desired
or convenient size The miscella of the respective concentration present in any particular tank may be of
any desired quantity, e g, the quantity advanced to the particular tank during or subsequent to
extraction with miscella of next lower concentration, or more In any event, the final miscella which is
produced by the extraction and which is withdrawn from tank 10, or its equivalent, should be of at least
the minimum solute content set forth herein to obtain the benefits of observing a relatively low ratio of
fresh solvent to the solute content of the original solids charged to centrifuge 8, as defined herein, and
this same principle is preferably observed in charging fresh solvent to tank 9, or its equivalent, and in
advancing miscella from stage to stage in the series.
In other words, the miscella in any one or more of the respective tanks may be permitted to build up
somewhat from previous extractions, if desired for any reason, and likewise miscella of the respective
concentration may be added to any one or more of these tanks, without departing from the spirit of the
invention For example tank 4510 may contain a reserve of niscella to be used for slurrying purposes in
charging solids to be extracted to the centrifuge 8, since liquid considerably in excess of that produced
by a single extraction is required for this purpose.
A number of centrifugal solvent extractors may be employed simultaneously Thus a second
centrifugal solvent extractor 8 ' with its loading device 7 ' and its series of tanks ending in tanks 9 ' and
10 ', is shown in the flow sheet in dotted lines.
The term "particles " as used in the claims is intended to include whole seeds, pulverized, flaked or
comminuted seeds.
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disintegrated or comminuted fish whale, or other fatty oil-containing solids of the animal class.
Also for convenience where reference is made in the claims to the use of iniscella as the extracting
inedium the term "iniscella " is intended to include fresn solvent as well as solvent having fatty oil fat
and, or wax in solution.Data supplied from the esp@cenet database - Worldwide
Claims:
Claims of GB707385
W;hat we claim is:1 A process for the extraction by means 70 of an organic solvent of at least one of the group
consisting of fatty oil, fat and wax from particles of solid matter of biological origin as herein defined
characterized in that the solvent to solute ratio by volume 75 as herein defined is low i e not
substantially greater than 1 5 to 1 I to produce a miscella of at least 40 per cent solute content by
volume.
2 The process of Claim 1 characterized 80 in that the solid matter is subjected to extraction in stepxxise manner with miscelle as herein defined of progressively decreasing solute content.
3 The process of Claim 2 characterized 85 in that the solid matter is maintained in a bed through
which the misceila is passed.
4 The process of Claim 3 characterized in that the bed is disposed in a revolving centrifuge basket to
assist in passing the 90 miscella through said bed and to assist in separating said miscella fronm said
bed.
The process of Claim 3 characterized in that the solid matter is vegetable matter containing fatty oil,
fat or wax 95 6 The process of Claim 5 characterized in that the solid matter is in the form of seeds
beans, or nuts.
7 The process of Claim 5 characterized in that the vegetable matter is pulverized or 100 flaked.
8 The process of either of Claims 6 or 7, characterized in that vegetable matter is cotton seed soya
bean linseed, sunflower seed, peanut corn germ or sesame seed 105 9 The process of Claim 3
characterized in that the solid matter is whale meal or fish meal.
The process of Claim 3 characterized in that the solid matter is transported to the 110 bed in the form
of a slurry with miscella of at least approximately 40 per cent solute content by volume.
11 The process of Claim 10 characterized in that the bed is formed from the 115 slurry in a revolving
centrifuge basket.
12 The process of an% of the preceding claims, characterized in that thile solvent to solute ratio by
volume as herein defined is sulfficiently low as not to exceed 1 4 to 1 120 13 The process of any of the
preceding claims, characterized in that the solvent employed is hexane.
14 The process of an\ of the preceding claims, characterized in thiat fibrous material 125 is admixed
with the material to be extracted.
so as to facilitate the separation of miscella from residue.
The process of anx of the preceding claims, characterized in that the liquid is 130 707,3 & 5 11 passed
in closed circulation through the before described.
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solid matter.
16 The process according to Claim 1, STEVENS, LANGNER, substantially as hereinbefore described
PARRY & ROLLINSON, 17 Apparatus for carrying out the pro Chartered Patent Agents, cess of
Claim 16, substantially as herein Agents for the Applicants.
Printed for Her Majesty's Stationery Office by Wickes & Andrews, Ltd, E C 4 391244 -1954.
Published at The Patent Office, 25, Southampton Buildings London, W C 2, from which copies may
be obtained.Data supplied from the esp@cenet database - Worldwide
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26. GB736134 - 31/8/1955
IMPROVEMENTS IN OR RELATING TO THE TREATMENT OF PALM OIL
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=GB736134
Applicant(s):
STANDARD OIL CO (--)
IP Class 4 Digits: B01D
IP Class:B01D17/00
E Class: A61K31/595; B01D17/00B
Application Number:
GB19530027705 (19531008)
Priority Number: USX736134 (19521031)
Family: GB736134
Abstract:
Abstract of GB736134
Concentration of carotene in palm oil is effected by forming a thin film of palm oil defined by opposed
surfaces of heat-conductive inert material closely and substantially uniformly spaced from 0.01 to 0.15
inch apart, maintaining a temperature gradient across the film of oil, and accumulating and
withdrawing from the film a carotene-enriched fraction concentrated by thermal diffusion adjacent to
the cooler surface. A lighter coloured fraction may be simultaneously withdrawn from adjacent to the
hotter surface, advantageously at more than ten times the rate of withdrawal of the carotene-enriched
fraction. Preferably the palm oil is previously dehydrated and has added to it an inert viscosityreducing agent and an antioxidant, though some antioxidant effect is in any case produced by
tocophenols which accumulate with the carotene adjacent to the cooler surface. Examples illustrate the
various features of the invention, employing film thicknesses varying from 0.019 to 0.044 inch, and
using in some cases chlorobenzene as diluent or rice bran extract as antioxidant.ALSO:Palm oil
impoverished in carotene and therefore lighter in colour than the starting material is obtained by
forming a thin film of crude palm oil defined by opposed surfaces of heat-conductive inert material
closely and substantially uniformly spaced from 0.01 to 0.15 inch apart, maintaining a temperature
gradient across the film of oil, and accumulating and withdrawing from the film the lighter-coloured
fraction concentrated by thermal diffusion adjacent to the hotter surface. Preferably the palm oil is
dehydrated before treatment.ALSO:Butter and margarine are coloured, and their Vitamin A content
increased, by adding thereto a carotene-enriched fraction obtained from palm oil by a thermal diffusion
process (see Group IV (b)).ALSO:As a colouring for butter and margarine is employed a caroteneenriched fraction obtained from palm oil by a thermal diffusion process (see Group IV (b)).Description:
Description of GB736134
COMPLETE SPECIFICATION
Improvements in or relating to the Treatment of Palm Oil
We, THE STANDARD OIL COMPANY, a corporation organised under the laws of the
State of Ohio, United States of America, of
Midland Building, Cleveland 15, Ohio,
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United States of America, do hereby declare the invention, for which we pray that a patent may be
granted to us, and the method by which it is to be performed, to be particularly described in and by
thefollowing statement:The present invention relates to a method of concentrating carotene in palm oil and provides a method
of resolving palm oil by thermal diffusion into two fractions, one of which is enriched in carotene,
contains a lower percentage of fatty acids than contained in the initial palm oil and has increased
stability against oxidation, and the other of which is lighter in colour.
Among the various vegetable oils that are available, palm oil is unique in containing an amount of
carotene that is relatively large as compared with the carotene content of other vegetable oils. The
concentration of carotene in palm oil usually varies between about 0.05 and0.2(1% and it is this
relatively large amount of carotene that is believed to be responsible for the deep orange-red colouring
of crude palm oil.
Carotene, which term as used herein idudes alpha-, beta-, and gamma- carotene, is a pro-vitamin A,
being converted into vitamin
A by a splitting of the carotene molecule.
Palm oil contains traces of tocopherols, also known as vitamin E. It is believed that the tocopherols in
palm oil act as anti-oxidants and as such inhibit to a certain extent the oxidation of the carotene and
other ingredients. Depending upon the geographical origin of the palm fruits from which it is extracted
and the procedure used in extraction, palm oil contains as little as 3% and as much as45% by weight of
free fatty acids. The presence of free fatty acids in palm oil is objectionable because of their relative
instability to heat and oxidation.
At present the extraction of carotene from palm oil is carried out by saponifying the crude palm oil
with sodium hydroxide or potassium hydroxide and then extracting the resulting soap with
ethylenedichloride. While approximately95 % carotene recovery is obtained by this method, the
extremely large bulk of palm oil that must be processed to obtain a small amount of carotene, e.g.,
approximately a thousand pounds of palm oil must be handled and separated from the solvent by
centrifuges to obtain a pound of carotene, makes the present method an extremely expensive one and
results in a correspondingly high price for concentrated carotene. In addition the oil is useless for food
and other purposes for which the oil is desirable.
It is recoverable only as a soap which greatly limits the use of the bulk of the oil.
It has now been found that a preliminary concentration of the carotene in palm oil can be obtained by
subjecting thecrude palm oil to liquid thermal diffusion and that, surprisingly, in effecting such
concentration the desirable tocopherols are retained with the carotene-enriched fraction and the
concentration of the undesirable free fatty acids is considerably reduced.
Liquid thermal diffusion, as is well-known in the art, consists essentially in forming a thin film of
liquid confined by closely-spaced, mutually parallel and opposed surfaces of heat-conductive material
that is inert to the liquid and its components, heating one or both the surfaces to maintain a temperature
gradient across the film and accumulating and withdrawing from the film two dissimilar fractions, one
fraction being concentrated by thermal diffusion adjacent to the cooler of the two surfaces and the other
fraction being concentrated by thermal diffusion adjacent to the hotter of the two surfaces.
It has been found that a fraction enriched in carotene and impoverished in free fatty acids becomes
concentrated adjacent to the cooler surfaces by thermal diffusion.
The film must be thin enough to permit the thermal diffusive forces to effect the separation, and the
temperature gradient and withdrawal rates must be related to the film dimensions to permit the desired
degree of separation. Film thicknessesbetween 0.01 and 0.15 inch, preferably between about 0.01 and
0.06 inch, are necessary from the standpoint of being thin enough to make effective use of the thermal
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diffusive forces and thick enough to make possible the accumulation of the separated fractions in
different portionsof-the slit.
The method of this invention comprises the steps of forming a thin film of palm oil defined by
opposed surfaces of heat-conductive, inert material, such as glass, stainless steel or aluminium, said
surfaces being closely and substantially uniformly spaced apart between 0.01 and 0.15 inch,
maintaining a temperature gradient across the film so formed, and accumulating and withdrawing from
the film of oil a carotene-enriched fraction concentrated by thermal diffusion adjacent to the cooler
surface.
It will be apparent that the method of this invention has a number of important advantages, among
which are a considerable reduction in the bulk of oil that must be handled to extract carotene by the
conventional solvent extraction method, a corresponding increase in the capacity of existing solvent
extraction equipment, and an increased stability against oxidation of the oil subjected to solvent
extraction by virtue of the lower content of free fatty acids and the presence, probably in increased
concentration, of tocopherols. In addition, the oil from which the carotene is separated is useful as oil
and available for purposes for which the soap is not suitable.
For many industrial applications the suitability of palm oil is considered to be dependent upon its
colour. The lighter oils containing a minimum concentration of carotene are considered more desirable
than the darker oils having a higher carotene content because the latter require more severe refining and
bleaching. This preference for the lighter coloured oils is reflected in the market by the higher prices of
the light coloured oils as compared with those at which the darker oils are quoted.
Inasmuch as the present invention is concerned primarily with the concentration of carotene, it is of
advantage to utilise the "lower grades" of darker coloured palm oils as source material for carotene. An
important ancillary advantage of the method of the invention is that the carotene-impoverished fraction
obtainable by this method is lighter in colour than the initial oil and possesses all the qualifications of
the lighter crude palm oils that command higher prices in the market. Thus, the method of the invention
is useful not only in the concentration of the carotene content in palm oil, but also in converting the
palm oil into a lighter coloured oil for which there is greater demand in the market than the initial and
comparatively dark palm oil.
It is also to be understood that the caroteneenriched product obtainable by the method of this invention
is suitable for use in purposes other than the conventional solvent extraction methods utilised in
obtaining highly concentrated carotene. Thus, for example, the carotene-enriched fraction is
particularly useful as a natural vegetable colouring for addition to butter, margarine and the like, while
at the same time increasing the vitamin A content of such products.
The thermal diffusion of palm oil according to this invention may be carried - out in a number of ways.
One such way is to fill a vertical slit formed by closely-spaced, mutually parallel and opposed surfaces
spaced apart between 0.01 and 0.15 inch with the crude palm oil, maintaining a temperature gradient
across the slit until the liquid has separated into an upper light-coloured fraction and a lower darker
fraction and then removing the lower fraction which is enriched in carotene and impoverished in fatty
acids.
Another method is substantially similar except that the crude palm oil is more or less continuously
introduced into the slit at any ,point therein and light and dark coloured fractions are more or less
continuously removed from the top and the bottom, respectively, of the slit.
A third method is to introduce the crude liquid palm oil continuously or intermittently at one point or
area in a thermal diffusion slit between 0.01 and 0.15 inch in width, the hot surface being above the
cold surface if the slit is other than vertical, and continuously or intermittently removing, at points or
areas remote from the point or area of introduction, light and dark coloured fractions from adjacent to
the hot and cold surfaces, respectively, or alternatively, removing the dark fraction at one end of the slit
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from adjacent to the cold surface and removing the light coloured fraction from adjacent to the hot
surface at the other end of the slit.
These modifications all have in common the step of subjecting a thin film of the crude palm oil to a
temperature gradient so that the thermal diffusive forces will operate to concentrate dissimilar fractions
adjacent to the hot and cold surfaces and the further step of accumulating and then withdrawing the
fractions so concentrated. For optimum results, it is desirable either or both to add an inert and easily
separable material, such as chlorobenzene, for reducing the viscosity of the liquid in the slit and to
dehydrate the palm oil before subjecting it to thermal diffusion.
The temperature of the hot and cold walls may vary widely so long as that of the hot wall is not so
high as to equal the temperature at which carotene decomposes under the conditions of thermal
diffusion, bearing in mind the residence time of the palm oil and its components and presence of a
residual anti-oxidant such as tocopherol, or of an added anti-oxidant, and the temperature of the cold
wall is not so low as to equal the congealing temperature of the oil or cause an appreciable increase in
its viscosity. Hot wall temperatures as high as about300 F. and cold wall temperatures as low as
about105 F. are preferred. Higher hot wall temperatures may be employed if anti-oxidant is present in
amounts sufficient to avoid oxidation of the carotene at such higher temperatures, especially if the
residence time of the carotene in the apparatus is relatively short. The extent of separation within the
permissible range is a function of the temperature gradient.
It is advantageous, in order to obtain acaroteneenriched fraction of maximum concentration, to reduce
the rate of withdrawal of said fraction to a small percentage of the rate of withdrawal of the caroteneimpoverished fraction. This may be accomplished in apparatus wherein the crude palm oil is introduced
at a point or area between the ends of the column and the two fractions are withdrawn at opposite ends
and is particularly effective in counter-current and concurrent end feed methods i,e. where the palm oil
is introduced at one point or area in the column and the carotene-enriched fraction is withdrawn at a
considerably lower rate, at a remote point or area from adjacent to the cold wall. The ratio of
withdrawal rates may desirably be as low as 1/10, 1/20 or even lower and if desired the larger volume
of caroteneimpoverished fraction may be re-subjected to continuous thermal diffusion in one or more
subsequent thermal diffusion columns.
Inasmuch as crude palm oil frequently contains some water, usually less than1%, and the presence of
such water reduces the efficiency of the process, it is desirable to dry the palm oil before it is subjected
to thermal diffusion. It is necessary, when operating the method of the invention in a continuous
manner, to introduce the crude palm oil into the thermal diffusion apparatus in a fluid and not too
viscous condition. To this end, it may be necessary to pre-heat the palm oil to a temperature of the
order of about110"F., the exact temperature depending upon the congealing temperature of the
particular palm oiL
The following examples illustrate the invention:
EXAMPLE 1.
An annular slit having a volume of approximately 50 cc., a slit width of 0.043 inch and a height of 8
feet, formed by two concentric glass tubes, was filled with crude palm oil.
One surface of the slit was maintained at a temperature of approximately2120 F. by means of steam at
atmospheric presure, continually passed through the inner tube. The other surface of the slit, formed by
the inner surface of the outer tube, was maintained at a temperature of110"F. by the continuous
circulation of hot water through a jacket surrounding the outer tube. After three nights and two days, or
approximately 60 hours, it was observed that the liquid in the upper portion of the slit was coloured
light orange and that the liquid in the lower portion of the slit was a dark red orange. Thesedifferentlv
coloured portions of the liquid were separately withdrawn and analysed. The results are tabulated in the
table immediately below:
Refractive% Fatty
Stream Index % Carotene Acids
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Feed 0.13 25.5
Top 1.4610 0.04 45.7
Bottom 1.4650 0.32 14.9
This type of operation is indicative of the extent of the separation that is possible with the equipment
and under the conditions described. It is to be noted that most of the carotene can be separated by the
process.
EXAMPLE 2
The same crude palm oil was subjected to thermal diffusion in the apparatus and under the conditions
described in Example 1, except that in the course of three successive days a total volume of 310 cc. was
introduced, at a temperature of110 F., into the slit at the centre and 230 and 80 cc. were withdrawn
from the top and bottom, respectively, of the column. The liquid was maintained in a static condition
during the two intervening nights while maintaining the temperature gradient.
The results are indicated in the table immediately below:
% Fatty
Stream % Carotene AcidsVolume cc.
Feed 0.13 25.5 310
Top 0.081 34.5 230
Bottom 0.208 20.9 80
The top productsobtainedwin Examples 1 and 2 were allowed to stand for approximately one month
while being exposed to air. It was observed that the products turned from a light orange to a yellow
colour.
This change is believed to result from oxidation and to indicate that the naturalantioxidants, i.e., the
tocopherols, had concentrated in the lower fraction enriched in carotene.
EXAMPLE 3
A number of separations were carried out in a vertical aluminium plate column having an effective
height of six feet and a breadth of 19 inches. The crude palm oil was preheated to110 F., introduced
into the column midway between the ends of the slit, and the hot and cold fractions were withdrawn
from the top and bottom of the column, respectively. The temperatures of the hot and cold walls and
the slit width of the column, the rate of feed and carotene concentration of the crude palm oil fed to the
column, the ratio of withdrawal rates at the top and bottom of the column, and the concentration of
carotene in the bottom fraction are listed in the table immediately below:
Hot Cold Ratio Carotene
Wall Wall Slit Feed Caroteneof with Conc. in
Temp., Temp., Width Rate, Conc. in drawal Bottom F. F. Inch ml./hour Feed, % Rates Fraction, %
31290-167 0.029 220 0.162 10/1 0.610
30092-155 0.019 480 0.142 50/50 0.238
30090-145 0.019 660 0.142 10/1 0.234
28590-153 0,019 330 0.139 10/1 0.206
28092-155 0.019 630 0.139 20/1 0.315
29790-151 0.037 1320 0.137 10/1 0.269
30098-157 0.037 660 0.137 10/1 0.283
284105-160 0.018 630 0.128 20/1 0.395
300 100-1580F036 420 0.121 50/50 0.200
The temperatures of the hot and cold wallswere measured by thermocouples at various locations in
each of the opposed aluminium plates. The reason for the spread in cold wall temperatures is believed
due to inefficient circulation of the cooling water.
The higher concentrations of carotene in the fraction withdrawn at the bottom of the column are
believed to be surprising in view of the initial low concentrations thereof in the crude palm oil
subjected to thermal diffusion. Since the degree of separation obtainable by thermaldiffusion is a
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function of the temperature gradient, it is evident that separations of even superior quality are
possiblewith more uniform and adequate cooling of the cold walltwo a temperature of the order of
about 105 to110 F.
EXAMPLE 4
A number of separations were carried out in the vertical aluminium plate column described in
Example 3. In some of the separations, as noted in the last column of the table, a miscible third
component such as15% by volume chlorobenzene (C1B) or 0.5% by weight rice bran extract (RBE)
was added to the feed, and in seme of these separations and others, the palm oil was dehydrated before
being introduced into the thermal diffusion column. Crude palm oil was preheated tolI0 F., introduced
into the column at the top adjacent to the cold wall of the slit or at the centre (as indicated by "EF"
and"CF", respectively, under "Remarks"), a carotene-enriched fraction was withdrawn from adjacent
to the cold wall or at the bottom of the column and a carotene-impoverished fraction was withdrawn
from adjacent to the hot wall or the top of the column. The average hot and dold wall temperatures, the
slit width, the rate of feed of crude palm oil, the concentrations of carotene in the feed and in the
bottom fraction, the ratio of ratesof - withdrawal of the top and bottom fractions, and the ratios of
concentration of carotene in the bottom fractions and the feed are listed in the table below: Ratio of
Carotene
Temperature, F. % Carotene Concentration Conc. in Ratio of
Slit Feed Bottom With
Hot Cold Width Rate in in Bottom Fraction drawal
Wall Wall Inches ml/hr Feed Fraction and Feed Rates Remarks 303 126 .030 480 .0893 .0938 1.05
50/50 CF-CIB 293 134 .029 660 .0413 .329 8.0 10/1 CF-CIB 297 130 .029 440 .113 .201 1.78 10/1 EF
289 126 .029 440 .0968 .254 2.62 10/1 EF-dried 297 133 .029 660 .0733 .217 2.96 10/1 EF-dried 294
136 .044 194 .057 .0936 1.64 7.4/1 EF-dried 283 155 .019 218 .076 .1042 1.37 9.5/1 EF-dried 293
126 .030 214 .0542 .133 2.46 10/1 EF-dried 293 127 .030 228 .077 .175 2.27 9.6/1 CF-dried 292
126 .030 440 .0513 .183 3.57 10/1 CF-dried 293 133 .030 224 .0914 .190 2.08 10.7/1 CF-RBE 294
135 .030 414 .0932 .404 4.34 9.7/1 CF-RBE
The results show that higher efficiencies of separation are obtained with higher feed rates and lower
ratios of product withdrawal, and that at a suitably high feed rate and low ratio of product withdrawal it
is possible to obtain a carotene-enriched fraction that is valuable for further processing to produce
concentrated carotene as well as a carotene-impoverished fraction useful as a by-product because of its
lighter colour. The data in the Table further indicate that even superior results are obtainable by (a)
dehydrating the palm oil before subjecting it to thermal diffusion, (b) adding to the feed a material,
such as chlorobenzene, that has a lower specific heat and viscosity and a higher density than palm oil,
and (c) adding to the feed an anti-oxidant, such as rice bran extract.
What we claimis : 1. A method of concentrating carotene in palm oil which comprises forming a thinfilm of palm oil
defined by opposed surfaces of heat-conductive inert material, said surfaces being closely and
substantially uniformly spaced apart between 0.01 and 0.15 inch, maintaining a temperature gradient
across the film of oil, and accumulating andwithdraw-- ing from the film of oil a carotene-enriched
fraction concentrated by thermal diffusion adjacent to the cooler surface.
2. A method as claimed in claim 1 which comprises also accumulating and withdrawing from the film
a lighter-coloured, caroteneimpoverished, fatty acid-enriched fraction con
centrated by thermal diffusion adjacent to the hotter surface.
3. A method as claimed in claim 2, wherein the ratio of the rate of withdrawal of the carotene-enriched
fraction to the rate of withdrawal of the carotene-impoverished fraction is below about 1 to 10.
4. A method as claimed in any one of the preceding claims wherein the palm oil is dehydrated before
being subjected to thermal diffusion.
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5. A method as claimed in any one of the preceding claims wherein an inert, viscosityreducing agent is
added to the palm oil before thepalm 'oil is subjected to thermal diffusion.
6. A method as claimed In any one of the preceding claims wherein an anti-oxidant is added to the
palm oil before the palm oil is subjected to thermal diffusion
7. A method of concentrating carotene in palm oil substantially as described with reference to any one
rof the Examples.
8. Carotene-enriched palm oil when produced by the method claimed in any one of the preceding
claims,
9. Carotene impoverished palm oil when produced by the method claimed in any one of the preceding
claims 2to; 7.
**WARNING** end of DESC field may overlap start of CLMS **.Data supplied from the esp@cenet
database - Worldwide
Claims:
Claims of GB736134
**WARNING** start of CLMS field may overlap end of DESC **.
The results show that higher efficiencies of separation are obtained with higher feed rates and lower
ratios of product withdrawal, and that at a suitably high feed rate and low ratio of product withdrawal it
is possible to obtain a carotene-enriched fraction that is valuable for further processing to produce
concentrated carotene as well as a carotene-impoverished fraction useful as a by-product because of its
lighter colour. The data in the Table further indicate that even superior results are obtainable by (a)
dehydrating the palm oil before subjecting it to thermal diffusion, (b) adding to the feed a material,
such as chlorobenzene, that has a lower specific heat and viscosity and a higher density than palm oil,
and (c) adding to the feed an anti-oxidant, such as rice bran extract.
What we claimis : 1. A method of concentrating carotene in palm oil which comprises forming a thinfilm of palm oil
defined by opposed surfaces of heat-conductive inert material, said surfaces being closely and
substantially uniformly spaced apart between 0.01 and 0.15 inch, maintaining a temperature gradient
across the film of oil, and accumulating andwithdraw-- ing from the film of oil a carotene-enriched
fraction concentrated by thermal diffusion adjacent to the cooler surface.
2. A method as claimed in claim 1 which comprises also accumulating and withdrawing from the film
a lighter-coloured, caroteneimpoverished, fatty acid-enriched fraction con
centrated by thermal diffusion adjacent to the hotter surface.
3. A method as claimed in claim 2, wherein the ratio of the rate of withdrawal of the carotene-enriched
fraction to the rate of withdrawal of the carotene-impoverished fraction is below about 1 to 10.
4. A method as claimed in any one of the preceding claims wherein the palm oil is dehydrated before
being subjected to thermal diffusion.
5. A method as claimed in any one of the preceding claims wherein an inert, viscosityreducing agent is
added to the palm oil before thepalm 'oil is subjected to thermal diffusion.
6. A method as claimed In any one of the preceding claims wherein an anti-oxidant is added to the
palm oil before the palm oil is subjected to thermal diffusion
7. A method of concentrating carotene in palm oil substantially as described with reference to any one
rof the Examples.
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8. Carotene-enriched palm oil when produced by the method claimed in any one of the preceding
claims,
9. Carotene impoverished palm oil when produced by the method claimed in any one of the preceding
claims 2to; 7.Data supplied from the esp@cenet database - Worldwide
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27. GB820423 - 23/9/1959
PRODUCTION OF CEPHALOSPORIN BY FERMENTATION
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=GB820423
Inventor(s):
COTTRELL ALAN REID (--)
Applicant(s):
ICI LTD (--)
IP Class 4 Digits: C12P
IP Class:C12P35/06; C12P35/00
E Class: C12P35/06
Application Number:
GB19570004363 (19570208)
Priority Number: GB19570004363 (19570208)
Family: GB820423
Abstract:
Abstract of GB820423
Cephalosporin is produced in increased yield by growing a cephalosporin-producing cephalosporium,
e.g. Cephalosporium IMI 49137 in a liquid nutrient medium containing a non-toxic ester derived from
a fatty acid containing at least 12 carbon atoms. The ester is used in quantities of 0.2 to 5.0 and
preferably 0.5 to 2.0% v./v. of the medium. The ester is an animal or vegetable oil such as palm,
arachis, sunflower seed, lard, castor or rape seed oils. It may be an ester of a monohydric alcohol such
as methanol and ethanol or a polyhydric alcohol such as glycerol, wherein one or more hydroxyl
groups are esterified, with one of the above fatty acids and particularly palmitic, stearic, oleic, linoleic,
ricinoleic or erucic acid, e.g. methyl oleate, ethyl oleate, glycerol ricinoleate and glycerol trioleate. The
medium may contain a source of (a) organic nitrogen, e.g. fish meal, meat meal, meat extract, casein,
dried autolysed yeast, malt extract, urea, soya bean meal, corn meal and corn steep liquor, and (b)
carbon, e.g. sucrose and/or lactose and ammonium acetate. A preferred medium contains corn steep
solids, sucrose, ammonium acetate, dl methionine and water.Description:
Description of GB820423
I,
t 1_ ;I I PATENT SPECIFICATIO Ni NO DRAWINGS Inventor: ALAN REID COTTRELL
Date of filing Complete Specification: Jan 29, 1958.
Application Date: Feb8, 1957 No 4363/57.
Complete Specification Published: Sept 23, 1959.
Index at acceptance:-Class 2 ( 3), AA( 1 B: 2 D).
International Classification:,-C 12 d.
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COMPLETE SPECIFICATION
Production of Cephalosporin by Fermentation We, IMPERIAL CHEMICAL INDUSTRIES
LIMITED, of Imperial Chemical House, Millbank, London, S W 1, a British Company, do hereby
declare the invention, for which we pray that a patent may be granted to us, and the method by which it
is to be performed, to be particularly described in and by the following statement:This invention relates to a fermentation process and more particularly it relates to a process for the
manufacture of cephalosporin antibiotic material.
According to the invention we provide a process for the manufacture of cephalosporin antibiotic
material which comprises culturing a cephalosporin-producing Cephalosporium in a liquid nutrient
medium containing a nontoxic ester derived from a fatty acid containing at least 12 carbon atoms.
It is to be understood that the said ester is non-toxic to the cephalosporin-producing Cephalosporium
and that the addition of the said ester to a fermentation medium results in the production of an
increased yield of cephalosporin antibiotic material.
The said ester may be used in the form of an animal or vegetable oil and suitable oils may be for
example palm oil, arachis oil, sunflower seed oil, lard oil, castor oil and rape seed oil These oils are
available commercially and may be used as such, or they may be used in the form in which they are
available commercially as antifoaming agents.
In this manner they thereby function not only in the production of an increased yield of cephalosporin
antibiotic material in the process of this invention but during such production they function also as
antifoaming agents for the fermentation medium The said ester may also be derived from a fatty acid
containing at least 12 carbon atoms and a monohydric alcohol such as methanol and ethanol or a
polyhydric alcohol such as glycerol, wherein one or more hydroxyl groups may be esterified by the
said acid Suitable fatty acids may lPri 820,423 be for example palmitic acid, stearic acid, oleic acid,
linoleic acid, ricinoleic acid and erucic acid and esters derived therefrom may be for example methyl or
ethyl oleate, glycerol ricinoleate or glycerol tri-oleate 50 The said ester may be added to the
fermentation medium in any proportion such as to be non-toxic to the cephalosporin-producing
Cephalosporium and to lead to an increased yield of cephalosporin antibiotic material Thus 55 the ester
or animal or vegetable oil may be present in the fermentation medium in a concentration of between 0
2 % (v/v) and 5 A% (v/v) and preferably the concentration of the ester is between 0 5 % O (v/v) and 2
0 % (v/v) 60 The fermentation medium to which is added the ester of the above stated formula may be
any fermentation medium known to the art to be useful for the growth of a cephalosporinproducing
Cephalosporium Thus the said 65 medium may contain a source of organic nitrogen which may be
present in the form of fish meal, meat meal or meat extract, casein, dried autolysed yeast, malt extract,
urea, soya bean meal, corn meal or corn steep liquor The 70 fermentation medium may advantageously
also contain a compound which is a carbon source, for example sucrose and/or lactose, and a
compound which is a nitrogen source, for example ammonium acetate 75 The cephalosporin antibiotic
material may be recovered from the fermentation medium after fermentation by any process known to
the art Thus the fermentation medium may be filtered or centrifuged and the cephalosporin 80
antibiotic material may then be recovered from the resulting impure solution by a process of contacting
the said impure solution with charcoal at a p H of 5 5 to 6 5, eluting the absorbed cephalosporin
antibiotic material 85 from the charcoal, contacting the eluate with a column of alumina and then
eluting the absorbed cephalosporin antibiotic material from the said column.
As stated above, the addition of the said 90 2 820,423 ester to the fermentation medium results in an
increased yield of cephalosporin antibiotic material Furthermore the addition of the said ester prolongs
the period of time over which a high content of cephalosporin antibiotic material is present in the
medium and thus it allows greater latitude in the time during which isolation of the said antibiotic
material can be carried out Moreover the presence of the said ester in the fermentation medium brings
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about a beneficial effect on the p H of of the substrate during fermentation and furthermore the ester
may act either alone or in conjunction with an added surface active agent for example octadecanol as
an antifoaming agent.
The invention is illustrated but not limited by the following Examples in which the units of activity
quoted are arbitrary units:EXAMPLE 1.
An aqueous nutrient medium is prepared containing 1 5 %/, (w/v) of corn steep liquor solids, 2 %/
(w/v) of sucrose and 0 5 % (w/v) of ammonium acetate, and the p H is adjusted to 6 5 by the addition
of 2 N aqueous sodium hydroxide solution 100 millilitres of the medium so obtained is placed into each
of six 500 ml conical flasks which are then plugged with cotton wool and sterilised by autoclaving
Each flask is then inoculated with 1 ml.
of a spore suspension containing 101 spores of Cephalosporium I M I 49137 and the flask is shaken
on a rotary shaker for 72 hours at 240 C The mycelial inoculum so obtained is used to inoculate
production flasks prepared as follows: An aqueous nutrient medium is prepared containing 2 5 % (w/v)
of corn steep liquor solids, 2 % (w/v) of sucrose, 0 5 % (w/v) of ammonium acetate and 0 1 % (w/v) of
dlmethionine The medium so obtained is dispensed into 500 ml conical flasks, 100 ml.
being put into each flask Some of these flasks receive no further additions To each of the remaining
flasks is added 1 ml of one of the following oils: palm oil, arachis oil, sunflower seed oil, lard oil,
castor oil and rape seed oil The flasks are then plugged with cotton wool and sterilised by autoclaving.
Each flask is then inoculated with 5 ml of the mycelial inoculum prepared as described above, and
shaken on a rotary shaker for 120 hours at 240 C After 72, 96 and 120 hours' shaking, the broths from
two flasks of each medium are assayed for their content of cephalosporin antibiotic material by a
cupplate method using Salmonella dublin as the test organism The average titres of the duplicate flasks
are shown in the table in units/ml.
Period of fermentation Oil added to medium 72 hours 96 hours 120 hours No oil 20 0 14 5 Palm oil 23
5 22 5 22 5 Arachis oil 25 0 24 0 23 5 Sunflower seed oil 23 0 24 0 26 0 Lard oil 23 0 27 0 22 5 Castor
oil 35 O 27 O 28 O Rape seed oil 25 0 34 5 32 0 It will be observed that the presence of an oil in the
fermentation medium leads to an increased yield of cephalosporin antibiotic material and furthermore
increased times of fermentation bring about little or no decrease in yield of cephalosporin antibiotic
material.
EXAMPLE 2.
Six flasks of mycelial inoculum of Cephalosporium I N I 49137 are prepared as described in Example 1
and used to inoculate production flasks prepared as follows: A basic aqueous nutrient medium is
prepared containing 1 5 %/, (w/v) of corn steep liquor solids, 2 % (w/v) of sucrose, 0 5 % (w/v) of
ammonium acetate and 0 1 % (w/v) of dlmethionine The medium so obtained is dispersed into 500 ml
conical flasks, 95 ml being put into each flask Some of these flasks receive no further additions To half
the remaining flasks is added 0 5, 1 0, 1 5 or 2 0 ml of castor oil, and to the other half similar volumes
of rape seed oil The flasks are then plugged with cotton wool and sterilised by autoclaving Each flask
is then inoculated with 820,423 separately, by the method described in Example 1, for their content of
cephalosporin antibiotic material The average titres of the duplicate flasks are shown in the table in
units/ml.
ml of the mycelial inoculum prepared as described above, and shaken on a rotary shaker for a
maximum of 120 hours at 240 C After 72, 96 and 120 hours shaking, the broths from two flasks of
each treatment are assayed Vol of Duration of fermentation Oil added oil added to medium (in mis) 72
hours 96 hours 120 hours None None 22 5 20 5 Castor oil 0 5 27 0 32 5 22 0 1.0 31 5 38 5 29 0 1.5 30
0 33 0 29 0 2.0 25 5 32 5 29 5 Rape seed oil 0 5 31 5 29 0 26 5 1.0 32 0 33 0 33 5 1.5 28 5 32 0 33 0
2.0 26 5 33 5 33 5 EXAMPLE 3.
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Four flasks of mycelial inoculum of Cephalosporium I M I 49137 are prepared as described in Example
1, and used to inoculate production flasks prepared as follows:Flasks containing basic medium are
prepared as described in Example 2 Some of these flasks receive no further additions To half the
remaining flasks is added 0 5, 3 0 or 5.0 ml of castor oil, and to the other half similar volumes of rape
seed oil The flasks are then plugged with cotton wool and sterilised by autoclaving Each flask is then
inoculated with 5 ml of the mycelial inoculum prepared as described above, and shaken on a rotary
shaker for a maximum of 120 hours at 240 C After 72, 96 and 120 hours shaking,, the broths from two
flasks of each medium are assayed separately, by the method described in Example 1, for their content
of cephalosporin antibiotic material The average titres of the duplicate flasks are shown in the table in
units/ml.
Vol of Duration of fermentation Oil added oil added to medium (in mils) 72 hours 96 hours 120 hours
None None 19 0 13 5 Castor oil 0 5 31 5 28 5 22 5 3.0 26 5 26 5 22 0 5.0 24 5 25 5 23 0 Rape seed oil
0 5 27 0 26 5 24 0 3.0 26 0 31 5 27 0 5.0 25 0 28 0 28 0 It will be observed that Examples 2 and 3 show
that the optimal increase in yield of cephalosporin antibiotic material is obtained by the addition of 1 %
(v/v) of castor oil or rape seed oil to the medium Further increase in the amount of oil added gives no
additional increase in yield, and the addition of % (v/v) of oil reduces the yield below what is obtained
with 1 % (v/v) of oil, EXAMPLE 4.
Six flasks of mycelial inoculum of Cephalosporium I M I 49137 are prepared as described in Example
1, and used to inoculate production flasks prepared as follows:Flasks containing basic medium are
prepared as described in Example 2 Some of these flasks receive no further additions To one quarter of
the remaining flasks is added 820,423 0.2, 1 0 or 2 ml of methyl oleate; to another quarter is added
similar volumes of ethyl oleate; to the third quarter similar volumes of glycerol ricinoleate and to the
remaining quarter similar volumes of glycerol trioleate.
The flasks are then plugged with cotton wool and sterilised by autoclaving Each flask is then
inoculated with 5 ml of the mycelial inoculum prepared as described above and shaken on a rotary
shaker for a maximum of 120 hours at 24 C After 72, 96 and 120 hours shaking, the broths from two
flasks of each treatment are assayed separately, by the method as described in Example 1, for their
content of cephalosporin antibiotic material The average titres of the duplicate flasks are shown in the
table in units/ml.
Ester of fatty Vol of Duration of fermentation acid added to ester added I medium (in mls) 72 hours
96 hours 120 hours None None 18 0 18 0 Methyl oleate 0 2 14 5 21 5 14 5 1.0 35 0 28 5 24 5 2.0 29 0
31 0 31 5 Ethyl oleate 0 2 24 5 22 0 18 5 1.0 Nil Nil 2.0 Glycerol 0 2 22 0 14 5 14 5 ricinoleate 1 0 25
0 25 5 24 0 2.0 25 0 15 5 16 5 Glycerol 0 2 22 0 14 5 13 0 trioleate 1 0 26 0 23 0 24 O 2.0 25 5 23 5 23
5 Ethyl oleate is toxic at 1 0 and 2 0 % (v/v).
With the other three esters of fatty acids, the optimal increase is obtained by adding 1 0 % (v/v) of the
ester to the fermentation medium.
EXAMPLE 5.
Six flasks of mycelial inoculum are prepared as described in Example 1, except that the flasks are
inoculated with spores of the mutant strain CB 226; and the mycelial inoculum so produced is used to
inoculate production flasks prepared as follows: Flasks of basic medium are prepared as described in
Example 2 Some of these flasks receive no further additions To the remainder is added either 0 5 or 1 0
ml of one of the following oils: palm oil, arachis oil, sunflower seed oil or lard oil The flasks are then
plugged with cotton wool and sterilised by autoclaving Each flask is then inoculated with 5 ml of the
mycelial inoculum prepared as described above and shaken on a rotary shaker for a maximum of 96
hours at 24 C After 72 and 96 hours shaking, the broths from two flasks of each treatment are assayed
separately, by the method as described in Example 1, for their content of cephalosporin antibiotic
material.
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The average titres of the duplicate flasks are shown in the table in units/mi.
820,423 820,423 Duration of fermentation Oil added Vol of oil to medium added (in mls) 72 hours 96
hours None None 34 0 26 0 Palm oil 0 5 43 5 49 0 1.0 40 5 44 5 Arachis oil 0 5 47 0 46 0 1.0 42 0 48 0
Sunflower O 5 45 5 50 5 seed oil 1 0 47 0 47 0 Lard oil 0 5 45 O 44 0 1.0 37 5 42 5 All the oils
produce an increase in yield of cephalosporin antibiotic material obtained from the mutant strain CB
226.
The mutant strain CB 226, used as starting material, is a higher-yielding mutant obtained by exposing
spores of Cephalosporium I M I.
49137 to ultra-violet light and screening the survivors for production of cephalosporin antibiotics.
EXAMPLE 6.
Six flasks of mycelial inoculum of the mutant strain CB 226 are prepared as described in Example 5,
and the mycelial inoculum so produced is used to inoculate production flasks prepared as follows:
Flasks of basic medium are prepared as described in Example 2 Some of these flasks received no
further additions To half the remaining flasks is added 0 5, 1 0, 1 5 or 2 0 ml of castor oil, and to the
other half similar volumes of rape seed oil The flasks are then plugged with cotton wool and sterilised
by autoclaving.
Each flask is then inoculated with 5 ml of the mycelial inoculum prepared as described above, and
shaken on a rotary shaker for a maximum of 120 hours After 72, 96 and 120 hours shaking the broths
from two flasks of each treatment are assayed separately, by the method as described in Example 1, for
their content of cephalosporin antibiotic material.
The average titres of the duplicate flasks are shown in the table in units/ml.
Vol of Duration of fermentation Oil added oil added to medium (in mls) 72 hours 96 hours 120 hours
None None 38 0 30 5 Castor oil 0 5 63 0 61 0 47 5 1.0 64 5 73 0 56 5 1.5 64 5 69 5 56 5 2.0 48 0 50 5
60 5 Rape seed oil 0 5 68 5 62 5 52 0 1.0 66 5 66 0 57 0 1.5 58 5 67 0 58 5 2.0 52 5 64 5 56 5 It will be
observed that both castor oil and rape seed oil at concentrations from 0 5 to 2.0 % (v/v) produce an
increase in yield of cephalosporin antibiotic material The optimum concentration of castor is 1 0 to 1
5 % (v/v), and of rape seed oil is 0 5 to 1.5 % (v/v).Data supplied from the esp@cenet database Worldwide
Claims:
Claims of GB820423
WHAT WE CLAIM IS:1 A process for the manufacture of cephalosporin antibiotic material which comprises culturing a
cephalosporin-producing Cephalo 45 sporium in a liquid nutrient medium containing a non-toxic ester
derived from a fatty acid containing at least 12 carbon atoms.
6 820,423 2 A process as claimed in Claim 1 wherein the ester is used in the form of an animal or
vegetable oil for example palm oil, arachis oil, sunflower seed oil, lard oil, castor oil or rape seed oil.
3 A process as claimed in Claim 1 wherein the ester is derived from a fatty acid containing at least 12
carbon atoms and a monohydric alcohol or a polyhydric alcohol wherein one or more hydroxyl groups
may be esterified by the said acid.
4 A process as claimed in Claim 3 wherein the alcohol is methanol, ethanol or glycerol and the fatty
acid is palmitic acid, stearic acid, oleic acid, linoleic acid, ricinoleic acid or erucic acid.
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A process as claimed in Claims 1-4 wherein the ester or animal or vegetable oil is present in a
concentration of between 0 2 % (v/v) and 5 0 % (v/v) and particularly between 0 5 % (v/v) and 2 0 %
(v/v).
6 A process, claimed in Claims 1-5, as hereinbefore particularly described and especially with
reference to the foregoing Examples 1-6.
7 Cephalosporin antibiotic material, whenever manufactured by the process as claimed in Claims 1-6.
ALFRED O BALL, Agent for the Applicants.
PROVISIONAL SPECIFICATION Production of Cephalosporin by Fermentation We, IMPERIAL
CHEMICAL INDUSTRIES LIMITED, of Imperial Chemical House, Millbank, London, S W 1, a
British Company, do hereby declare this invention to be described in the following statement: This
invention relates to a fermentation process and more particularly it relates to fermentation media for
use in the production of cephalosporin antibiotic material.
According to the invention we provide a fermentation medium for use in the production of
cephalosporin antibiotic material from a cephalosporin-producing mould, or a mutant thereof, which
comprises a nutritional substrate for the said mould or mutant thereof, in admixture with an ester
derived from a fatty acid containing at least 12 carbon atoms.
It is to be understood that the said ester is non-toxic to the cephalosporin-producing mould and that
the addition of the said ester to a fermentation medium results in the production of an increased yield of
cephalosporin antibiotic material.
The said ester may be used in the form of an animal or vegetable oil and suitable oils may be for
example palm oil, arachis oil, sunflower oil, lard oil, castor oil and rape seed oil These oils are
available commercially and may be used as such or they may be used after being subjected to a suitable
heat treatment process when they are sometimes available commercially as antifoaming agents In this
manner they thereby function not only in the production of an increased yield of cephalosporin
antibiotic material in the process of this invention but during such production they function also as
antifoaming agents for the fermentation medium The said ester may also be derived from a fatty acid
containing at least 12 carbon atoms and a monohydric alcohol such as methanol and ethanol or a
polyhydric alcohol such as glycerol, wherein one or more hydroxyl groups may be esterifled by the
said acid Suitable fatty acids may be for example palmitic acid, stearic acid, oleic acid, linoleic acid,
ricinoleic acid and erucic acid 75 The said ester may be added to the fermentation medium in any
proportion such as to be non-toxic to the cephalosporin-producing mould and to lead to an increased
yield of cephalosporin antibiotic material Thus the 80 ester may be present in the fermentation medium
in a concentration of between 0 1 % (v/v) and 2 0 % (v/v) and preferably, the concentration of the ester
is about 0 5 % (v/v).
The fermentation medium to which is added 85 the ester of the above stated formula may be any
fermentation medium known to the art to be useful for the growth of a cephalosporin-producing mould
or a mutant thereof.
Thus the said medium may contain a source 90 of organic nitrogen which may be present in the form
of fish meal, meat meal or meat extract, casein, dried autolysed yeast, malt extract, urea, soya bean
meal, corn meal or corn steep liquor The fermentation medium 95 may advantageously also contain
such ingredients as sucrose and/or lactose and ammonium acetate.
The cephalosporin antibiotic material may be recovered from the fermentation medium 100 after
fermentation by any process known to the art Thus the fermentation medium may be filtered or
centrifuged and the cephalosporin antibiotic material may then be recovered from the resulting impure
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solution by a process of 105 contacting the said impure solution with charcoal under mildly acidic
conditions, eluting the absorbed cephalosporin antibiotic material from the charcoal, contacting the
eluate with a column of alumina and then eluting the ab 110 sorbed cephalosporin antibiotic material
from the said column.
As stated above, the addition of the said ester to the fermentation medium results in an increased yield
of cephalosporin anti 115 biotic material Furthermore the addition of 820,423 spores and the flask is
shaken on a rotary shaker for 72 hours at 240 C The mycelial inoculum so obtained is used to inoculate
production flasks prepared as follows: An aqueous nutrient medium is prepared containing 2 5 % (w/v)
of corn steep liquor solids, 2 % (w/v) of sucrose, 0 5 % (w/v) of ammonium acetate and 0 1 % (w/v) of
dlmethionine The medium so obtained is dispensed into 500 ml conical flasks, 100 ml.
being put into each flask Some of these flasks receive no further additions To each of the remaining
flasks is added 1 ml of one of the following oils: palm oil, arachis oil, sunflower seed oil, lard oil,
castor oil and rape seed oil.
The flasks are then plugged with cotton wool and sterilised by autoclaving Each flask is then
inoculated with 5 ml of the mycelial inoculum prepared as described above, and shaken on a rotary
shaker for 120 hours at 240 C After 72, 96 and 120 hours' shaking, the broths from two flasks of each
medium are assayed for their content of cephalosporin antibiotic material by a cup-plate method using
Salmonella dublin as the test organism.
The average titres of the duplicate flasks are shown in the table in units/ml.
the said ester prolongs the period of time over which a high content of cephalosporin antibiotic
material is present in the medium and thus it allows greater latitude in the time during which isolation
of the said antibiotic material can be carried out Moreover the presence of the said ester in the
fermentation medium brings about a beneficial effect on the p H of the substrate during fermentation
and furthermore, the ester may act either alone or in conjunction with an added surface active agent for
example octadecanol as an antifoaming agent.
The invention is illustrated but not limited by the following Example in which the units of activity
quoted are arbitrary units: EXAMPLE:
An aqueous nutrient medium is prepared containing 1 5 % (w/v) of corn steep liquor solids, 2 % (w/v)
of sucrose and 0 5 % (w/v) of ammonium acetate, and the p H is adjusted to 6 5 by the addition of 2 N
aqueous sodium hydroxide solution 100 millilitres of the medium so obtained is placed into each of six
500 ml conical flasks which are then plugged with cotton wool and sterilised by autoclaving Each flask
is then inoculated with 1 ml of a spore suspension containing 108 Period of fermentation Oil added to
medium 72 hours 96 hours 120 hours No oil 20 0 14 5 Palm oil 23 5 22 5 22 5 Arachis oil 25 0 24 0 23
5 Sunflower oil 23 0 24 0 26 0 Lard oil 23 0 27 0 22 5 Castor oil 35 0 27 0 28 0 Rape seed oil 25 0 34 5
32 0 It will be observed that the presence of an oil in the fermentation medium leads to an increased
yield of cephalosporin antibiotic material and furthermore, increased times of fermentation bring about
little or no decrease in yield of cephalosporin antibiotic material.
ALFRED O BALL, Agent for the Applicants.
Leamington Spa: Printed for Her Majesty's Stationery Office, by the Courier Press -1959.
Published by The Patent Office, 25, Southampton Buildings, London, W C 2, from which copies may
be obtaize 4.
820,423Data supplied from the esp@cenet database - Worldwide
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28. GB847517 - 7/9/1960
PROCESS FOR THE PRODUCTION OF ESTER MIXTURES BY THE INTERESTERIFICATION OF FATTY ACID TRIGLYCERIDES
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=GB847517
Applicant(s):
EMILE MAHLER (--); MARCEL GATTEFOSSE (--)
IP Class 4 Digits: A01N; A21D; A61K; A61Q; C11C
IP Class:A01N25/30; A21D2/16; A61K8/39; A61K8/92; A61K9/02; A61K9/20; A61K47/14;
A61K47/44; A61Q19/00; C11C3/04; A21D2/00; A61K8/30; C11C3/00
E Class: C11C3/04; A01N25/30; A21D2/16; A61K8/39; A61K8/92C; A61K9/02; A61K9/20H4;
A61K47/14; A61K47/44; A61Q19/00
Application Number:
GB19570005880 (19570221)
Priority Number: FR19560710245 (19560310)
Family: GB847517
Equivalent:
FR1274354; DE1298976
Abstract:
Abstract of GB847517
Ester mixtures having surface active properties are obtained by reacting a triglyceride fat or fatty oil
with a polyethylene glycol of the formula HO CH2-(CH2O.CH2)n-CH2OH where n is an integer from
2 to 12 in the ratio of substantially 2 moles of triglyceride per mol of polyethylene glycol at an elevated
temperature and in the presence of an esterification catalyst under such conditions as to effect limited
inter-esterification of the reactants while avoiding the complete de-esterification of the triglyceride and
the formation of glycerol. The product comprises a mixture of unreacted triglycerides, mono- and diglycerides, and mono- and di-esters of the polyethylene glycol. Suitable esterification catalysts are lime,
soda, and phosphoric acid and the reaction is preferably carried out in an inert atmosphere at from 205
DEG to 225 DEG C. under atmospheric pressure for about 2 hours. Specified triglycerides are
hydrogenated and non-hydrogenated drying, semi-drying or non-drying oils and fats, e.g., linseed oil,
ground nut oil, apricot kernel oil, almond oil, olive oil, palm oil, neat's foot oil, hydrogenated whale oil,
tallow and lard. Examples are given in which polyethylene glycol 300 is reacted with linseed oil,
ground nut oil, apricot kernel oil, olive oil and hydrogenated palm oil. The products may be used as
constituents of foundry cores (see Group XXII), paints, varnishes and lubricants (see Group III), textile
sizing agents (see Group V), insecticidal, cosmetic, and pharmaceutical compositions, and foodstuffs
(see Group VI) and for coating paper (see Group VIII) or cotton wool.ALSO:A paint, varnish,
lubricating composition, or emulsion contains a proportion of an ester mixture having surface active
properties, said mixture being obtained by reacting a triglyceride fat or fatty oil with a polyethylene
glycol of the formula: - HO.CH2-(CH2-O-CH2)n-CH2OH, wherein n is an integer from 2 to 12, in the
ratio of substantially 2 mols of triglyceride per mol of polyethylene glycol to effect limited interesterification of the reactants without formation of glycerol (see Group IV(b)). The ester mixture is also
completely miscible with hydrocarbons such as kerosene, paraffin and heavier petroleum fractions and
with natural and synthetic fatty acid triglycerides and these mixtures as such or in solution in organic
liquids can be formed into fine emulsions with water. In examples: (1) a paint is obtained by diluting
with an organic solvent or with water a white ground pigment prepared from a mixture of natural
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linseed oil and linseed oil treated with polyethylene glycol 300 as above; (2) a varnish is prepared from
ordinary linseed oil and linseed oil treated with polyethylene glycol 300 as in (1); (3) a glycero-phthalic
paint is obtained by adding linseed oil treated as in (1) to a paint based on a solution of a
glycerophthalic resin in a solvent such as kerosene; (4) ground nut oil treated with polyethylene glycol
300 as above is incorporated in cutting oils to render the oil readily emulsifiable.ALSO:A textile sizing
agent contains a proportion of an ester mixture having surface active properties said mixture being
obtained by reacting a triglyceride fat or fatty oil with a polyethylene glycol of the formula: HO.CH2(CH2-O-CH2)n-CH2OH wherein n is an integer from 2 to 12 in the ratio of substantially 2 mols of
triglyceride per mol of polyethylene glycol to effect limited esterification of the reactants without
formation of glycerol (see Group IV(b)). A suitable ester mixture is obtained by treating ground-nut oil
with polyethylene glycol 300 as above.ALSO:An insecticidal, pharmaceutical or cosmetic composition
or a foodstuff contains a proportion of an ester mixture having surface active properties obtained by
reacting a triglyceride fat or fatty oil with a polyethylene glycol of the formula HO.CH2(CH2OCH2)n-CH2OH where n is an integer from 2 to 12 in the ratio of substantially 2 mols of
triglyceride per mol of polyethylene glycol at an elevated temperature and in the presence of an
esterific catalyst under such conditions as to effect limited inter-esterification of the reactant while
avoiding the complete de-esterification of the triglyceride and the formation of glycerol (see Group
IV(b)). Specified compositions are: (1) a water-dispersible derris extract comprising a chloroform
extract of Derris Elliptica, acetone, chloroform, ground nut oil treated with polyethylene glycol 300 as
above, an emulsifying agent and water; (2) a water-dispersible pyrethrum extract comprising pyrethrum
extract, ground nut oil treated as in (1), an emulsifying agent and water, (3) a nasal oil comprising
eucalyptol, apricot kernel oil treated with polyethylene glycol 300 as in (1), and olive oil; (4) a
vitaminised oil comprising shark liver oil, cod liver oil and apricot kernel oil oil treated as in (3); (5) a
water-dispersible olive oil comprising pure olive oil and olive oil treated with polyethylene glycol 300
as in (1); (6) a cosmetic lotion comprising hydrogenated palm oil treated with polyethylene glycol as in
(1), polyethylene glycol 300 stearate, petroleum jelly, water, fungicide and perfume; (7) an excipient
comprising hydrogenated palm oil treated as in (6) and untreated hydrogenated palm oil of melting
point 38-40 DEG C., the excipient obtained in (7) may also be incorporated with antibiotics to preserve
the latter; and (8) an excipient for suppositories comprising hydrogenated palm oil treated as in (6) and
untreated hydrogenated palm oil of m.p. about 36 DEG C. A solution of ground nut oil treated as in (1)
may also be mixed with the facts or oils normally employed in the manufacture of cakes, bread, sponge
fingers, biscuits and rusks.Description:
Description of GB847517
PATENT SPIECIFICATION
NO DRAWINGS / 847,517 Date of Application and ifiling Complete PATENT ACT,1_949
SPECIFICATIONNO. 4,
In azc,ordan-ze with -.he Deci.ion of the Superinzendirg Exalrfrnei aotnlhg for the In Cocrnprolle-1r-Gnerai', dated the twentysecond day of Narzh., 962, this Specification has been anended unmder
Section 33 in the followling ranner; Page 1, Jieries 24 tlo 27 and Page 5, lnes 506,,c 32. dt n- ele-a-edc
I' temperature and in the presence of anetrlctn cSZlyst under such ccnidiz.Ions as', and iinsert 4a tempeiature o-f from, 205 to. 2250 C at atm.spheilc presauuro ard ifn the presence of 0.05 to 0.2% of an
esterification catallyst based r.the weigh:- of the fatty acid -rig).yceride for a period of 2 hours so- ats!
Page 2, lines 5-9 to 62. deflete Page 2, 1-Ine 63 d1E 6 te 1'afid t.rlglycerf'te Page 2, lir.4n._65 delete
i'and ithe reaction. I-spefrb Page 2, l1ines 66 to 68. delete Page 6 6r&'o. delete Page 5, 61 Tycr? read1"2: and de,'ete r- 21; page 5, 1lines 'i4 to0 70. Helete Page. 5., 11ne 7t- faor t-61; read 131 and for
'Vany?-re doo 'ihr" Page 5,! no 77 for- 7' read 1"41 page 5, line. 83, for "61 rEa cfr.:
Page 5, I Ine 67, fo r i reed "t6V Page.5 12fle 69, foar -eueV1 Page 5, l InE) 93. for '6' 1 r-e d i6 ' THE
PATENT OF'F.2-E, 24th Aprti1, 1902 509 D'S 630741.I 2)'RE.. 200 4/-62 FL CH-OOCR HOCH,(CH.-O-CH,)n-CH.OH ; 2 CH-OOCR CH.-OOCR RCOO-CH.-(CH.,-O-CH 0)r--CH.-OOC R + 50
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CHI di-ester where R is the carbon chain of the fatty acid present in the triglyceride starting material
and n is an integer from 2 to 12.
60' ft is known to react fatty acid triglycerides with polyethylene glycol to give a variety of ester
products, but we have found that by using the above-specified proportion-, of the starting- materials
and approporiate reaction conditions, ester mixtures containing, a 65 large proportion of the diester of
the polyethylene glycol and having particularly valuable properties are obtained.
The mono- and di-esters of polyethylene glycols constitute a class of non-ionic 70 surface-active
agents and since they form a substantial proportion of the total reaction I I5C PATENT
SPECIFICATION
NO DRAWINGS Date of Application and filing Complete Specification: Feb. 21, 1957.
Application made in France on March I0, 1956.
Complete Specification Published: Sept. 7, 1960.
847,517 No. 5880/57.
Index at acceptance:-Classes 1(1), J(2A:3D); 2(3), C3A7(Al:B:C:El:E2:Fl:F2:Jl); 49, B1C; 81(1),
Bl(M:N:R2), B2(M:N:R2), E1C(lA:3A4:3B3:11:14D), L1I 83(1), F6BX; 91, F4; 95, A4(E:P),
A9(B:C);96, B6, B14(A:D); and 121, D2.
International Classification:-A01n. A23d. A61k. B01l. B22c. C07c. C09d, k. C10m. D21h.
COMPLETE SPECIFICATION
Process for the Production of Ester Mixtures by the Inter-esterification of Fatty Acid Triglycerides
We, EMILE MAHLER, of French Nationality, HOCH.-(CH2 -O- CH2)n-CH2OH 21 of 30, Rue
Malesherbes, Lyon, (Rhone), France and MARCEL GATTEFOSSE, of French wherein n is an integer
from 2 to 12, in the Nationality, of 33, Cours Eugenie, Lyon ratio of substantially 2 moles of
triglyceride (Rhone), France do hereby declare the per mole of polyethylene glycol at an elevated
invention for which we pray that a patent temperature and in the presence of an 2 may be granted to us,
and the method by esterification catalyst under such conditions which it is to be performed to be
particularly as to effect limited inter-esterification of the described in and by the following statereactants while avoiding the complete dement:- esterification of the triglyceride and the The present
invention is concerned with formation of glycerol. 3 a method for the production of ester mixtures The
product of the invention is the mixture by the limited inter-esterification of fatty of esters forming the
total reaction product acid triglycerides and polyethylene glycols obtained at the conclusion of the
reaction.
and with the ester mixtures so obtained. This mixture is made up of unreacted According to the
present invention this triglycerides, mono- and di-glycerides, and 3 method comprises reacting a
triglyceride fat mono- and di-esters ofthe polyethylene glycol, or fatty oil with a polyethylene glycol of
the latter being obtained by the following the formula reactions:
CH2-OOCR I CH-OOCR +- HOCH2-(CH2-O-C I CH2-OOCR RCOO-CH2 = (CH mono CH2-OOCR
I CH-OOCR + HOCH2-(CH2-O-C CH2-OOCR CH2-OOCR 40 I H2)n-CH2OH ; CH-OOCR + CH2OH [2-O-CH2),-CH2OH 45 (1) -ester CH2-OOCR I H2)n-CH2OH ;2 CH-OOCR + 50 CH2OH (2'
where R is the carbon chain of the fatty acid present in the triglyceride starting material and n is an
integer from 2 to 12.
It is known to react fatty acid triglycerides with polyethylene glycol to give a variety of ester products,
but we have found that by using the above-specified proportions of the starting materials and
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approporiate reaction conditions, ester mixtures containing a 65 large proportion of the diester of the
polyethylene glycol and having particularly valuable properties are obtained.
The mono- and di-esters of polyethylene glycols constitute a class of non-ionic 70 surface-active
agents and since they form a substantial proportion of the total reaction Pric t5 RCOO-CH2-(CH2-OCH2)n-CH2-OOCR di-ester 047,517 mixture, they confer surface-active properties and miscibility
with both aqueous and nonaqueous media to the mixture. Miscibility with aqueous media is conferred
by the ether oxide groups of the polyoxyethylene 5 chain -CH2-CH.-O-CH0-CH.2- H.OH ; -CH2-CH.O-CH2-CH2H(+) OH(-) and by the terminal hydroxyl group of the mono-esters, while miscibility with
nonaqueous media is conferred by the carbon chains of the fatty acid radicals present in all the esters
making up the mixture.
The above-mentioned valuable properties of the ester mixtures produced by the method according to
the invention may be summarised as follows:(1) The mixtures are miscible in all proportions with
hydrocarbons, such as kerosene, paraffin and heavier petroleum fractions, and with natural and
synthetic fatty acid triglycerides, such as vegetable oils and oils prepared by the esterification of a
variety of fatty acids with glycerol, giving limpid solutions thereof.
The mixtures, as such or in solution in So organic liquids, can be formed into fine emulsions with
water of the " oil-in-water " type; such emulsions are opaque and not translucent and are comparatively
stable on storage, while with the majority of known surface-active products which are soluble in
hydrocarbons, such as kerosene, only very crude or translucent emulsions of the "oil-in-water " type
can be obtained.
(2) The mixtures are practically neutral; their acid number does not exceed 2 and a dispersion of 10%
by weight of the mixture in water has a pH between 6.7 and 7.3.
(3) The mixtures possess anti-oxidant properties, which are applicable, for example, to the
preservation of mono- or polyethylenic triglycerides by preventing the formation of peroxides.
(4) The mixtures have no toxic or " primary irritant " character with respect to mucous membranes,
nor have they a haemolytic character.
The present invention also comprises foundry cores, paints, varnishes, insecticidal compositions,
textile sizing agents, lubricants, cosmetic and pharmaceutical compositions containing a proportion of
an ester mixture produced by the process according to the invention.
In carrying out the method according to the invention, it is preferred that the amount of esterification
catalyst employed should be from 0.05 to 0.2% by weight of the fatty acid triglyceride. Suitable
esterification catalysts are, for example, lime, soda and phosphoric acid and the reaction is preferably
carried out at a temperature of from 205 to 2250C. under atmospheric pressure and, preferably, for a
period of about 2 hours.
Advantageously the reaction is carried out under an inert atmosphere with continuous 70 agitation and
in a stainless steel reaction vessel in order to prevent the formation of coloured metal soaps.
Among the fatty acid triglycerides which may be employed as starting materials are 75 hydrogenated
or non-hydrogenated drying, semi-drying or non-drying vegetable oils, such as linseed oil, ground-nut
oil, apricot kernel oil, almond oil, olive oil and palm oil, and drying, semi-drying or non-drying animal
80 oils and fats, such as neat's foot oil, hydrogenated whale oil, tallow and lard.
In order that the invention may be more fully understood, the following examples are given, by way
of illustration only:The same conditions of reaction and the same polyethylene glycol were employed
in each of the following examples. The fatty acid triglyceride and a polyethylene glycol having a
molecular weight of about 300 in 90 the ratio of 2 moles of the former per mole of the latter were
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placed in a stainless steel reaction vessel together with 0.08% by weight of pure soda based on the
weight of fatty acid triglyceride. The reaction mixture was maintained at a temperature of 210'C. under
an inert atmosphere at atmospheric pressure for 2 hours. At the end of this time phosphoric acid having
a density of 60' Baume was added to the reaction mixture to form insoluble 100 disodium phosphate
with the catalyst and the phosphate was separated by filtration.
EXAMPLE I
The fatty acid triglyceride employed was 105 a light yellow linseed oil.
The mixture obtained by the foregoing method had the following characteristics:
Acid number 1.6 Iodine number 123 110 Saponification number 128 Peroxide number (de Lea's hot
method) below 10 It was miscible with natural linseed oil in all proportions. 115 Applicarions (1)
Foundry practice: as an additive to linseed oil in the preparation of foundry cores with a view to
increasing the tensile strength thereof, for example: 120 Core A composed of:
Core making sand (Bourron sand) kilograms Linseed oil 0.075 " Water 0.075 " 123 normally
employed; by adding the solution to such fats or oils the latter are rendered dispersible in water and the
dough mixture is thereby more readily formed and the solution also brings about a better rising of the
70 doughs and a finer dispersion of air in cakes, bread, sponge fingers, etc.
(2) The incorporation of the above solution in insecticide compositions promotes the water dispersion
of the insecticide (e.g. 75 chlorinated derivatives), especially in dipping baths and increases the wetting
power of the latter particularly in the protection of cattle against gad-fly or bot-fly larvae.
Applications:- 80 (A) Water-dispersible derris extract:Chloroform extract of Derris Elliptica 8 grams
Acetone 8 Chloroform 8 " 85 Ground-nut oil treated according to the present invention 8 Emulsifying
agent 8 Water, enough to make up to 1 litre (B) Water-dispersiblepyrethrum extract:Pyrethrum extract
10 grams Ground-nut oil treated according to the present invention 48 Emulsifying agent 10 Water,
enough to make up to 1 litre 95 When these insecticide emulsions are applied to the thick tegument
(skin) of cattle for the treatment of gad-fly larvae infestations, they wet the fur and skin without
causing any irritating reaction, and diffuse rapidly through 100 the pilo-sebaceous system in order to
reach the larvae of the gad-fly which are deposited below the derm(true skin).
(3) In the sizing of textiles, the use of ground-nut oil treated according to the 105 invention facilitates
dispersion of the size in water and also the breaking of the size emulsion by heating the latter to a
temperature above 60'C.
(4) The incorporation of ground-nut oil 110 treated according to the invention in cutting oils used in
machinery, renders such oils readily emulsifiable and the oils, with such addition, are non-toxic, nonirritant and less likely to cause allergic reactions. 115 EXAMPLE III
The fatty acid triglyceride employed was apricot kernel oil.
The mixture obtained by the foregoing method had the following characteristics 120 Acid number 1.4
Saponification number 160-165 Iodine number 75-85 Peroxide number (method of Lea in the hot)
below 35 125 Viscosity: Engler degrees at 19'C. 11.9 This mixture may be used:
(1) In cosmetics, as a non-ionic emulsifying agent in the production of beauty lotions, detergents or
make-up removers. These 130 Core B composed of:Core making sand (Bourron sand) kilograms
Natural linseed oil 0.0682 " Linseed oil treated according to the present invention 0.0682 " Water
0.0342" After baking at 240'C. the tensile strength expressed in kilograms per square centimetre for
each of these cores was:Duration of baking in minutes Core A Core B 20.... 0 0 29.... 6.3 6.7 42.... 12.6
17.2 60.... 15.4 20.6 87.... 13.6 21.9 125.... 11.8 19.5 180.... 9.5 16.2 260.... 8.8 12.9 It will be seen that
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core B prepared with natural linseed oil with the addition of 10% of linseed oil treated according to the
present invention had a much higher tensile strength than the core A.
(2) Paints: white ground pigments prepared from a mixture of 85% natural linseed oil and 15% of
linseed oil treated according to the present invention could be diluted with any of the usual organic
solvents, such as linseed oil and petroleum distillation fractions, to form paints. These mixtures can
also be diluted with from 20 to 30% of their weight of water to form emulsion paints which can be
applied to any surface whether dry or wet by means of the usual appliances, e.g. brushes, rollers, or
guns, to give a matt finish.
(3) Varnish: linseed oil treated according to the invention when added to ordinary linseed oil delays
the oxidation of the latter and this property is useful in the preparation of supple varnishes.
(4) Glycero-phthalic paints: when linseed oil treated according to the present invention is added to
paints based on solutions of glycero-phthalic resins in solvents such as kerosene, the affinity of the
paint to the surfaces to be coated is increased.
ExAMPLE II
The fatty acid triglyceride employed was ground-nut oil.
The mixture obtained by the foregoing method had the following characteristics:Acid number 1.2
Saponification number 165 Iodine number 70 Hydroxyl number 58 A solution of 10% by weight of the
mixture in ground-nut oil constitutes a stabilising and water-dispersing agent for the following
purposes:(1) The manufacture of biscuits, rusks, cakes is facilitated by mixing a proportion of the
above solution with the fats or oils -47,517 847,517 preparations are stable and non-irritant.
(2) In pharmaceutics: as an oily base or as a wetting agent in pharmaceutical preparations based on oil,
in order to promote the contact of the excipient or of the vehicle with moist mucous membranes.
Water-dispersible olive oil Pure olive oil 90 grams Olive oil treated according to the present invention
10" 100" Applications:(1) Pharmaceutical nasal oil Eucalyptol according to pharmacopoeia 5 grams
Apricot kernel oil treated according to the present invention 10 grams Olive oil according to
pharmacopoeia 85 grams grams The contact of this oily preparation with the mucous membrane and
aqueous body serum is excellent owing to the hydrophilic character of the kernel oil treated according
to the present invention. The globules of oil which are thus formed do not prevent the movements of
the vibratory cilia of the mucous membrane, while simple oily solutions inhibit them completely.
(2) Water-dispersible vitamninised oil Shark-liver oil titrating 100,000 I.U./gram 30 grams Cod-liver
oil 30 " Apricot-kernel oil treated according to the present invention 40 " 100" This oily solution of
vitamins presents the following two advantages over similar preparations: firstly this oil can be
dispersed without difficulty in medicines, foods, etc., while the usual oily preparations remain fixed to
the walls of the receptacle; and secondly the vitamin A is stabilised against oxidation by the antioxidising property of the kernel oil treated according to the present invention.
EXAMPLE IV
The fatty acid triglyceride employed was pure olive oil.
The mixture obtained by the foregoing method had the following characteristics:Acid number 0.6
Saponification number 168 Peroxide number (by Lea's hot method) below 10 and may be used:
(1) In cosmetics as a non-ionic emulsifying agent in the preparation of nourishing beauty lotions (2)
In pharmaceutics as a wetting agent for pharmaceutical oily vehicles, and as a dispersing and antioxidising agent in the preparation of fat-soluble vitamin solutions.
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Applications:This mixture emulsifies perfectly in cold water and its absorption by the patient is thus
made much easier. In addition the 75 preservation of the pure olive oil is favoured by the presence of
the olive oil treated according to the present invention, and the latter also facilitates the dissolution of
pharmaceutically active materials in the 80 preparation.
EXAMPLE V
The fatty acid triglyceride employed was a hydrogenated palm oil having a melting point of about 39
C. 85 The mixture obtained by the foregoing method had the following characteristics:Acid number 0.4
Iodine number 3 Saponification number 195 90 Melting point 350C.
and may be used:
(1) In cosmetics as a non-ionic emulsifying agent in the production of creams or lotions.
An example of such a lotion is:Hydrogenated palm oil treated according to the present invention 5
grams Polyethylene-glycol 300 stearate 5 " Petroleum jelly according to pharmacopoeia 2 " Water 88 "
Fungicide as required Perfume " This non-ionic emulsion is stable on 105 storage: it may be used as a
non-ionic makeup remover lotion, or serve as a base for a vegetable-oil lotion (almond, avocado).
(2) In pharmaceutics, this hydrogenated palm oil treated according to the present 110 invention may
be used in the production of anhydrous or emulsified excipients, suppositories, water-dispersible tablets,
etc.
Application: excipient for pomade Hydrogenated palm oil treated 115 according to the present
invention 18 grams Hydrogenated palm oil of 38 -40 C melting point 82 100" This mixture is
homogeneous and plastic when it has been suitably homogenised. In the anhydrous state it may be used
as a 125 vehicle for antibiotics which are perfectly preserved when incorporated therewith, and also for
powders and for oily or aqueous solutions of pharmaceutically active materials.
This same water-dispersible excipient can 13o absorb 10 to 30% of its weight of water, temperature
and in the presence of an while still remaining in a pasty state: the esterification catalyst under such
conditions as water may be introduced by homogenisation. to effect limited inter-esterification of the
This non-ionic excipient is non-irritant and reactants while avoiding the complete decan be very readily
spread on the skin. esterification of the triglyceride and the 55 Application: excipient for suppositories
formation of glycerol.Data supplied from the esp@cenet database - Worldwide
Claims:
Claims of GB847517
Hydrogenated palm oil treated 2. A method according to Claim 1, in
according to the present inven- which the amount of esterification catalyst tion 50 grams employed is
from 0.05 to 0.2% by weight of Hydrogenated palm oil of m.p. the fatty acid triglyceride. about 360C.
50 " 3. A method according to Claim 1 to 2, in which the esterification catalyst is lime, " soda or
phosphoric acid.
4. A method according to any of the This mixture can be moulded and stripped preceding claims, in
which the reaction is 65 from the mould perfectly under the usual carried out at a temperature of from
2050 to conditions employed in the production of 225 C. at atmospheric pressure.
suppositories. The mixture can be used as 5. A method according to any of the a vehicle for numerous
water or oil-soluble preceding claims, in which the reaction time materials; antibiotics are perfectly
preserved amounts to 2 hours. 70 when incorporated therewith. 6. A method according to any of the In
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use, the diffusion of pharmaceutically preceding claims, in which the fatty acid active materials takes
place rapidly owing to triglyceride is a hydrogenated or nonthe hydrophilic character of this mixture.
hydrogenated drying, semi-drying or non(3) Paper industry: paper or cotton wool drying vegetable oil
or a drying, semi-drying 75 may be coated with hydrogenated palm oil or non-drying animal oil or fat.
treated according to the present invention, 7. A method according to any of the either for the purpose
of covering the paper preceding claims, in which the fatty acid with a hydrophilic fatty body or for
covering triglyceride is linseed oil, ground-nut oil, the paper with a layer of a water-dispersible apricot
kernel oil, almond oil, olive oil, 80 fatty body containing an antiseptic, such as palm oil, neat's foot oil,
hydrogenated whale a chlorinated derivative, the antiseptic having oil, tallow or lard.
been previously dissolved in the hydrogenated 8. A method for the production of ester palm oil treated
according to the present mixtures having surface-active properties invention. substantially as herein
described with referSuch a layer of a fatty body may be applied ence to any of the Examples.
to the paper either by callandering, or by 9. Ester mixtures when produced by the spraying an
atomised emulsion of the water- method claimed in any of the preceding claims.
dispersible fatty body onto the paper and 10. Foundry cores, paints, varnishes, then drying the latter.
insecticidal compositions, textile sizing agents, go WHAT WE CLAIM IS:- lubricants, cosmetic and
pharmaceutical com1. A method for the production of ester positions containing a proportion of an
ester mixtures having surface-active properties mixture as claimed in Claim 9.
which comprises reacting a triglyceride fat or fatty oil with a polyethylene glycol of the A.A.
THORNTON & CO., formula Chartered Patent Agents, HOCH2-(CH2-O-CH2)n-CH2OH
Northumberland House, where n is an integer from 2 to 12, in the 303-306, High Holborn, ratio of
substantially 2 moles of triglyceride London,W.C.1., per mole of polyethylene glycol at an elevated For
the Applicants.
Printed for Her Majesty's Stationery Office by Wickes & Andrews, Ltd., E.C.4. 684/2.-1960.
Publisbed at The Patent Office, 25, Southampton Buildings, London. W.C.2, from which copies may
be obtained.
847,517Data supplied from the esp@cenet database - Worldwide
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29. GB953451 - 25/3/1964
PROCESS FOR THE PREPARATION OF COCOA BUTTER SUBSTITUTES AS
WELL AS FOR THE PREPARATION OF CHOCOLATE CONTAINING SUCH
SUBSTITUTES
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=GB953451
Applicant(s):
TWINCON NV (--)
IP Class 4 Digits: A23G; C11B
IP Class:A23G1/00; A23G1/38; C11B7/00; A23G1/30
E Class: A23G1/00K; A23G1/38; C11B7/00B4
Application Number:
GB19600016657 (19600511)
Priority Number: NL19590239150 (19590513)
Family: GB953451
Equivalent:
CH432995; SE302560; DE1299991
Abstract:
Abstract of GB953451
Cocoa butter substitutes are obtained from fats containing mono-unsaturated di-saturated triglycerides
of palmitic and/or stearic acid and oleic acid, e.g. Shea butter, Borneo tallow, seed fat of Pentadesma
butyracea, tallow and lard, but especially palm oil, by extracting the fat in a solid or semi-solid state in
one or more stages at -5 DEG to 10 DEG C. with a total of 2-20 c.c. acetone per g. fat to remove a low
melting fraction, and then extracting the residue in one or more stages at 10-35 DEG C. with a total of
1-15 c.c. acetone per g. fat originally taken to obtain the fat in the form of an extract, the acetone being
subsequently removed. It is preferred that the extractions be carried out by countercurrent extraction in
two or more operations at successively increasing temperatures, suitably with the fat supported on a
horizontally moving filter. If desired, the fat may be mixed with a carrier such as kieselguhr or sand or
crystallized on to Raschig rings. The product may be used in the preparation of chocolate (see Division
A3). Specifications 827,172, 841,316, 841,317, 953,452, 953,453 and U.S.A. Specification 2,678,937
are referred to.ALSO:Chocolates are prepared from (a) 182g. cocoa liquor (56% cocoa butter), 180g.
sugar and 38g. cocoa butter substitute (b) 112g. cocoa powder (11% cocoa butter), 225g. sugar, 75g.
cocoa butter and 87g. cocoa butter substitute (c) 112g. cocoa powder (11% cocoa butter), 225g. sugar
and 163g. cocoa butter substitute, the substitute used being obtained from fats containing monounsaturated di-saturated triglycerides of palmitic and/or stearic acid and oleic acid, e.g. palm oil, by
extracting the fat in a solid or semi-solid state in one or more stages at -5 to 10 DEG C. with a total of
2-20 ml. acetone per g. fat to remove a low melting fraction, and then extracting the residue in one or
more stages at 10-35 DEG C. with a total of 1-15 ml. acetone per g. fat originally taken to obtain the
substitute in the form of an extract (see Division C5). Specifications 827,172, 841,316, 841,317,
953,452, 953,453 and U.S.A. Specification 2,678,937 are referred to.Description:
Description of GB953451
PATENT SPECIFICATION
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DRAWINGS ATTACHED 953451 e, z l ll MDate of Application and filing Complete Specification:
May I 1, 1960.
No 16657/60.
Application made in Netherlands (No 239,150) on May 13, 1959.
Complete Specification Published: March 25, 1964.
Crown Copyright 1964.
Index at acceptance:-05 C( 3 A 4, 4); A 2 B 15 International Classilfication:-C 11 b (A 23 g)
COMPLETE SECIFICATION Process for the preparation of Cocoa Butter Substitutes as well as for
the preparation of Chocolate containing such Substitutes We, N V TWINCON, a limited liability
company, organized and existing under the Laws of the Kingdom of the Netherlands, residing at
Zaandijk, Province of North Holland, the Netherlands, do hereby declare the invention, for which we
pray that a patent may be granted to us, and the method by which it is to be performed, to be
particularly described in and by the following statement: The invention relates to the preparation of cocoa butter substitutes and of products in which they are
used.
Cocoa butter is used for a great many purposes; chief among these is its use in chocolate, although
large quantities of cocoa butter are also employed in the pharmaceutical and the cosmetic industries.
Among naturally occurring fats cocoa butter occupies a special place because it is solid and fairly
hard up to 250 C, has a short melting range, and is almost completely liquid at 350 C.
Because cocoa butter is an expensive product, it has long been replaced completely or partly by
cheaper fats, while attempts are constantly being made to find improvements.
A more recent solution of the problem of the substitution of cocoa butter is known from the British
Specification No 827,172; it describes a process starting from palm oil, from which at least 50 % of a
low-melting glyceride fraction is removed by cooling and crystallisation.
The solid fat can subsequently be dissolved again and a quantity of the high-melting fraction can be
removed from it The procedure in this fractionation is such that the fat it dissolved in a solvent and is
caused to undergo partial crystallisation by cooling or evaporation of the solvent According to British
Specification No 841,316 the starting material for the same purpose is lard, which is treated in the same
way, while British Specification
No 841,317 takes tallow as the initial fat.
I, U.S Patent Specification No 2,678,937 describes a process for the removal of high 45 molecular
weight saturated esters of fatty acids from oils and fats by dissolution in a solvent and cooling to a
temperature at which the esters of high molecular weight crystallise.
The material is kept at this temperature for 50 some hours, then cooled to a temperature about 100 C
lower, and kept at this temperature again for at least 5 hours, whereupon the crystals are separated from
solution The process in question therefore involves crystallisa 55 tion alone.
In contradistinction to such prior proposals the present invention uses fractional extraction for
preparing the cocoa butter substitute, the fat being first brought into, extractable form 60 by a known
method, such as by melting and deposition in a thin film on a cooled surface, from which it may be
scraped off, or by crystallisation with a small quantity of a solvent to produce a semi-solid granular
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mass 65 According to the invention at least one fat containing at least one of the mono-unsaturated disaturated triglycerides of palmitic and / or stearic acid and oleic acid in a solid or semisolid extractable
form is extracted whilst still 70 solid or semi-solid in a first step in one or more stages at a temperature
between -5 and + 100 C with a total number of cubic centimetres of acetone that is from twice to
twenty times as great as the number of grams 75 of fat, this first extract containing a lowmelting
fraction of the fat is removed, the residue is extracted in a second step in one or more stages at a
temperature between 10 and 350 C with a total number of cubic centi 80 metres of acetone that is from
one to fifteen times as great as the number of grams of fat originally taken to yield a second extract
containing the mono-unsaturated di-saturated triglyceride as the cocoa butter substitute and a 85 second
residue including high-melting triglyr-i II cerides, and the cocoa butter substitute is recovered by
evaporation of the acetone from the second extract.
Thus by the invention a fat or a mixture of fats is separated into at least three fractions, one fraction
being recovered as a solid residue from the original fat.
It is advisable to divide the fat into small pieces before or during the extraction If desired, the fat may
be in the presence of a carrier, for example by being mixed with kieselguhr or sand, or by being caused
to crystallise onto Raschig rings.
If desired, a number of extractions may be carried out in each step, successive operations being
carried out at successively increasing temperatures within the temperature range at which the particular
extraction step may be effected.
Since the solubility of the more saturated compounds which are to be separated from the mcre
unsaturated compounds is greater when more unsaturated compounds are present in the solvent (see
Hilditch, The Chemical Constitution of Natural Fats, 1947, p 521), carrying out each extraction in
several stages has the advantage that the greater part of the more unsaturated compounds can be
removed at a relatively low temperature, i e when the solubility of the more saturated compounds is
lower The removal of the remainder of the more unsaturated compounds can then take place at a higher
temperature, since then the concentration of these compounds in the solvent is lower, and accordingly
the solubility of the more saturated glycerides is lower In this way a sharper separation of the fractions
is ensured.
Preferably the extractions are carried out 0 o by counter-current extraction in several stages, in which
case the extract from one stage is used as the extractant for a preceding stage in which the fat contains
more of the fraction it is desired to extract Such a counter current extraction is preferably effected with
the fat supported on a horizontally moving filter.
The process according to the invention has considerable advantages over the known methods:
1) From the point of view of heat economy it is superior to the crystallisation method, where the
desired cocoa butter substitute is obtained by repeated dissolution of the fat or the fat crystals in a large
quantity of solvent.
In this case heating to 450 C, for instance, is necessary After this, the solution has to be cooled again
Thus a large quantity of solvent has repeatedly to be heated and cooled again.
The fat, too, is repeatedly melted and crystallised, also consuming heat.
2) Extraction removes occluded components of lower melting point from the crystals, which is not the
case with crystallisation and washing Thus the third fraction, of high melting-point, can be purer when
extraction is used If the same degree of purity were to be attained using crystallisation, it would be
necessary either to crystallise very slowly or to re-crystallise the product In both cases further
equipment would be necessary.
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3) Extraction on a filter presents advantages over crystallisation if unsaponifiable constituents are
present in the fat, since these are more easily removed in the case of extraction.
Upon crystallisation of the fat the constituents in question tend to enter the crystalline fraction With
extraction on a filter, no stirring takes place and the permeability of the unsaponifiable constituents is
greater (the filter resistance smaller) than with repeated dissolution, stirring, and crystallisation After
such operations it is more difficult and may even be impossible to filter these constituents.
4) A great advantage of the extraction method is that it can easily be carried out continuously
Continuous extraction on a horizontal extractor, for instance, can be effected more readily than a series
of continuous crystallisations followed by filtrations.
5) Continuous extraction yields a more constant product and can readily be controlled automatically
With crystallisation supersaturation and irregular attainment of equilibrium occur, resulting in
fluctuations in the yield and the composition of the separated fractions.
The mother liquors of the crystallisation are also liable to these fluctuations and tend to have an
adverse effect on the process if they are used again This is aggravated even further by the fact that the
concentration of the more unsaturated compounds in the solvent affects the solubility of the more
saturated compounds.
This results in fluctuations in the yield and the quality of the desired product, so that, if such
variations are to be kept as small as possible, intensive supervision and repeated interference in the
process may be necessary.
The extraction process of this invention avoids such difficulties The yield of the first extraction step
for the removal of an oil fraction is constant and a constant product is passed on to the subsequent
extractions.
By the process of the invention it is possible to obtain from fats and mixtures of fats a fraction which
can be used as a cocoa butter substitute and which is suitable in particular for the chocolate industry
Suitable initial products are palm oil, Shea butter, Borneo tallow, fat from the seed of Pentadesma
butyracea, tallow and lard as well as mixtures of these products.
A suitable cocoa butter substitute can also be obtained by mixing fractions obtained by the
independent extraction of such products.
If palm oil is the starting material, this substance, which may or may not be mixed with other fats, is
first brought into an extractable form This may be done by cooling the oil, which may or may not have
been precooled and pre-crystallised, on a surface, by 953,451 Referring to Figure 1, palm oil flakes and
acetone are added simultaneously to a stirred vessel 1 The suspension of solid fat is then deposited on a
horizontally moving filter 2, which may comprise a series of vessels carried by a chain Alternatively a
suspension in acetone of palm oil crystals may be fed to the vessel 1 or directly to the extraction
apparatus 2 For the first extraction two, operations are carried out, one at about 00 C, labelled A, and
another at 50 C, labelled Al In both cases counter-current extraction is employed.
A first extract is recovered from the operation A, while the extract from operation Al is used for
stirring with the palm oil flakes, or for obtaining palm oil flakes from palm oil by crystallisation The
residue remaining on the filter 2 is then treated with acetone at 280 C.
(entering at B) by counter-current extraction to yield a second extract containing the desired cocoa
butter substitute, which is recovered upon evaporation of the acetone Lastly the solid residue of
products of high meltingpoint is recovered at the right-hand end of the filter 2.
The following examples illustrate the invention:EXAMPLE I
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A thin layer 2 to 3 mm thick of solidified palm oil was obtained on the outside of a 1litre roundbottomed flask cooled with a mixture of ice and salt by immersion in palm oil at 500 C The palm oil
was cooled once more by placing the flask for 15 minutes in an icebox at 150 C.
After having solidified and set, the palm oil was readily removed from the flask with a knife and 115
g of the solidified product were extracted twice at 20 C and twice at 70 C.
with 500 cc of acetone for each extraction according to the scheme given below After each extraction
the flakes and crystals were filtered off on a B Uchner funnel and washed each time with 100 cc of
acetone having a temperature equal to the extraction temperature.
allowing the oil, which may or may not have been pre-cooled with stirring, to solidify ion a carrier, or
by bringing the oil into the crystalline form by crystallisation from acetone In the last-mentioned case it
is preferred in view of the above considerations to use as little acetone as possible.
The fat in the solid or semi-solid condition may then be extracted with acetone which may be at a
temperature equal to, lower than or higher than that of the fat The fraction first separated is an oily
fraction which may constitute more than 50 % of the palm oil, with an iodine value greater than 50
After this, by extraction at a temperature of for example 300 C, a second fraction is obtained with an
iodine value between 30 and 40 and a dilation at 200 C of more than 1200 The residue of the
extractions is a product with an iodine value preferably less than 10.
By varying the temperature, the duration, and the number of extractions it is possible to obtain a
middle fraction which is more or less similar to cocoa butter, as will be explained with reference to a
number of examples given below.
The process according to the invention may be employed, where appropriate, to prepare fat fractions
for use in the processes described and claimed in our co-pending Applications Nos.
16658/60 (Serial No 953,452); and 16659/60 (Serial No 953,453).
The invention includes a process in which chocolate is made by using a cocoa butter substitute made
in accordance with the invention in addition to or instead of cocoa butter.
The nature of the invention may be further appreciated by reference to the accompanying drawings in
which: Figure 1 is a diagrammatic drawing of apparatus suitable for carrying out the process of the
invention; Figure 2 is a graph comparing the dilatations of products according to the invention and
cocoa butter; and Figure 3 is a graph comparing the cooling curves of cocoa butter and a product
according to the invention.
Extraction Yield of the fat extract temperature after evaporation of Iodine value deg C acetone 2 46 5 g
72 2) 2 -553 26 % ( 1st extract) 7 69 9 7 14 7 g J 62 6 J 22 42 4 g = 36 90 % ( 2nd extract) 37 0
Residue 11 3 g = 9 83 % 7 4 953,451 EXAMPLE II g of palm oil with an iodine value of 50.8 and
containing 4 8 % of free fatty acids, calculated as palmitic acid, were slowly cooled to 10 C with
stirring.
The thick paste of crystals so obtained was applied as a thin film to the outer surface of a number of 1litre round-bottomed flasks and cooled further to 20 C The hard film of fat produced was scraped off
with a knife, as a result of which approximately 2 mm thick flakes were obtained.
g of these flakes were extracted at 20, 50, and 70 C, with a total quantity of 880 cc of acetone, the
material being slowly stirred during the extractions After each extraction the flakes and crystals
(liberated in the extraction) were allowed to settle for 15 minutes and the liquid was siphoned off The
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individual extracts were combined to form a first extract, and after evaporation of the acetone, 41 g of
oil (i e 63 1 %'I) with an iodine value of 64 6 were obtained.
The remaining flakes were subsequently extracted at 220, 250, 280, and 300 C with a total quantity of
780 cc of acetone to yield a second extract After evaporation of the acetone, this extract yielded 18 83
g of fat (i e.
29.01 %,/o of the palm oil) with an iodine value of 32 5 and a dilatation at 200 C of 1935 (see Fig 2),
the dilatations being determined after a standardised stabilisation of the fat according to the D G F
Einheitsmethoden C-IV 3rd ( 1957) The remainder of the crystals, after evaporation of the extracting
agent, amounted to 4 97 g (= 7 64 %') and had an iodine value of 4 5.
EXAMPLE III
Crude palm oil was cooled to 150 C with stirring and subsequently brought into the form of flakes by
cooling with brine at 10 C on a cooling drum.
g of these flakes were subjected to a series of extractions at 2 and 30 C After being stirred and
extracted, the flakes were filtered on a Biichner funnel and washed At C the extraction was performed
four times, the total quantity of extracting agent and washing liquor used being 1550 cc.
so The filtrate collected, forming a first extract, contained 114 5 g= 57 25 % of oil with an iodine
value of 68 0.
In order to obtain the cocoa butter substitute as a second fraction the solid material was extracted for
one hour with 200 cc of acetone at 300 C, filtered, and washed with 15 cc, followed by a second
extraction at 300 C with cc and washing with 15 cc The total quantity of acetone used was 330 cc.
After evaporation, a cocoa butter substitute fraction of 67 7 g= 33 85 %, with an iodine value of 33 7,
was obtained.
The residue amounted to 16 2 g= 8 1 %, with an iodine value of 5 8.
EXAMPLE IV
8 kg of crude palm oil were warmed with 38 1 of acetone mother liquor (the 70 C extraction of an
earlier run) to 400 C and subsequently crystallised by cooling to 20 C with stirring.
After siphoning off the clear liquid the crystals (almost 8 kg) were extracted three times for 20
minutes with 8 1 of acetone at 20 C.
After each extraction the material was allowed to settle for 15 minutes, upon which the clear liquids
were siphoned off The combined liquids, forming a first extract, contained 4848 g of oil = 60 8 % of
the palm oil, with an iodine value of 65 8.
After this, an extraction was performed four times with a total quantity of 37 1 of acetone at 70 C
Each extraction lasted 20 minutes.
The combined liquids formed a mother liquor, in which palm oil could be dissolved for a subsequent
run.
Three extractions were then made at 300 C, with a total duration of 135 minutes, and with 47 1 of
acetone From the liquids siphoned off as a second extract, 2292 g= 28 O % of cocoa butter substitute
were obtained, with an iodine value of 32 3 and a dilatation at 200 C of 1930 and at 300 C of 900 (see
Fig 2) Fig.
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3 shows the solidification curves of this substitute and of natural cocoa butter.
After evaporation, the residue consisted of 663 g of fat= 8 3 %', with an iodine value of 8.7.
EXAMPLE V kg of palm oil (iodine value= 52 2, percentage of free fatty acids 4 3) were crystallised
from 15 75 1 of mother liquor ( 60 C.
extract from a preceding run) to 1 50 C, after which the material was stirred for 45 minutes at this
temperature.
The crystals were filtered off on a large Bichner funnel and washed with 5 1 of acetone at 1 50 C A
layer of crystals 4 cm deep was obtained, using suction such that the pressure difference was 120 mm
Hg The crystals about 5 kg were subsequently returned to the crystalliser and extracted at 20 C for 30
minutes with 6 5 1 of acetone with stirring, after which they were filtered off again on the Bichner
funnel and washed once more with 5 1 of acetone at 20 C.
From the combined filtrates and wash liquors forming a first extract, 2978 g of oil ( 59 56 %) with an
iodine value of 66 8 were obtained.
The crystals were subsequently extracted with 10 1 of acetone at 60 C for 45 minutes After being
filtered off on the Bfichner funnel, they were washed with 5 1 of acetone at 60 C The filtrate and wash
liquor formed the liquid from which a new charge of palm oil was subsequently crystallised.
After the crystals had been removed from the filter, they were extracted for 45 minutes with 7 5 1 of
fresh acetone and 2 1 of a wash 953,451 953,451 liquor M 2 from a previous run, prepared as described
below, at 300 C.
After filtration, the crystals were washed once with 1 25 1 of fresh acetone at 300 C, the wash liquor
being added to the extract of this temperature to form a second extract.
The crystals were then washed again with 2 1.
of acetone, which was kept as wash liquor M 2 for a subsequent experiment.
From the second extract, 1607 g= 32 141 % of cocoa butter substitute were obtained, with an iodine
value of 32 8 and a dilatation at 200 C of 1940 After evaporation of the solvent the residue on the filter
amounted to 386 g= 7 72 %, with an iodine value of 7 1.
EXAMPLE VI g of palm oil were crystallised from 600 cc of acetone at -20 C The crystals were
filtered off on a cooled Biichner funnel at -20 C and washed with cc of acetone at 2 C The thickness
of the layer of crystals was about 3 cm The crystals filtered very well at a pressure difference of 10 to
12 mm Hg.
The crystals were subsequently extracted with 250 cc of acetone on the B Uchner funnel at 20 C The
filtrate was then passed through the crystals another four times so that the crystals were extracted five
times The filtrate formed a first extract.
The crystals were then washed with 200 cc of acetone Subsequently they were extracted with 425 cc
of acetone at 6 50 C at a pressure difference of 22 mm Hg and the filtrate was again passed through the
crystals another four times The crystals were then washed once more with 200 cc of acetone at 6 50 C
The filtrate and wash liquor at 6 50 C formed a liquid from which a further 200 g of palm oil could be
crystallised for a subsequent run.
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Without being removed from the filter, the crystals were now extracted with 375 cc of acetone of 300
C five times, as in the previous extraction The extraction took place at a pressure difference of 120 r
mm Hg The crystals were washed once more with 50 cc of acetone at 300 C From the combined filtrate,
forming a second extract, 57 4 g of substitute was obtained, with an iodine value of 32 2 and a
dilatation at 200 C of 1835 The residue on the filter, after evaporation of the solvent, amounted to 14 6
g with an iodine value of 8.4.
EXAMPLE VII
Chocolate was made according to the following formulations:
A 182 g of cocoa liquor (containing about 56 % of natural cocoa butter) 180 g of sugar 38 g of cocoa
butter substitute, made in accordance with Example IV, but having an iodine value of 31 9, and a
dilatation at 200 C of 1950; percentB age of substitute in the total fat in the chocolate = 27 % 112 g of
cocoa powder with 111 %, of cocoa butter 225 g of sugar 87 g of substitute, as in A g of cocoa butter
percentage of substitute in the total fat in the chocolate= 50 %, C 112 g of cocoa powder with 11 % of
cocoa butter fat 225 g of sugar 163 g of substitute, as in A.
percentage of substitute in the total fat in the chocolate = 93 %, In each case, the ingredients were
thoroughly mixed at 600 C in a mortar The mixture was cooled, with constant stirring, until it was
almost solid and the paste was subsequently 85 placed for 1 hour in a stove at 320 C The chocolate mix
was then poured into moulds and placed for 2 hours at 110 C in a refrigerator After being stored for 2
days at room temperature, the chocolate was judged g 9 for fracture, appearance, and melting
characteristics in the mouth In all three cases the fracture, the appearance, and the melting
characteristics in the mouth were satisfactory.Data supplied from the esp@cenet database - Worldwide
Claims:
Claims of GB953451
WHIAT WE CLAIM IS: 95
1 A process for the preparation of a cocoa butter substitute in which at least one fat containing at least
one of the mono-unsaturated di-saturated triglycerides of palmitic and/or stearic acid and oleic acid in a
solid or semi 100 solid extractable form is extracted whilst still solid or semi-solid in a first step in one
or more stages at a temperature between 5 and + 100 C with a total number of cubic centimetres of
acetone that is from twice to twenty 105 times as great as the number of grams of fat, this first extract
containing a low-melting fraction of the fat is removed, the residue is extracted in a second step in one
or more stages at a temperature between 10 and 350 C with a 110 total number of cubic centimetres of
acetone that is from one to fifteen times as great as the number of grams of fat originally taken to yield
a second extract containing the monounsaturated di-saturated triglyceride as the 115 cocoa butter
substitute and a second residue including high-melting triglycerides, and the cocoa butter substitute is
recovered by evaporation of the acetone from the second extract.
2 A process according to claim 1 in which 120 the solid or semi-solid fat is in the presence of a carrier.
3 A process according to claim l or claim 2 in which either or both of the extraction steps is carried
out in two or more operations 125 at successively increasing temperatures.
4 A process according to any one of the preceding claims in which either or both of the 953,451
extraction steps is carried out by countercurrent extraction in several stages.
A process according to any one of the preceding claims in which the extractions are carried out with
the fat supported on a horizontally-moving filter.
6 A process according to any one of the preceding claims in which the fat used is palm oil.
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7 A process for producing a cocoa butter substitute substantially as herein described in any one of the
Examples I-VI.
8 A cocoa butter substitute produced by a process according to any one of the preceding claims.
9 A process for the preparation of chocolate which comprises using a cocoa butter substitute produced
by the process of any one of claims 1 to 7 in addition to or instead of cocoa butter.
Shaped chocolate products obtained by the process according to claim 9.
For the Applicants:
GILL, JENNINGS & EVERY, Chartered Patent Agents, 51/52, Chancery Lane, London, W C 2.
Leamington Spa: Printed for Her Majesty's Stationery Office, by the Courier Press (Leamington) Ltd 1964 Published by The Patent Office, 25 Southampton Buildings, London W C 2, from which copies
may be obtained.Data supplied from the esp@cenet database - Worldwide
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30. GB954241 - 2/4/1964
PROCESS FOR THE PRODUCTION OF READY-FOR-USE SOUPS AND
SAUCES IN POWDERED FORM
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=GB954241
Applicant(s):
KOOPMANS MEELFABRIEKEN N V (--)
IP Class 4 Digits: A23L
IP Class:A23L1/39
E Class: A23L1/39
Application Number:
GB19610017297 (19610511)
Priority Number: GB19610017297 (19610511)
Family: GB954241
Abstract:
Abstract of GB954241
Soup and sauce powders which comprise fat and insoluble and soluble non-fatty constituents and
which disperse readily in hot or cold liquid are made by melting the fat, blending the insoluble
constituents with the molten fat to form a uniform paste, allowing the paste to harden by cooling,
grating the hardened paste, and mixing the gratings with the soluble constituents. The process allows
the use of rapid-swelling ingredients such as potato flour and alginates without agglomeration on
adding the liquid. Examples are of making (1) a tomato soup preparation by incorporating a melted
arachis oil with soyabean lecithin at 60 DEG C into a mixture of potato flour and potato and tomato
powders, moulding to slabs and hardening at 10 DEG C, grating the slabs through a 1-3 mm. hole
rotary grater, and enveloping the gratings in a mixture of skim milk powder, sodium chloride,
monosodium glutamate, sugar, pepper, citric acid and onion powder (2) an oxtail soup preparation by
incorporating a melted fractionated palm oil with soyabean lecithin and soya sauce at 60 DEG C into a
mixture of tomato, carrot, turnip, onion, leek and parsley powders and meat extract in potato flour,
moulding to a slab, allowing to cool and harden, grating, and mixing the gratings with a mixture of a
meat extract-lactose preparation, skim milk powder, sodium chloride, monosodium glutamate, pepper
and curry, garlic, laurel and clove powders (3) a Julienne soup preparation by incorporating a melted
hydrogenated cottonseed oil at 60 DEG C into a mixture of potato flour, solubilized starch, mixed
vegetables in powdered form and soyabean lecithin, moulding to a slab, allowing to cool and harden,
grating, and mixing the gratings with a mixture of a meat extract on lactose preparation, skim milk
powder, sodium chloride and monosodium glutamate.Description:
Description of GB954241
PATENT
SPECIFICATION
NO DRAWINGS 954,241 Date of Application and filing Complete Specification May II, 1961.
No. 17297/61.
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Application made in Netherlands (No. 5794) on May 20, 1960.
Complete Specification Published April 2, 1964.
Crown Copyright 1964.
Index at acceptance: -A2 B(1C, IF, 1H, 1J, 1R, is, IT) International Classification: -A 23 b, d, I
COMPLETE SPECIFICATION
Process for the Production of Ready-for-use Soups and Sauces in Powdered Form We, KOOPMANS
MEELFABRIEKEN N.V., a Dutch Body Corporate, of 3 de Merodestraat, Leeuwarden, Holland, do
hereby declare the invention, for which we pray that a patent may be granted to us, and the method by
which it is to be performed, to he particularly described in and by the following statement: The present
invention relates to a process O10 for the production of ready-for-use soups and sauces in powdered
form, from which the ready-for-use dish can be prepared by immediate dispersion of the constituents in
a hot or cold liquid.
Soups and sauces in powdered form are mixtures of various ingredients, among which may be
mentioned different types of flour, solubilized starches, powdered or chopped vegetables, meat extracts,
sugar, salt, fat, oil and spices. The products of this type now known and used are known to have the
disadvantage that it is difficult to disperse them in hot or boiling water because they give rise to the
formation of lumps, which can only be eliminated by careful rubbing or sifting. For this reason it is
recommended by manufacturers of these products first to disperse the products in a small quantity of
cold water, subsequently to add the mixture to hot or boiling water, and then to boil it for a more or less
prolonged period. It will be evident that such a method of preparation does not meet present-day
requirements, since there is now a marked tendency to use foodstuffs which are at once ready for
consumption. Such products accordingly cannot be used in slot machines, in which they have to be
distributed immediately in hot water, without being previously dispersed or subsequently boiled.
Experiments carried out by the applicants have shown that the said disadvantage is due to the fact that
some of the constituents of such products, in particular those which have to act as binders, will swell
very rapidly in hot water, so that the particles will stick together before they get chance to be dispersed
in water. From these experiments it may be concluded that it would be possible to avoid clotting or
lump formation by dispersing the powder very gradually in hot water, with very thorough mixing. In
order to prevent the formation of large agglomerates as the powdered product comes into contact with
the hot liquid, binders are used which consist of less rapidly swelling constituents, which only reach the
fully hydrated state after a more or less prolonged period, in view of which the product has to be boiled.
Various methods have been proposed for improving the dispersion of such products in hot water. A
method according to which the particles that are capable of swelling are enveloped in a fatty substance
makres it possible to retard the hydration of the particles and consequently to improve their dispersion,
if the fatty substance used is one with a high melting point. Unfortunately, fatty substances with a high
melting point are unacceptable from a physiological and organoleptical point of view, so they cannot
be used in products of this kind. The granulation method, which is applied advantageously in order to
improve the dispersion of the given products in a liquid, does not prevent the formation of lumps in hot
water. This is due to the fact that the granules are too compact and the ratio between area and weight is
too small for the area coming into contact with water to ensure rapid dispersion of the constituents
present in the granules.
The process according to the invention differs from the known methods in that the fatty constituents
are caused to melt, upon which they are intimately mixed with all the insoluble constituents in such a
way that a P.W NR 954,241 practically homogeneous paste is obtained, the paste then being allowed to
harden and subsequently being converted into gratings, whicli are mixed with the soluble constituents.
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According to this process therefore gratings are first prepared, which contain constituents capable of
swelling, to which the formation of lumps is due, and fatty constituents, upon which they are mixed
with all the soluble constituents. The specific area of such gratings is very large, which favours a rapid
dispersion of the constituents, accrding as the melting of fatty constituents. The distance between the
swelling constituents in a chip of gratings is so great that they are dispersed before a lump can be
formed from the chip itself.
The powdered soluble constituents, such as salt, monosodium glutamate, sugar and milk powder,
which in combination with the gratings from the final product, prevent mutual agglomeration of the
chips of gratings and owing to their solubility permit very rapid moistening of the chips over their
entire surface.
To facilitate the grating process, it is preferable to mould the paste into a cake before the hardening
process. The cake can be formed by compression in an alternatively or a continuously operating press.
In order to ensure favourable hardening, it is necessary to cool the cake at a temperature below 15 C.
Grating obtained with the aid of graters having holes with a diameter between 1 mm and 3 mm
produce the best results.
The process according to the invention may, for instance, be carried out as follows.
EXAMPLE I
CREAM OF TOMATO SOUP The following mixture is started from:
95 g of potato flour g of potato powder g of tomato powder When the mixture is thoroughly
homogeneous, 90 g of alimentary fats (hydrogenated arachid oil M.P. 40 C), molten at a temperature of
60 C and containing 1 g of soyabean lecithin, are incorporated therein.
After thorough mixing and kneading, a plastic mass is obtained, which is moulded into cakes or slabs,
and cooled (to about 10 C). The hardened cakes are grated with a rotary grater (cheese-grater type)
(diameter of the holes: 1-3 mm).
The gratings thus obtained are enveloped in a powdered mixture having the following composition:
84 g of skim milk powder g of NaCI g of monosodium glutamate 20 g of crystallised sugar mg of white
pepper mg of citric acid 400 mg of onion powder The product obtained is a granular powder.
It can be dispersed equally well in hot or 65 in cold water.
EXAMPLE II
OXTAIL SOUP A mixture is prepared from the following powdered ingredients: 70 g of tomato
powder g of carrot powder g of turnip powder g of onion powder g of leek powder 75 2.5 g of parsley
powder g of meat extract bound to potato flour.
In this mixture, are incorporated homogeneously 150 g of alimentary fats molten at 80 6GC
(fractionated palm oil M.P. 38 C) and containing 2 g of soyabean lecithin and 10 g of soya sauce. From
this mass a cake is formed, which is allowed to cool and grated, alter which the gratings thus obtained
are 85 mixed with the following mixture:
g of meat extract ("Liebig meat extract" registered Trade Mark) bound to lactose g of skim milk
powder 90 g of NaCI g of monosodium gluatamate mg of pepper mg of curry powder mg of garlic
powder 95 mg of laurel powder mg of clove powder.
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A product is obtained in the form of a granular powder, which can be immediately dispersed in a
liquid. 100 EXAMPLE III
JULIENNE SOUP A mixture is prepared, consisting of:
56 g of potato flour 12 g of solubilized starch 105 28 g of mrrixed vegetables in powdered form 0.4 g
of soyahean lecithin.
In this mixture are incorporated 40 g of alimentary fats, molten at a temperature of I10 about 60WC
(hydrogenated cotton seed oil M.P. 41 C), then a cake is formed and the latter is cooled and grated over
the following mixture:
11 g of meat extract ("Liebig meat extract" registered Trade Mark) bound to lactose 54 g of skim milk
powder 17 g of NaCI 2 g of sodium glutaminate. 120 When the gratings have been thoroughly mixed
with the powder, a homogeneous granular product is obtained, which forms the complete ready-for-use
soup which can be dissolved immediately in a liquid. 125 According to the process of the invention it is
possible to use constituents which swell hardened paste is grated and the gratings mixed with the
soluble constituents.
2. A process as claimed in claim 1, wherein the paste is allowed to harden at a temperature below 15
C.
3. A process as claimed in claim 1 or claim 2, wherein the paste is moulded into a cake before its fatty
constituents have been hardened.
4. A process as claimed in any of claims 1 to 3, wherein the cake is formed by compression in a
batchwise or a continuously operating press.
5. A process as claimed in any of claims 1 to 4, wherein a rotary grater is used, having holes with a
diameter of from between 1 mm and 3 mm.
6. A process for the production of ready-foruse soups and sauces in powdered form, substantially as
hereinbefore described.
KOOPMANS MEELFABRIEKEN N.V.
Per: Boult, Wade & Tennant, 111/112, Hatton Garden, London, E.C.1.
Chartered Patent Agents.
very rapidly, such as potato flour and alginates, without forming large agglomerates when coming
into contact with a liquid. Because the complete hydration of the constituents is thus attained very
rapidly, the boiling period of such products is practically reduced to the period required for dispersion,
so that these products are really ready-for-use products.Data supplied from the esp@cenet database Worldwide
Claims:
Claims of GB954241
WHAT WE CLAIM IS:1. A process for the production of readyfor-use soups and sauces in powdered form, consisting of
edible fats, insoluble and soluble non-fatty constituents from which the ready-for-use dish is obtained
by immediate dispersion of the constituents in a hot or cold liquid, characterised in that the proportion
of edible fat to be used is caused to melt and is subsequently blended intimately with all the insoluble
constituents, so that a practically homogeneous paste is obtained, which is allowed to harden by
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cooling, after which the Leamington Spa: Printed for Her Majesty's Stationery Office by the Courier
Press.-1964.
Published at The Patent Office, 25, Southampton Buildings, London, W.C.2, from which copies may
be obtained.
954,241Data supplied from the esp@cenet database - Worldwide
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31. GB971022 - 23/9/1964
IMPROVEMENTS IN OR RELATING TO MARGARINE
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=GB971022
Inventor(s):
PARDUN HERMANN (--)
Applicant(s):
UNILEVER LTD (--)
IP Class 4 Digits: A23D; A23L
IP Class:A23D7/005; A23L1/20
E Class: A23D7/005N; A23D7/005S; A23L1/20D4
Application Number:
GB19610015992 (19610503)
Priority Number: GB19610015992 (19610503)
Family: GB971022
Equivalent:
US3245802; CH425431
Abstract:
Abstract of GB971022
A non-spattering milk margarine, preferably, de-aerated, contains, as an anti-spattering agent, a small
proportion, e.g. 0.2 to 1.2% by weight of the fat content, of de-bittered soya bean flour, e.g.
substantially free from oil, in which the protein matter is not substantially denatured. The de-bittered
soya bean flour may be added, during the preparation of the margarine, to the fatty phase, the aqueous
phase or to the emulsified mixture thereof. The fatty phase may contain the following substances, in
parts by weight:- 25 cottonseed oil, 40 coconut oil, 25 hardened cottonseed oil (M.P. 32 DEG -34 DEG
C.), 5 palm oil, 5 hardened palm oil (M.P. 40 DEG -42 DEG C.), 0.4 fatty acid mono-diglycerides, 0.4
lecithin. The aqueous phase may contain 25%, by weight of acidified milk and may comprise 19.8% of
the weight of margarine. In making the de-bittered soya bean flour, washed soya beans containing
8.5%, by weight, of water are steamed for 20 minutes at 100 DEG C. and are then de-hulled and dried,
at 65 DEG C. under reduced pressure, until they attain their original water content. they are then
ground to pass a sieve having 50 meshes per cm. The resulting flour may be treated with ethanol or
hexane to extract oil and then dried to yield a de-bittered flour substantially free from oil. Specification
614,593 is referred to.Description:
Description of GB971022
PATENT SPECIFICATION
NO DRAWINGS Inventor: HERMANN PARDUN.
Date of filing Complete Specification: May 1, 1962.
Application Date: May 3, 1961.
Complete Specification Published: Sept 23, 1964.
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g) Crown Copyright 1964.
971,022 No 15992:61.
Index at acceptance:-A 2 B 12; A? Q ( 5 A, 7 A, 7 B, 13, 14 X, 16 D, 16 X, 17) International
Classification:-A 23 d (A 21 d) COMPLETE SPECIFICATION
Improvements in or relating to Margarine We, UNILEVER LIMITED, a Company registered under
the laws of Great Britain, of Port Sunlight, in the County of Chester, England, do hereby declare the
invention for which we pray that a patent may be granted to us and the method by which it is to be
performed, to be particularly described in and by the following statement:This invention relates to soya bean products and to margarine and provides a new kind of margarine
having improved frying properties.
In margarine the aqueous phase may or may not be derived from milk A milk-margarine contains
proteins derived from the milk which improves the frying properties of the margarine in one respect in
that they play a part in the formation, during frying, of a brown, very fine powder of pleasant aroma
which is much valued.
It is known, with a view to imparting this browning property on frying to water-margarine to
introduce proteins, for instance in the form of defatted soya flour, groundnut protein and glutencontaining wheat flour.
(Defatted soya flour is made, as described by K S Markley in Volume II, page 956 " Soya Beans and
Soya Bean Products " by dehulling soya beans, comminuting the dehulled product and forming it into
flakes by passage between fluted r o 11 e r s, extracting with solvent, e v a p o r a t i N g the solvent
from the extracted residue under normal or reduced pressure and at the same time removing bitter
flavour c o N S t i t u e N t S and finally cooling the residue in an air stream, drying it and reducing it to
to a fine powder).
Another frying property which is much desired in margarine is the ability to lose its water during
frying without spattering.
In a water-margarine this property can be imparted to some degree by incorporating lecithin The
addition of lecithin to a milkmargarine, on the other hand, does not greatly reduce its tendency to
spatter, apparently lPrice 4 owing to some interaction between lecithin and the milk protein Reduction
of the tendency of milk-margarine to spatter has, in consequence, presented a problem to which many
solutions, none altogether satisfactory, have been proposed.
It has now been found, contrary to expectation, that the tendency of milk-margarine to spatter can be
greatly reduced by incorporating small proportions (for instance 0 1 to 1 5 % based on the weight of
fat) of debittered, that is disembittered, finely divided soya bean material, (referred to below as "
debittered soya bean flour "), in which the protein is not denatured to a substantial extent Especially
good results are obtained when the debittered soya bean flour is substantially free from oil The addition
of this soya bean material is effective even when the margarine has been de-aerated so as to contain
less than 5 % of even less than 0 5 % of its volume of air, which increases its tendency to spatter.
The present invention, therefore comprises milk-margarine having a reduced or negligible tendency to
spatter in frying owing to the presence therein of a small proportion (preferably 0 2 to 1 % of the
weight of the fat) of the said debittered soya bean flour, and the manufacture of such margarines by
incorporating the debittered soya bean flour at a suitable stage of manufacture as set out below.
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In the preferred method of making the debittered soya bean flour, soya beans of good quality are
debittered by mildly heating the beans with hot water, steam or other hot gases in the presence of
moisture, during which treatment alkaline or acid reacting compounds may be present.
Next the soya beans are dehulled, dried and ground The activity of the additive is improved if the
debittered soya beans before or after the grinding, are extracted with fat solvents, for example lowboiling hydrocarbons, alcohols and ketones.
In margarines according to the invention the fat phase may be of conventional composition Preferably,
as is usual, it contains small proportions of fatty acid mono-diglycerides and lecithin but these are not
essential.
The aqueous phase (apart from its contents of debittered soya bean flour) may also be of a
composition conventional for milk margarines.
The debittered soya bean flours obtained as described above can be added, during the margarine
preparation, to the aqueous phase, the fat-phase or to the emulsion itself Preferably they are added to an
aqueous liquid which is to form the aqueous phase, or part thereof, the p H of that liquid being adjusted
if necessary to within the range 4 5 to 5 The debittered soya bean flours are preferably used in
conjunction with emulsifiers such as lecithin and fatty acid mono-diglycerides Generally the said soya
bean flour is suspended in a part of the aqueous liquid and the suspension obtained is pasteurised after
the p H is adjusted to the desired value.
It has been proposed in British Patent Specification No 614,593 to add to margarine 0 1 to 1 /( by
weight of a composition containing a vegetable phosphatide together with 0 1 to 1/ of its weight of
soluble soya protein Such compositions are very different in constitution from the debittered soya bean
flours used in the present invention, especially in that the amount of vegetable protein they contain is
very small As will be shown below they are much less effective as anti-spattering agents for milkmargarine than the said debittered soya bean flours.
The following Examples 1 to 3 illustrate the preparation of debittered soya bean flour for use in the
invention.
Debittered soya bean flours were obtained according to the following methods:
EXAMPLE 1.
Washed soya beans with a water content of 8 5,0/, by weight, were steamed during 20 minutes at 100
C; after this treatment the water content of the beans was 10 5 /- Thereafter the beans were dehulled,
dried in vacuum at 65 C to the original water content and ground to pass a sieve of 50 meshes/cm.
E Xa NMPLE 2.
Soya beans were treated as described in Example 1 The powder obtained was thereafter extracted with
960/% by volume ethanol till it was substantially free from oil and again dried.
EXAMPLE 3.
Soya beans were treated according to Example 1 The powder obtained was extracted with technical
hexane until the oilcontent of the product was lower than 11.
EXAMPLES 4 r TO 6.
These examples illustrate the preparation of margarine according to the invention.
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Samples of de-aerated margarine containing different proportions, ranging from 0 2 to 1 2/, by weight
of the fat-content, of different debittered soya bean flours were prepared in the usual way on a Votator
(registered Trade Mark) The debittered soya bean flours used in Examples 4 to 6 were made according
to Examples 1 to 3 respectively The debittered soya bean flour was suspended in an aqueous liquid of
the composition given below, which was adjusted to a p H value of 4 5 with citric acid The fatty phase
of the margarine had the following composition, the parts being by weight:
parts of cottonseed oil parts of coconut oil parts of hardened cottonseed oil (M P.
32 34 C) parts of palm oil parts of hardened palm oil (M P.
' 42 o C) 0.4 parts of fatty acid mono-diglycerides 0.4 parts of lecithin.
In all the margarines the aqueous phase (apart from an additive as specified in Table I below)
contained 25-/, by weight of acidified milk, the remainder being water and minor amounts of
conventional watersoluble flavouring agents All the margarines contained 19 8-/ by weight of the
aqueous phase.
All samples were completely de-aerated.
The resulting margarines were tested 24 hours after the debittered soya bean flour was added to the
aqueous phase during their preparation, as described below.
A pan with a diameter of 18 cm was preheated to 200 C A sheet of filter-paper was fixed horizontally
20 cm above the bottom of the pan 50 g of margarine was put into the pan and heated until the
evaporation of water had ceased Spattered fat was caught by the filter-paper, forming more or less
coherent fat spots on it The extent of thse fat spots is a measure of the spattering The anti-spattering
property of the margarines of these examples as shown by the test referred to and of a similar
margarine made with egg yolk in place of the debittered soya bean flour is indicated in Table I below
by ratings having the following significance:=excellent 8 =good 6 = sufficient 4 = insufficient 2 =very
bad 971,022 971,022 TABLE I
Proportion of additive (g /1000 g of fat) Nature of additive O 2 4 8 1 12 Anti-spattering rating Egg
Yolk 1 1 2 4 5 Product of Example 1 1 4 5 7 9 Product of Example 2 1 10 10 10 10 Product of Example
3 1 10 10 10 10 Table II below shows the results of applying the test described above to margarines
containing:
A The composition of British Patent Specification No 614,593, Example VI,
No 4 in the proportions specified in the first column of the Table; B Soya lecithin in the proportions
specified in the first column; C Debittered soya bean flour in the proportions specified in the first
column plus 2 g /1000 g of fat of lecithin.
The margarines were all made from the fat blend used in Examples 4 to 6 and contained 19 8 % by
weight of an aqueous phase containing 25 ^-/ by weight of acidified milk and an additive of the kind
and in the amount specified in Table II, the remainder being water and minor amounts of conventional
water-soluble flavouring agents The margarines were de-aerated.
TABLE II ฆ Additive in g I 11000 g of Anti-spattering rating of Iฆ of fat A B C 0 1 1 1 1 1 3 9 2 1 4
10 4 10 7 6 L These results illustrate the considerable advantage obtained by the use of the debittered
soya bean flour plus lecithin over both lecithin alone and the compositions of the British Patent
Specification referred to, even when the last two are used in relatively high proportions.
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Similar inferior results were obtained in trials with the sodium globulinates which are mentioned in
the aforementioned British Patent Specification.Data supplied from the esp@cenet database Worldwide
Claims:
Claims of GB971022
WHAT WE CLAIM IS:
1 A milk margarine having a reduced or negligible tendency to spatter in frying due to the presence
therein of a small proportion of a debittered soya bean flour in which the protein is not denatured to a
substantial extent.
2 A margarine according to Claim 1, wherein the debittered soya bean flour is substantially free from
oil.
3 A margarine according to Claim 1, wherein the debittered soya bean flour has been made by
debittering soya beans with hot water or steam, or with hot gases in the presence of moisture, dehulling
and drying the beans, followed by grinding.
4 A margarine according to Claim 3, wherein before or after grinding, the soya bean material has been
extracted with a solvent for fats.
A margarine according to Claim 4, wherein said solvent is ethanol.
6 A margarine according to Claim 4, wherein said solvent is a low-boiling hydrocarbon.
7 A margarine according to any of Claims 1 to 6, containing also a small proportion of lecithin.
8 A margarine according to any of Claims 1 to 7, containing also a small proportion of fatty acid
mono-diglycerides.
9 A margarine according to any of Claims 1 to 8 which has been de-aerated.
Process for making a margarine claimed in any of Claims 1 to 9, wherein the debittered soya bean flour
is added to the aqueous phase before or during the emulsification step.
11 Process according to Claim 10, wherein the p H of the aqueous phase containing the debittered
soya bean flour is within the range 4.5 to 5.
12 Process for making a milk margarine substantially as described in any of Examples 4 to 6.
13 Milk margarines substantially as described in any of Examples 4 to 6.
UNILEVER LIMITED.
R JONAS.
Agent for the Applicants.
Leamington Spa: Printed for Her Majesty's Stationery Office by the Courier Press (Leamington) Ltd 1964 Published by the Patent Office, 25 Southampton Buildings, London, W C 2 from which copies
may be obtained.
971,022Data supplied from the esp@cenet database - Worldwide
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32. GB993308 - 26/5/1965
IMPROVEMENTS IN OR RELATING TO DIETARY PRODUCTS
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=GB993308
Inventor(s):
GOWER LESLIE JOHN (--); CLEAVER DAVID FREDERICK (--)
Applicant(s):
PFIZER LTD (--)
IP Class 4 Digits: A21D; A23L
IP Class:A21D2/18; A21D2/26; A21D13/00; A23L1/308; A21D2/00
E Class: A21D13/00D4; A21D2/18; A21D2/26B; A23L1/308
Application Number:
GB19610003851 (19610201)
Priority Number: GB19610003851 (19610201)
Family: GB993308
Abstract:
Abstract of GB993308
Sandwich biscuits for a restricted calorie diet comprise layers from a farinaceous mixture filling of a
finely-divided bulking agent, e.g. sodium carboxymethyl cellulose, methyl cellulose, p sodium alginate,
psyllium, carrageenin, agar or guar gum and a carbohydrate, e.g. starch, sucrose, glucose, dispersed in a
fatty matrix. Protein of the farinaceous mixture may be supplemented by casein or egg albumen.
Examples are concerned with (1) baked layers of a mixture of soya, white and wholemeal flour, malt
extract, sucrose, golden syrup, margarine, palm kernel oil, lard, dried milk, dibasic calcium phosphate
and reduced iron and a filling of a paste of deodourized coconut oil, sucrose, sodium carboxymethyl
cellulose, dibasic calcium phosphate, a mix containing Vitamin A, Vitamin B1, Vitamin B2, Vitamin D,
nicotinamide and ascorbic acid, and if desired flavouring and colouring, (2) baked layers of a mixture
of soya, white and wholemeal flours, sucrose, malt extract, golden syrup, margarine, palm kernel oil,
lard, dried milk and reduced iron and a filling of a paste of hydrogenated palm kernel oil, maize starch,
sodium carboxymethyl cellulose, dibasic calcium phosphate, full fat soya flour, spray-dried yeast
extract, synthetic cheese flavour, methionine and the vitamin mix of Example 1.Description:
Description of GB993308
PATENT SPECIFICATION
NO DRAWINGS ๚htctr: LESLIE JOHN GOWER and DAVID FREDERICK CLEAVER Date of
filing Complete Specification April 30, 1962.
Application Date Feb.!, 196,.
Complete Specification Published May 26, 1965.
) Crown Copyright 1965.
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993,308 No. 3851/61 Index at acceptance: -A2 B(IB, 1C, 1G, 1H, 1K,]L, IS, IW) It_( Cl.:-A 21 d 13/06
COMPLETE SPECIFICATION
Improvements in or relating to Dietary Products PATENTS ACT 1949 SPECIFICATION NO 993308
in accordance with the Decision of the Superintending Examiner, acting Comptroller-General, dated 22
January 1974 this Specification has been
Section 33 in the following manner:for the amended under Page 1, line 46, page 3, line 8, after fat
delete full stop insert, and the biscuits themselves containing no bulking agent.
TE PATENT OFFICE 23 A4pril 1974 o01 emptiness, nausea bowel rhythm.
By virtue of their same other effect, va act systemically, sui phenmetrazine, thyroic tracts and diuretics,
h use'/n bringing about ever, though they ma' inl weight. most if no have powerful side efl
sleeplessness, emotions tion), and their use ac supervision by a phy The present invent:
of bulking agents to agents are hvYdratable function by swelling t stomach or intestines mass that gives
a feening o tion of this bulky mass als bowel function.
According to the invenrti vided a dietary product ir sandwich of two or more bis a farinaceous mixture.
the fi carbohydrate and a finely [Price ERRATA SPECIFICATION No. 993,308
Amendment No. 1 Page 1, line 42, after "mixture," insert "and filling," Page 2, line 53, for
"carboxylmethyl" read "carboxymethyl" THE PATENT OFFICE 23rd rune 1965 n assists normal
tively, if a less sweet product is desired, a starch may be employed as carbohydrate.
on there is pro- Examples of suitable bulking agents are n the form of a methyl cellulose, sodium
carboxymethyl cellucuits formed from lose, psyllium, guar gum, sodium alginate, lling comprising a
agar, pectin, and caragenin, the cellulose divided bulking derivatives being particularly preferred.
O-E.E. EPJ,, ': i t A-.,.&.TigL, m SO E PATENT SPECIFICATION
NO DRAWINGS Invsutor: LESLIE JOHN GOWER and DAVID FREDERICK CLEAVER Date of
filing Conmplete Specification April 30, 1962.
Application Date Feb.!, 1961.
Complete Specification Published May 26, 1965.
Crown Copyright 1965.
9939308 No. 3851161 Index at acceptance: -A2 B(1B, IC, IG, 111, 1K, IL, IS, IW) Int Cl.:-A 21 d
13/06 COMPLETE SPECIFICATION
Improvements in or relating to Dietary Products We, PFIZER LIMITED, a British Company, of
Ramsgate Road, Sandwich, Kent, do hereby declare the invention, for which we pray that a patent may
be granted to us, and the method by which it is to be performed, to be particularly described in and by
the following statement: This invention relates to dietary products, that is, products usable in a restricted calorie diet.
Many people who are above average weight can lose weight if they adhere to a diet whose calorific
value is restricted. Conventional foodstuffs of low calorific value are available for such use, but to rely
en a diet based on these foodstuffs can lead to a feeling of emptiness, nausea and a disturbance of
bowel rhythm.
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By virtue of their appetite-depressant or some other effect, various substances which act systemically,
such as amphetamines, phenmetrazine, thyroid extracts, pituitary extracts and diuretics, have been
suggested for use in bringing about a loss in weight. However. though they may be effective in
reducing weight, most if not all of these substances have powerful side effects (they may produce
sleeplessness, emotional disturbance or addiction), and their use accordingly requires close supervision
by a physician.
The present invention utilises the capacity of bulking agents to reduce appetite. Such agents are
hydratable colloidal substances and function by swelling through hydration in the stomach or intestines,
so producing a bulky mass that gives a feeling of fullness; formation of this bulky mass also assists
normal bowel function.
According to the invention there is provided a dietary product in the form of a sandwich of two or
more biscuits formed from a farinaceous mixture, the filling comprising a carbohydrate and a finely
divided bulking [Price agent dispersed throughout a fatty matrix, the bulking agent being substantially
insoluble in the fat.
The dietary prcduct may consist of two biscuits with filling between them, or it may take the form of a
multi-layer sandwich, in which two or more layers of filling are separated by and contained between
biscuits. The biscuits may take the form of conventional wholemeal biscuits. Advantageously the
texture of the biscuits is such that they require thorough chewing before they can comfortably be
swallowed. Mastication leaves the particles of bulking agent exposed for hydration, which thus begins
in the saliva produced during chewing and continues in the stomach fluids.
The farinaceous mixture from which the biscuits are formed may contain ingredients, such as casein
and egg albumen, that supplement the protein content of the flour employed. The mixture may also
contain other nutritional ingredients, such as physiologically acceptable amino acids, malt extract,
vegetable oil and calcium phosphate and ferrous salts or other mineral salts providing calcium,
phosphorus and iron.
The filling comprises a carbohydrate and a finely divided bulking agent dispersed throughout a fatty
matrix.
The carbohydrate may be a sugar, such as glucose or sucrose. These are relatively rapidly
metabolisable, so that after ingestion of the dietary product a rise in the level of the blood sugar occurs
quickly, so Dhysiologically depressing the appetite. Alternatively, if a less sweet product is desired, a
starch may be employed as carbohydrate.
Examples of suitable bulking agents are methyl cellulose, sodium carboxymethyl cellulose, psyllium,
guar gum, sodium alginate, agar, pectin, and caragenin, the cellulose derivatives being particularly
preferred.
SEE ERE' 2Ai- A? A2 ED 00 c:
e:
j.I The fat (i.e. edible glyceride of a higher fatty acid) constituting the fatty matrix is preferably a
vegetable fat, such as coconut oil or palm kernel oil.
Dispersion of the bulking agent in finely divided form in the fatty matrix (as distinct from a cooked
dough matrix, such as a biscuit forms) renders the bulking agent more thoroughly hydratable, and its
swelling capacity is accordingly more effectively utilised.
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Apart from the carbohydrate, bulking agent and fat, the filling may also contain vitamins, mineral
salts and flavours. If desired, enough vitamins and mineral salts can be incorporated in the product as a
whole to ensure that it is sufficient to supply substantially all the nutritional requirements to maintain
the health of a person consuming the product as sole diet. Alternatively, it can be arranged that the
dietary product contains only part of the nutritional requirements; the consumer will then rely on a
foodstuff such as milk to make up the balance. It is convenient to prepare the dietary product in units of
such a size and containing such proportions of nutrients that six units taken in one day yield a calorie
level of approximately 1100, thus providing an acceptable weight-reducing diet.
The following examples further illustrate the present invention.
EXAMPLE 1
Biscuit formula Soya flour - - - - 140 grams white flour - - - 140 grams wholemeal flour - - - 140 grams
sucrose - - - - 100 grams malt extract - - - - 8 grams golden syrup - - - - 15 grams margarine - - - - 56
grams palm kernel oil - - - 45 grams lard - - - - - 56 grams dried milk - - - - 10 grams dibasic calcium
phosphate - 30 grams reduced iron - - - 0.065 grams The materials are blended and formed into a dough.
Pieces are formed to the requisite shape and weight and then baked to produce the biscuits.
Sandwich filling deodorised coconut oil - sucrose sodium carboxylmethyl cellulose vitamin A.
vitamin B - - vitamin B2.
vitamin D.
nicotinamide.
ascorbic acid - - - dibasic calcium phosphate The vitamins A and D are mixed with the calcium
phosphate to be absorbed therein and the dry particles of sodium carboxymethyl cellulose (all passing
BSS No. 30 sieve; 90"/, passing BSS No. 60 sieve), the vitamins B1 and Be, the nicotinamide and the
ascorbic acid are then thoroughly blended with the treated calcium phosphate in a mixer and the
resultant blended powdery mass is sieved and then carefully dispersed in the coconut oil together with
the sugar to form a homogeneous stiff paste in which, if desired, a flavouring material and a colouring
material may be incorporated.
An appropriate amount of this sandwich filling is placed between two biscuits to form a sandwich
product.
Soya flour white flour whole meal flour sucrose malt extract golden syrup margarine EXAMPLE 2
Biscuit formula - - - 140 grams - - - 140 grams - - - 140 grams - - - 50 grams - - - 8 grams - - - 15 grams
- - - 56 grams - 4.5 grams - - 5.5 grams - - 1.0 grams - 1000 international units - - 0.3 milligrams - 0.35 milligrams - _ 15 international units - - 2.5 milligrams - - 12 milligrams - - 500 milligrams palm
kernel oil - - - 45 grams lard - - - - 56 grams dried milk - - - - 10 grams reduced iron - - - - 0.065 grams
The materials are blended and formed into a dough. Pieces are formed to the requisite shape and weight
and then baked to produce the biscuits.
Sandwich filling 95 hydrogenated palm kernel oil 3.805 grams maize starch - - - - 2.330 grams sodium
carboxymethyl cellulose - - - - 0.852 grams dibasic calcium phosphate - 0.497 grams 100 full fat soya
flour - - 0.426 grams spray dried yeast extract - 0.512 grams synthetic cheese flavour - 0.0125 grams
vitamin mix (as in Example 1) - - - - 0.021 grams 105 methionine - - - 0.050 grams The constituents of
the sandwich filling are mixed and blended as described in Example 1.
An appropriate amount of this sandwich 110 filling is placed between two biscuits to form a sandwich
product.
182/321
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เกี่ยวกับ น้ามันปาล์ ม สกัด (Palm oil Extract)
993,308 993,308Data supplied from the esp@cenet database - Worldwide
Claims of GB993308
Claims:
WHAT WE CLAIM IS: 1. A dietary product in the form of a sandwich of two or more biscuits formed from a farinaceous
mixture, and filling, the filling comprising a carbohydrate and a finely divided bulking agent dispersed
throughout a fatty matrix, the bulking agent being substantially insoluble in the fat.
2. A dietary product according to Claim 1 in the form of two biscuits with filling between them.
3. A dietary product according to Claim 1 in the form of a multi-layer sandwich, in which two or more
layers of filling are separated by and contained between biscuits.
4. A dietary product according to any one of Claims 1 to 3, in which the farinaceous mixture from
which the biscuits are formed contains ingredients to supplement the protein content of the flour
employed.
5. A dietary product according to Claim 4, in which the protein-supplementing ingredient is casein.
6. A dietary product according to Claim 4, in which the protein-supplementing ingredient is egg
albumen.
7. A dietary product according to any one of the preceding claims, which contains vitamins and
mineral salts providing calcium, phosphorus and iron.
8. A dietary product according to any one of Claims 1 to 7 in which the carbohydrate is a sugar.
9. A dietary product according to Claim 8, in which the sugar is glucose.
10. A dietary product according to Claim 8, in which the sugar is sucrose.
11. A dietary product according to any one of Claims 1 to 7, in which the carbohydrate is a starch.
12. A dietary product according to any one of Claims 1 to 11, in which the bulking agent is sodium
carboxymethyl cellulose or methyl cellulose.
13. A dietary product according to any one of Claims 1 to 11, in which the bulking agent is sodium
alginate or psyllium.
14. A dietary product according to any one of Claims 1 to 11, in which the bulking agent is carageenin,
agar or guar gum.
15. A dietary product according to any one of the preceding Claims, in which the fat constituting the
fatty matrix is a vegetable fat.
16. A dietary product according to Claim 15, in which the vegetable fat is coconut oil.
17. A dietary product according to Claim 15, in which the vegetable fat is palm kernel oil.
18. A dietary product substantially as described in Example 1 herein.
19. A dietary product substantially as described in Example 2 herein.
183/321
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เกี่ยวกับ น้ามันปาล์ ม สกัด (Palm oil Extract)
STEVENS, LANGNER, PARRY & ROLLINSON, Chartered Patent Agents, Agents for the Applicants.
Leamington Spa: Printed for Her Majesty's Stationery Office by the Courier Press.-1965.
Published at The Patent Office, 25, Southampton Buildings, London, W.C.2, from which copies may
be obtainedData supplied from the esp@cenet database - Worldwide
184/321
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เกี่ยวกับ น้ามันปาล์ ม สกัด (Palm oil Extract)
33. JP10004888 - 13/1/1998
GEL-STATE SUPPLEMENTAL FEED FOR LIVESTOCK AND PRODUCTION
THEREOF
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=JP10004888
Inventor(s):
OSHIBE AKINORI (--); WAN ZAHARI BIN MUHAMMAD (--)
Applicant(s):
NORIN SUISANSYO KOKUSAI NORIN (--)
IP Class 4 Digits: A23K
IP Class:A23K1/02; A23K1/06; A23K1/175
Application Number:
JP19960182709 (19960625)
Priority Number: JP19960182709 (19960625)
Family: JP10004888
Abstract:
Abstract of JP10004888
PROBLEM TO BE SOLVED: To obtain the subject feed capable of suitably being used even in a rainy
season and a dry season in a (sub)tropical zone, and improving tasting properties and preserving
properties under a high temperature and humidity by blending a specific component such as a palm
kernel cake, etc., to a supple mental feed component containing minerals and a theriac. SOLUTION:
This gel-state supplemental feed for a livestock is obtained by blending a component containing 38wt.% palm kernel cake, 3-8wt.% beer- lees, 0.1-1wt.% zeolite, 0.1-1wt.% yeast or yeast extract
and ;=1wt.% palm oil to a supplemental feed component containing 0.4-1wt.% calcium phosphate,
3.5wt.% sodium chloride, 0.4-1wt.% mineral mixture, 3-4wt.% urea, 3-8wt.% sugar, 3-7wt.% calcium
oxide and 55-80wt.% theriac.
185/321
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เกี่ยวกับ น้ามันปาล์ ม สกัด (Palm oil Extract)
34. JP1023841 - 26/1/1989
PRODUCTION OF BAKED CONFECTIONARY
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=JP1023841
Inventor(s):
ISHIDA KUNIO (--); HANEDA AKINAKA (--); SHIMAKAWA TOYOHIRO (--);
TAMURA KOICHI (--); TAGUCHI NOBUO (--)
Applicant(s):
MEIJI SEIKA KAISHA (--)
IP Class 4 Digits: A21D
IP Class:A21D2/36; A21D2/10; A21D2/14; A21D2/16; A21D8/00; A21D8/02; A21D13/08;
A21D2/00; A21D13/00
Application Number:
JP19870178199 (19870718)
Priority Number: JP19870178199 (19870718)
Family: JP1023841
Abstract:
Abstract of JP1023841
PURPOSE: To obtain baked confectionery having an eating feel and flavor by adding an oil-in-water
type emulsified liquid contg. nonplastic solid type oils and fats and edible materials having flavor or
powdered seasoning formed by drying this emulsified liquid to baked confectionery dough and
kneading this dough. CONSTITUTION: The oil-in-water type emulsified liquid contg. the oils and fats
such as cacao butter and palm nucleus oil having 58 to 100 at 10 deg.C, 300 to 100 at 20 deg.C and
>;=4 at 40 deg.C in S.F.I. (an index of the crystallized and solidified quantity at the measuring temp. of
the oils and fats and the numerical value obtd. by multiplying the numerical value, which expresses the
expansion before the solidified parts in the oils and fats of 1kg melt completely from the measuring
temp., by 100), emulsifiers, coating agents, water and the edible parts having the flavor, such as seed
paste of peanut, almond, plant extract, such as herb extract, etc., or the powdered seasoning formed by
drying this emulsified liquid is added to the baked confectionery dough and the dough is kneaded, by
which the baked confectionery dough is obtd.
186/321
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เกี่ยวกับ น้ามันปาล์ ม สกัด (Palm oil Extract)
35. JP11021764 - 26/1/1999
APPLICATION OF EXTRACT FROM BURNED ASH OF OIL PALM BARK
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=JP11021764
Inventor(s):
AZUMA AKIO (--)
Applicant(s):
SANTOU KAGAKU KOGYO KK (--)
IP Class 4 Digits: D06M
IP Class:D06M11/00; D06M11/38; D06M11/64
Application Number:
JP19970217946 (19970708)
Priority Number: JP19970217946 (19970708)
Family: JP11021764
Abstract:
Abstract of JP11021764
PROBLEM TO BE SOLVED: To impart antimicrobial activity, non-electroconductive property and,
hand and feel to fibers without polluting the environment by processing the fibers using materials
extracted from firing ash of trunks, etc., of oil palm as a fiber-processing alkali agent. SOLUTION:
Fibers are processed by using materials extracted from firing ash generated by burning trunks and barks
of oil palm (Elaeis guineensis) as a fiber-processing alkali agent. Further, it is preferable that the
extract from firing ash of oil palm barks and a silver compound (silver nitrate) are subjected to a heat
processing which is carried out in a single bath together with fibers to deposit metallic silver in the
fibers.
187/321
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เกี่ยวกับ น้ามันปาล์ ม สกัด (Palm oil Extract)
36. JP11199461 - 27/7/1999
MEDICAL HERB CREAM AND PREPARATION SOLUTION FOR MEDICAL
HERB CREAM
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=JP11199461
Inventor(s):
RATTAN RARU BINDORA (--); RASHUMI GUPUTA (--); YOGENDORA
NASU SHUKURA (--); SAMRESH DUIVEDI (--); SASUHIRU KUMAA (--)
Applicant(s):
COUNCIL SCIENT IND RES (--)
IP Class 4 Digits: A61K; A61P; A61Q
IP Class:A61K8/96; A61K8/00; A61K8/31; A61K8/73; A61K8/97; A61K8/98; A61K36/18;
A61P17/00; A61Q19/00; A61K8/30; A61K8/72; A61K7/48; A61K7/00
Application Number:
JP19970325095 (19971127)
Priority Number: JP19970325095 (19971127)
Family: JP11199461
Abstract:
Abstract of JP11199461
PROBLEM TO BE SOLVED: To obtain a preparation solution effective as medical herb cream for
cracked heel and palm by including an extract of medical herbs for heeling wound, gum arabic, etc.,
natural wound-heeling aromatic oil, natural wax, petroleum jelly and a preservative. SOLUTION: This
prepared solution comprises (A) 2-10 pts.wt. extract for medical herbs for healing wound (preferably
aqueous curcuma extract, allantoin extract or Azadirachta indica extract), (B) 2-10 pts.wt. gum arabic,
colophonium or Shorea robusta Gaertn. fil., (C) 0.5-2 pts.wt. natural wound heeling aromatic oil
(preferably camomile oil, basil oil or peppermint oil), (D) 50-70 pts.wt. natural wax (preferably
purified beeswax or spermaceti wax), (E) 10-20 pts.wt. petroleum jelly and (F) 0.5-20 pts.wt.
preservative (preferably nepagin-m (phoneic), tocopherol, rosemary oil). The solution is prepared by
melting purified beeswax in steam bath, adding a wound-heeling medical herb extract in low water
content thereto and adding rubber and petroleum jelly thereto.
188/321
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เกี่ยวกับ น้ามันปาล์ ม สกัด (Palm oil Extract)
37. JP11346744 - 21/12/1999
PRODUCTION OF POWDERY COMPOSITION, AND POWDERY
COMPOSITION
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=JP11346744
Inventor(s):
MIYAMOTO ITARU (--); KOJIMA YUKIYA (--); ABEJIMA TOSHIYUKI (--)
Applicant(s):
NOF CORP (--)
IP Class 4 Digits: A23L; A23P
IP Class:A23L1/30; A23L1/00; A23L1/22; A23L1/238; A23L1/304; A23P1/02
Application Number:
JP19980154045 (19980603)
Priority Number: JP19980154045 (19980603)
Family: JP11346744
Abstract:
Abstract of JP11346744
PROBLEM TO BE SOLVED: To obtain a powdery composition capable of inhibiting the affection of
water, capable of being prepared without deteriorating the activity, having excellent flowability and
stability, and useful for medicines, etc. by preliminarily coating a water-repellent powder with an oil
and fat and subsequently granulating the coated powder with a water-soluble binder. SOLUTION: This
method for producing a powdery composition comprises preliminarily coating a water-repellent
powder such as a galenical extract powder with an oil and fat such as palm oil and subsequently
granulating the coated powder with a water-soluble binder such as dextrin preferably in an amount of
0.5-50 pts.wt. (per 100 pts.wt. of the water-repellent powder). In the oil and fat-coating process, a
particulate fat having a melting point of ;=40 deg.C is preferably subjected to a contact collision with
the water-repellent powder to coat the water-repellent powder, or sprayed on the water-repellent
powder in a liquid state in a fluidized bed layer to coat the water-repellent powder. The water- repellent
powder and the oil and fat are preferably used in a weight ratio of 95/5 to 50/50.
189/321
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เกี่ยวกับ น้ามันปาล์ ม สกัด (Palm oil Extract)
38. JP2000044997 - 15/2/2000
SKIN CARE SOAP
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=JP2000044997
Inventor(s):
BOKU KENKI (--); BOKU TEIIN (--)
Applicant(s):
BOKU KENKI (--)
IP Class 4 Digits: A61K; A61Q; C11D
IP Class:A61K8/00; A61Q19/10; C11D9/18; C11D9/38; C11D17/04; C11D9/04; A61K7/50
Application Number:
JP19980225188 (19980727)
Priority Number: JP19980225188 (19980727)
Family: JP2000044997
Abstract:
Abstract of JP2000044997
PROBLEM TO BE SOLVED: To obtain a skin care soap which does not injure or deactivate skin,
does not excessivly irritate skin, and accelerates the reactivation of skin cells by incorporating a fine
powder of a far-infrared radiator into the same. SOLUTION: 1.5-4 wt.%, pref. 2-3 wt.%, fine powder
of a far-infrared radiator having a particle size of 500-700 mesh and optionally 2.0-4.5 wt.% extract
such as of aloe, apricot fruits, Sium suave japonicum, Angelica acutiloba, carrot, or sugarcane are
incorporated into soap produced from a natural oil such as coconut oil, palm oil, or papaya oil, Farinfrared rays penetrate deep into skin to enable the waste of skin to be adsorbed and guided to the
outside, preventing wrinkles, protecting skin from troubles such as atopic dermatitis, pimples, or
freckles, and accelerating the reactivation of skin cells and the circulation of blood to increase the
softness of skin. Since the soap is friendly to and does not irritate skin, it does not cause the feeling of
being stretched, makes skin more beautiful when it is used more frequently, protects a weak skin, and
can eliminate a rough skin or dark spots of a sunburned skin.
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เกี่ยวกับ น้ามันปาล์ ม สกัด (Palm oil Extract)
39. JP2001003079 - 9/1/2001
DEGRADATION INHIBITOR FOR OIL OR FAT UNDER HEATING
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=JP2001003079
Inventor(s):
SAKAI HIDEAKI (--); SHIBUYA YUSUKE (--); ISHIBASHI MINORU (--)
Applicant(s):
KAO CORP (--)
:
A23L; A23D; C09K; C11B
IP Class:A23L3/3562; A23D9/00; C09K15/06; C11B5/00; A23L3/3463; C09K15/00
Application Number:
JP19990169273 (19990616)
Priority Number: JP19990169273 (19990616)
Family: JP2001003079
Abstract:
Abstract of JP2001003079
PROBLEM TO BE SOLVED: To decrease the diffusion of odor inherent in an oil or fat in cooking and
inhibit the degradation of an oil or fat under heating by using a (di) galactosyldiglycerol compound as
an active component. SOLUTION: The degradation inhibitor of an oil or fat under heating contains a
(di)galactosyldiglycerol compound of the formula [wherein two of R1 to R3 are each a 12-22C
(un)saturated fatty acid-derived acyl group and the rest is a saccharide residue]. This compound is
contained in food materials, such as wheat flour, spinach, and carrots, and the inhibitor may be based
on a synthetic product or an extract from food materials. The compound can be extracted with hexane,
acetone, chloroform, methanol, ethanol, or a mixture of these solvents. The inhibitor is added in an
amount of 0.05-1,000 ppm to natural oil or fat, e.g. a vegetable oil such as safflower oil, olive oil,
cotton seed oil, rapeseed oil, corn oil, soy bean oil, palm oil, sunflower oil, or sesame oil.
191/321
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เกี่ยวกับ น้ามันปาล์ ม สกัด (Palm oil Extract)
40. JP2001003080
- 9/1/2001
DEGRADATION INHIBITOR FOR OIL OR FAT UNDER HEATING
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=JP2001003080
Inventor(s):
ISHIBASHI MINORU (--); SAKAI HIDEAKI (--); KOBORI JUN (--)
Applicant(s):
KAO CORP (--)
IP Class 4 Digits: A23D; C09K; C11B
IP Class:A23D9/00; C09K15/08; C11B5/00; C09K15/00
Application Number:
JP19990169274 (19990616)
Priority Number: JP19990169274 (19990616)
Family: JP2001003080
Abstract:
Abstract of JP2001003080
PROBLEM TO BE SOLVED: To decrease the diffusion of odor inherent in an oil or fat in cooking and
inhibit the degradation of an oil or fat under heating by using a degradation inhibitor containing a
turmeric extract. SOLUTION: A rhizome of turmeric, a plant of the ginger family, is dried, pulverized,
and extracted with an organic solvent, such as chloroform, methanol, hexane, ethanol, or a mixture of
these solvents, thus giving the objective degradation inhibitor containing a turmeric extract. By
compounding this turmeric extract and another antioxidant into an oil or fat, an excellent oil or fat
composition for thermal cooking can be obtained. The inhibitor is added preferably in an amount of
0.05-1,000 ppm to a vegetable oil such as safflower oil, olive oil, cotton seed oil, rapeseed oil, corn oil,
soy bean oil, or palm oil. The other antioxidant is added preferably in an amount of 100-2,000 ppm to a
vegetable oil. Examples of the other antioxidant are an L-ascorbic ester, tocopherol, and extracts from
natural substances.
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เกี่ยวกับ น้ามันปาล์ ม สกัด (Palm oil Extract)
41. JP2001039848
- 13/2/2001
SKIN LOTION
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=JP2001039848
Inventor(s):
NAKAJIMA ATSUSHI (--); SUNAGO MIYUKI (--)
Applicant(s):
KAO CORP (--)
IP Class 4 Digits: A61K; A61P; A61Q
IP Class:A61K9/107; A61K8/00; A61K8/02; A61K8/06; A61K8/30; A61K8/60; A61K8/73;
A61K8/92; A61K8/96; A61K8/97; A61K36/00; A61K36/02; A61K36/18; A61K36/25; A61K36/28;
A61K36/60; A61K36/73; A61K36/899; A61K47/06; A61K47/10; A61K47/12; A61K47/14;
A61K47/24; A61K47/28; A61P17/16; A61Q19/00; A61K8/04; A61K8/72; A61K36/185; A61K36/88;
A61P17/00; A61K7/48; A61K7/00; A61K35/78; A61K35/80
Application Number:
JP19990212020 (19990727)
Priority Number: JP19990212020 (19990727)
Family: JP2001039848
Abstract:
Abstract of JP2001039848
PROBLEM TO BE SOLVED: To obtain a skin lotion having improved moisture-retaining property of
skin, excellent roughened skin improving effect, little sticky feeling and excellent moistness by
including trehalose, an oil and a natural extract having moisturizing effect. SOLUTION: The objective
skin lotion contains (A) trehalose, (B) an oil and (C) a natural extract having moisturizing effect. The
component A is present in selaginella, Lentinus edodes, yeast, etc., and producible by extracting the
above plant or by synthesis. The formulation amount is preferably 0.01-30%. The component B is an
oily substance commonly used in skin lotions, e.g. solid or liquid paraffin and hardened palm oil and its
formulation amount is preferably 0.001-50%. The component C is preferably an extract extracted from
plants (e.g. eucalyptus and hop) or seaweeds (e.g. brown algae and red algae) and its formulation
amount is preferably 0.00001-20% expressed in terms of solid.
193/321
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เกี่ยวกับ น้ามันปาล์ ม สกัด (Palm oil Extract)
42. JP2002220306
- 9/8/2002
INSECT PROOF ROPE, INSECT PROOF ROPE APPARATUS, INSECT PROOF
NET AND SIMPLE INSECT PROOF APPARATUS
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=JP2002220306
Inventor(s):
TAKEGAWA MASAMI (--); IWAZAWA NOBUO (--)
Applicant(s):
TAKEGAWA MASAMI (--); NIPPON MITSUBISHI OIL CORP (--)
IP Class 4 Digits: A01M; A01N; C08L; D07B
IP Class:A01M1/02; A01M29/00; A01N25/00; A01N25/34; A01N37/18; A01N65/00; C08L101/16;
D07B5/06; C08L101/00; D07B5/00
Application Number:
JP20010158502 (20010528)
Priority Number: JP20010158502 (20010528); JP20000359682 (20001127)
Family: JP2002220306
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Abstract:
Abstract of JP2002220306
PROBLEM TO BE SOLVED: To repel insect and animal pests such as stinkbugs that interrupt the
growth of rice, crops, and fruits by using an easy, appropriate and non-toxic means without using
pesticides. SOLUTION: An insect proof rope 5, used for repelling insects, is made of organic fibers
such as flax, palm, nonwoven fabric of flax or Chinese alpine rush. The insect proof rope 5 is
impregnated with one of or a blend of plant essential oil extracts, and further with a capsicum extract
and/or a garlic extract. The insect proof rope 5 is also used for an insect proof rope apparatus. In the
insect proof rope apparatus, poles 1-4 are positioned around a plant area 10 such as a paddy or a furrow,
and one or more insect proof ropes 5 are stretched along the poles. The lowermost rope is positioned at
a height where stinkbugs or Lissorhoptrug oryzophilus live. An irritating odor from the herb extracts
impregnated within the insect proof rope exercises a repellent effect against insect pests. The insect
proof ropes can be used not only as the insect proof rope apparatus but also as insect proof ropes or
insect proof nets.
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43. JP2003049199
- 21/2/2003
SAKE SOAP AND METHOD FOR PRODUCING SAKE SOAP
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=JP2003049199
Inventor(s):
ISHIGE YASUO (--)
Applicant(s):
TOKUN SHUZO KK (--)
IP Class 4 Digits: A61K; A61Q; C11D
IP Class:A61K8/30; A61K8/00; A61K8/36; A61K8/96; A61K8/97; A61Q19/08; A61Q19/10;
C11D9/38; C11D13/16; C11D9/04; C11D13/00; A61K7/00; A61K7/50
Application Number:
JP20010236157 (20010803)
Priority Number: JP20010236157 (20010803)
Family: JP2003049199
Abstract:
Abstract of JP2003049199
PROBLEM TO BE SOLVED: To provide a new sake soap soft for the skin and capable of feeding to
the skin. SOLUTION: This sake soap is obtained by comprising a refined sake extract and a soda soap
made from a fatty acid originating from vegetable oil, wherein a mixed oil containing olive oil, almond
oil palm oil and jojoba oil is especially preferable as the vegetable oil. The sake soap can be produced
by adding a caustic soda aqueous solution into a warmed vegetable oil under sufficient agitation to
emulsify the oil, mixing a optional amount of the refined sake with the emulsified reaction product
completed saponification reaction, injecting the obtained mixture into a mold, letting the mold cool to
solidify and removing the molded soap from the mold and aging for 4 weeks or more.
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44. JP2004203848
- 22/7/2004
COMPOSITION CONTAINING VEGETABLE EXTRACT
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=JP2004203848
Inventor(s):
UCHIYAMA CHIYOKO (--); SOMEYA KEITA (--); TOKIDA FUMIHIKO (--);
TAKENAKA GEN (--); MIKOSHIBA SHIGERO (--)
Applicant(s):
LION CORP (--)
IP Class 4 Digits: A23L; A01N; A61K; A61P; A61Q; C09K; C11D
IP Class:A23L1/30; A01N65/00; A61K8/00; A61K8/11; A61K8/96; A61K8/97; A61K36/18;
A61P1/02; A61P17/00; A61P17/02; A61P17/14; A61P39/06; A61Q5/00; A61Q5/02; A61Q5/06;
A61Q5/12; A61Q7/00; A61Q11/00; A61Q15/00; A61Q19/00; A61Q19/10; C09K15/34; C11D3/382;
A61P1/00; A61P39/00; C09K15/00; C11D3/38; A61K35/78; A61K7/00; A61K7/06; A61K7/075;
A61K7/08; A61K7/11; A61K7/26; A61K7/32; A61K7/48; A61K7/50
Application Number:
JP20020383411 (20021220)
Priority Number: JP20020383411 (20021220)
Family: JP2004203848
Abstract:
Abstract of JP2004203848
PROBLEM TO BE SOLVED: To obtain a composition preferably containing one or more highpolarity components of the shell, kernel, leaf or stem of especially a plant of the genus Elaeis, family
Palmae, enabling the effective utilization of a wide range of palm oil extraction residue discharged as
an industrial waste and having excellent deodorizing/odorproofing property, mildness to the skin and
antioxidation property.
SOLUTION: This composition contains the high-polarity components of the plant of the genus Elaeis,
family Palmae.
COPYRIGHT: (C)2004,JPONCIPI
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45. JP2004359664
- 24/12/2004
COMPOSITION FOR SKIN CARE PREPARATION FOR EXTERNAL USE AND
SKIN CARE PREPARATION FOR EXTERNAL USE
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=JP2004359664
Inventor(s):
ITO YASUMICHI (--); TANAKA MOTOHARU (--)
Applicant(s):
KOTOBUKI CHEMICAL KK (--)
IP Class 4 Digits: A61K; A01N
IP Class:A61K8/96; A01N65/00; A61K8/30; A61K8/33; A61K8/34; A61K8/37; A61K8/97;
A61K7/00
Application Number:
JP20040023398 (20040130)
Priority Number: JP20040023398 (20040130); JP20030131165 (20030509)
Family: JP2004359664
Abstract:
Abstract of JP2004359664
PROBLEM TO BE SOLVED: To obtain a composition for a skin care preparation for external use,
excellent in antibacterial activity even by blending an anti-bacterial component gentle to the skin and
derived from a plant, and the skin care preparation for external use by using the same.
SOLUTION: The composition for the skin care preparation for external use is provided by
cutting/removing the pericarp of a hard nut (so called an acorn) of a plant belonging to the genus
Quercus of Fagaceae, crushing the obtained kernel part and blending an extract obtained from the
crushed material into the skin care preparation for external use such as a cosmetic. Preferably, further a
fatty acid monoglyceride derived from a plant oil such as palm oil is added, and in addition, a small
amount of a conventional preservative, an antibacterial polyhydric alcohol, or the like, may be
incorporated.
COPYRIGHT: (C)2005,JPONCIPI
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46. JP2006070140
- 16/3/2006
YACON-CONTAINING SOAP
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=JP2006070140
Inventor(s):
ISHIGURO MICHIKO (--)
Applicant(s):
ISHIGURO MICHIKO (--)
IP Class 4 Digits: C11D; A61K; A61Q
IP Class:C11D9/38; A61K8/00; A61Q19/10; C11D1/04; C11D9/04; C11D1/02
Application Number:
JP20040254364 (20040901)
Priority Number: JP20040254364 (20040901)
Family: JP2006070140
Abstract:
Abstract of JP2006070140
PROBLEM TO BE SOLVED: To provide a method for taking in yacon that contains many substances
that profit human body, such as fructo-oligosaccharide and polyphenol, without being bothered with
peculiar taste of yacon, by directly taking it in through the skin instead of the mouth.
SOLUTION: A yacon-containing soap comprises 97.0-99.5 wt.% total soap substrate such as palm oil
and various additives in total and 0.5-3.0 wt.% yacon extract component.
COPYRIGHT: (C)2006,JPONCIPI
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47. JP2069142
- 8/3/1990
EDIBLE OIL FOR FRYING AND EATING RAW FOOD
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=JP2069142
Inventor(s):
OCHI HIROTOMO (--)
Applicant(s):
OCHI HIROTOMO (--)
IP Class 4 Digits: A23D
IP Class:A23D9/00
Application Number:
JP19880221593 (19880905)
Priority Number: JP19880221593 (19880905)
Family: JP2069142
Abstract:
Abstract of JP2069142
PURPOSE:To provide an edible oil, balanced in nutrition and excellent in stability by blending plural
kinds of grain oils as principal materials with embryo bud oil containing much polyfunctional
unsaturated resin acids and antioxidant. CONSTITUTION:An edible oil for frying and eating raw food
obtained by blending plural grain oils as principal materials with an embryo bud oil containing much
polyfunctional unsaturated resin acids and an antioxidant. In this case, the grain oils consist of 30-60%
palm olein oil, 10-30% high oleic safflower oil, 10-30% sesame oil and 2-10% beefsteak plant grain oil
for the frying. The grain oils consist of 30-60% pressed soybean oil, 10-30% pressed corn oil, 5-10%
high oleic safflower oil and 5-10% palm olein oil for eating raw food. The antioxidant is 0.1-1%
soybean lecithin, 0.01-1% green tea extract polyphenol or 0-0.1% propyl gallate alone or 0.1-1%
mixture thereof.
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48. JP3183480
- 9/8/1991
IMMOBILIZED LIPASE AND ESTER EXCHANGE REACTION OF FAT OR OIL
WITH THE SAME
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=JP3183480
Inventor(s):
FUDO RYOSUKE (--); YAMANAKA SHIGERU (--)
Applicant(s):
AJINOMOTO KK (--)
IP Class 4 Digits: C12P; C11C; C12N
IP Class:C12P7/64; C11C3/10; C12N11/00; C11C3/00
Application Number:
JP19890322909 (19891213)
Priority Number: JP19890322909 (19891213)
Family: JP3183480
Abstract:
Abstract of JP3183480
PURPOSE:To provide an immobilized lipase shortening times for the ester exchange reactions of fats
or oils, depressing the progress of side reactions and useful for modifying the edible fats or oils, etc., by
immobilizing lipase and a hydrophilic amino acid, a peptide, etc., as an activity-generating agent.
CONSTITUTION:A lipase enzyme originated from a Rhizopus strain fungus, etc., and at least one
kind of hydrophilic amino acid and/or peptide (e.g. yeast extract) are dissolved in distilled water and
subsequently homogeneously mixed with a carrier (e.g. celite) with stirring to immobilize the enzyme
and the activity-generating agent on the carrier, followed by drying the carrier e.g. at 40 deg.C for 16
hours under vacuum to provide the immobilized lipase. When a mixture of palm oil and rapeseed oil is
subjected to an ester exchange reaction at 60 deg.C for 3 hours with the immobilized lipase, the fats or
oils can be modified in the high ester exchange activity in a short time.
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49. JP4071464
- 6/3/1992
PRODUCTION OF GARLIC EXTRACT FREE FROM SMELL AFTER
INGESTING
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=JP4071464
Inventor(s):
HIBI KOKICHI (--)
Applicant(s):
HIBI KOKICHI (--)
IP Class 4 Digits: A23L
IP Class:A23L1/212; A23L1/221
Application Number:
JP19900180300 (19900707)
Priority Number: JP19900180300 (19900707)
Family: JP4071464
Abstract:
Abstract of JP4071464
PURPOSE:To obtain the title extract having excellent antimicrobial property and binding property to
vitamin B1 and useful as spices and condiments by blending edible oil and fat with garlic, e.g. finely
cut and then carrying out squeezing, etc., to separate and purifying the oil layer, etc., and packing and
packaging the purified oil layer, etc. CONSTITUTION:Edible oil and fat consisting essentially of
middle chain fatty acid triglyceride extracted from palm oil, etc. and composed of 6-10C fatty acid
containing no unsaturated fatty acid is added to finely cut or ground garlic in the range up to 50% based
on total weight and these ingredients are sufficiently blended, and the blend is subjected to separation
and purification by squeezing or centrifugation, etc. The resultant oil layer or mixture of the oil layer
and water layer is packed and packaged to provide the objective extract.
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50. JP4207179
- 29/7/1992
SUSTAINED RELEASE ANTIMICROBIAL FORMULATION
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=JP4207179
Inventor(s):
YAMADA NOBORU (--); ISHII KOJI (--)
Applicant(s):
GREEN CROSS CORP (--); OJIRO YUKAGAKU KENKIYUUSHIYO K (--)
IP Class 4 Digits: A23L; A01N
IP Class:A23L3/00; A01N47/46; A23L3/3517; A23L3/3535; A01N47/40; A23L3/3463
Application Number:
JP19900317715 (19901126)
Priority Number: JP19900317715 (19901126)
Family: JP4207179
Abstract:
Abstract of JP4207179
PURPOSE:To obtain the subject formulation useful for retaining quality of processed livestock
products, agricultural products, cosmetics, etc., by using a specific oil-soluble substance as a base and
holding allyl isothiocyanate in the aforementioned base. CONSTITUTION:The objective formulation
is obtained by blending glycerol esters of fatty acids (e.g. palm oil) with higher alcohol esters of fatty
acids (e.g. beeswax), using the resultant oil-soluble substance which is in a solid or a pasty form at
ordinary temperature as a base and holding allyl isothiocyanate that is an oil-soluble extract separated
from Eutrema wasabi Maxim., Armoracia rusticana or mustard in the above-mentioned base.
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51. JP4230308
- 19/8/1992
COSMETIC COMPOSITION
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=JP4230308
Inventor(s):
ORIBUIE KUURUTAN (--)
Applicant(s):
KURARANSU (--)
IP Class 4 Digits: A61K; A61Q
IP Class:A61K8/19; A61K8/00; A61K8/06; A61K8/30; A61K8/37; A61K8/41; A61K8/44; A61K8/55;
A61K8/63; A61K8/70; A61K8/92; A61K8/96; A61K8/97; A61K8/98; A61Q1/00; A61Q1/02;
A61Q1/12; A61Q17/00; A61K8/04; A61K7/00; A61K7/02
E Class: A61K8/37; A61K8/44; A61K8/55; A61K8/63; A61K8/70; A61K8/92C; A61K8/98F2;
A61Q1/02; A61Q17/00
Application Number:
JP19910164552 (19910704)
Priority Number: FR19900008507 (19900704)
Family: JP4230308
Equivalent:
FR2664162
Abstract:
Abstract of JP4230308
PURPOSE: To provide a cosmetic composition usable for esp. face makeup, and capable of protecting
the skin from the attack of the air. CONSTITUTION: This cosmetic composition contains a
combination of a vegetable oil from babassu palm and wild rose, a perfluoropolyether, gamma orizanol, ethylenediaminetetraacetate, potassium cetyl phosphate, 18beta -glycyrrhetinic acid, and
glycolic extract of honey.Description:
Description of corresponding document: FR2664162
COMPOSITION COSMETIQUE
La pr้้sente invention a pour objet une composition cosm้้tique, notamment une composition
cosm้้tique de maquillage.
Plus pr้้cis้้ment, la pr้้sente invention propose une composition cosm้้tique susceptible de prot้้ger
la peau, en particulier celle du visage, contre les agressions de l'air atmosph ้้rique, de nos jours de plus
en plus pollu้้.
En effet, l'air atmosph้้rique en milieu urbain ou industriel est charg้้ de substances dissoutes ou
dispers้้es pouvant pr้้senter vis-เ-vis du tissu cutan้้ une agressivit้้ sensible. On peut citer เ titre
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d'exemple, les oxydes tels les oxydes de soufre et d'azote, les hydrocarbures volatils, les gaz halog ้่nes,
notamment le chlore, et les poussi้่res de nature diverses.
En plus de l'action directe sur le tissu cutan้้, les agents atmosph้้riques polluants sont susceptibles de
r้้agir avec un ou plusieurs composants du produit cosm้้tique appliqu้้ sur la peau pour donner
naissance เ un ou plusieurs compos้้s qui se r้้v้่leraient tout เ fait ind้้sirables par leur nature
agressive sur la peau.I1 est ainsi essentiel de tenir compte de cette ้้ventualit้้ dans la s้้lection des
composants des produits cosm้้tiques tels que les produits de maquillage du visage qui une fois
appliqu้้s sur la peau sont susceptibles d'้tre au contact de l'atmosph้่re pendant plusieurs heures.
Ceci s'applique tout particuli้่rement aux fonds de teint qui sont destin้้s เ recouvrir une large partie
du visage.
D'une fa้on g้้n้้rale, une composition cosm้้tique protectrice doit pr้้senter des propri้้t้้s
d'isolation physique et/ou chimique de la peau vis-เ-vis de l'air atmosph้้rique, cette isolation
r้้sultant ้้ventuellement d'une action neutralisante des agents polluants.
L'invention a pour but de proposer des compositions cosm้้tiques comportant une association de
composants pr้้sentant une propri้้t้้ protectrice d'ensemble vis-เ-vis des cons้้quences
dommageables pour le tissu cutan้้ de l'action des agents atmosph้้riques polluants. Ces
cons้้quences dommageables peuvent ้tre class้้es en quatre cat้้gorie - Effets r้้sultant d'une
oxydation, avec la formation dans le tissu cutan้้ de radicaux libres, g้้n้้rateurs de d้้gโts
semblables เ ceux provoqu้้s par la d้้g้้n้้rescence due au vieillissement chronologique.
- Effets r้้sultants d'une r้้duction, avec un appauvrissement superficiel en oxyg ้่ne entra้nant une
modification du m้้tabolisme respiratoire des cellules de l'้้piderme (k้้ratinocytes).
- Effets r้้sultants de l'acidit้้; la peau, bien que pr้้sentant un pH l้้g้่rement acide1 devient
facilement irritable d้่s que le niveau d'acidit้้ d้้passe un seuil de tol้้rance.
- Effets r้้sultants de l'alcalinit้้; des d้้gradations entam้้es apparaissent si l'alcalinit้้ d้้passe un
seuil de tol้้rance pendant une longue dur ้้e (plusieurs heures).
A cette fin, l'invention propose une composition cosm ้้tique contenant les composants de nature
hydrophobe suivants - huiles v้้g้้tales de babassu et de rosier sauvage - perfluoropolyether - Y
orizanol et les composants de nature hydrophile suivants - cethyl phosphate de potassium - sel de
l'acide ้้thyl้่ne diamine t้้trac้้tique- acide 18 P glyccyrh้้tinique - extrait glycolique de miel.
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Avantageusement, la composition cosm้้tique selon l'invention se pr้้sente sous la forme
d'une ้้mulsion d'une phase hydrophobe dispers้้e dans une phase aqueuse, la phase hydrophobe ้้tant
comprise entre 15 et 45 % en poids de la composition. ~~
Selon une variante de l'invention เ usage de maquillage pour le visage, la composition cosm ้้tique
contient des composants เ base de st้้arates, des agents stabilisateurs เ et/ou conservateurs
et ้้ventuellement des pigments color้้s notamment des oxydes m้้talliques.
Selon un autre aspect de l'invention, l'acide 18 glyccyrh ้้tinique est associ้้ de
fa้on ้้quimol้้culaire เ un compos้้ phospholipidique appartenant de pr้้f้้rence เ la famille des
l้้citines.
De pr้้f้้rence, les compositions cosm้้tiques selon l'invention contiennent en poids - entre 4 et 10 %
d'huiles v้้g้้tales de babassu et de rosier sauvage.
- entre 2 et 5% de perfluoropolyether - entre 2 et 5 % dez orizanol - entre 2 et 5 % de c้้thyl
phosphate de potassium - environ 0,1 % de sel de l'acide ้้thyl้่ne diamine t้้trac้้tique- environ 1 %
d'acide 18 glyccyrh้้tinique - environ 10 % d'extrait glycolique de miel.
L'action protectrice des divers composants essentiels pour l'invention est pr ้้sent้้e ci-dessous - les
huiles v้้g้้tales de babassu et de rosier sauvage sont stables เ l'oxydation et att้้nuent l'้้ventuelle
attaque oxydante du milieu ambiant.
- Le perfluoropoly้้ther pr้้sente une structure mol้้culaire qui permet l'isolation de la peau par
perm้้abilit้้ s้้lective du film d้้pos้้ sur l'้้piderme.
- Lez orizanol, ester de l'acide f้้rulique et d'un alcool terp้้nique de formule C40 H58 03 est un bon
protecteur vis-เvis des r้้actions d'oxydo-r้้duction.
- Le c้้tyl phosphate de potassium est un agent tensio actif dont la structure mol ้้culaire conf้่re aux
compositions un pouvoir tampon qui se traduit par une certaine insensibilit ้้ aux variations d'acidit้้
ou d'alcalinit้้.
- Les sels d'acide ้้thyl้่ne diamine t้้trac้้tique (par exemple l'้้thyl้่ne diamine t้้tra ac้้tate de
sodium ou E.D.T.A.) ont la propri้้t้้ de neutraliser les agressions d'origine m้้tallique.
- L'acide 18 glyccyrh้้mitique, extrait de la r้้glisse, soit seul, soit associ้้ de
fa้on ้้quimol้้culaire เ un compos้้ phospholipidique appartenant par exemple เ la famille des
l้้citines favorise l'assimilation de la composition par1 '้้pider- me.
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- Enfin l'extrait glycolique du miel a pour effet de favoriser la tol ้้rance par l'้้piderme des compos้้s
ci-dessus.
I1 est int้้ressant de constater que l'association des sept composants ci-dessus conf้่re เ la
composition cosm้้tique selon l'invention sa propri้้t้้ protectrice d'ensemble.
Une formule type de composition cosm้้tique de maquillage selon l'invention du type fond de teint est
donn้้e ci-apr้่s เ titre d'exemple non limitatif (composition donn ้้e en pourcentage
poids):Monost้้arate de polypropyl้่ne glycol 3Stearate de glyc้้rol 2
Alcool c้้tylique 1Stearyl ether 3
Triglyc้้rides C8-C10 5
Octyldod้้cyl st้้aroyl st้้arate 5
Huile de silicone 5Perfl uoropol yether 5
X Orizanol 1
Huile de babassu 3
Huile de rosier sauvage 3
Sel de l'acide ethyl้่ne diamine t้้trac้้tique 0,1
Potassium c้้tyl phosphate 4
Acide 18 glyccyrhetinique 1
Extrait glycolique de miel 5
Oxydes de fer 8
Oxyde de titane 3
Conservateurs 0,5
Antioxydant 0,5
Eau d้้min้้ralis้้e QSP 100
La pr้้paration de cette composition est obtenue sans difficult ้้ particuli้่re apr้่s liqu้้faction
par ้้l้้vation de temp้้rature des compos้้s st้้ariques et adjonction des autres composants au
refroidissement en terminant par les compos้้s thermiquement les moins stables (huiles v้้g้้tales et
extrait de miel). On obtient ainsi une ้้mulsion d'huile dans l'eau avec une phase dispers้้e de nature
hydrophobe (dans le cas pr้้sent เ repr้้sentant 36 % en poids de la composition totale) associ้้e เ une
phase aqueuse et เ une suspension de particules solides (oxydes m้้talliques), le tout ้้tant stabilis้้ par
des agents tensio actifs non ioniques et anioniques. La composition ainsi pr้้par้้e a un pH compris
entre 6,5 et 7.
Les compositions selon l'invention se pr้้sentent ้้galement sous toute autre forme appropri้้e telles
que cr้่mes ou lotions, ้้tant entendu qu'une augmentation du pourcentage de potassium c้้tyl
phosphate fluidifie la composition et qu'une augmentation du pourcentage de st ้้arate et/ou d'alcool
c้้tylique ้้paissit la composition. De plus l'้้limination des pigments color้้s et leur remplacement
par du talc ou kaolin permettent d'obtenir une cr้่me dite de jour poss้้dant ้้galement les propri้้t้้s
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protectrices recherch้้es.Data supplied from the esp@cenet database - Worldwide
Claims:
Claims of corresponding document: FR2664162
REVENDICATIONS
1/ Composition cosm้้tique de maquillage caract้้ris้้e en ce qu'elle contient les composants de
nature hydrophobe suivants - huiles v้้g้้tales de babassu et rosier sauvage - perfluoropolyether -w
orizanol et les composants de nature hydrophile suivants - c้้thyl phosphate de potassium - sel de
l'acide ้้thyl้่ne diamine t้้trac้้tique - acide 18y glyccyrh้้tinique - extrait glycolique de miel.
2/ Composition cosm้้tique selon la revendication 1, caract้้ris้้e en ce qu'elle se pr้้sente sous la
forme d'une ้้mulsion d'une phase hydrophobe dispers้้e dans une phase aqueuse, la phase
hydrophobe ้้tant comprise entre 15 et 45 % en poids de la composition.
3/ Composition selon la revendication 2 caract้้ris้้e en ce qu'elle contient des composants เ base de
st้้arates, des agents stabilisateurs et/ou conservateurs et ้้ventuellement des pigments color้้s,
notamment des oxydes m้้talliques.
4/ Composition selon 1 l'une des revendications pr้้c้้dentes caract้้ris้้e en ce que l'acide18P
glyccyrh้้tinique est associ้้ de fa้on ้้quimol้้culaire เ un compos้้ phospholipidique appar tenant
de pr้้f้้rence เ la famille desl้้citines.
5/ Composition selon l'une des revendications pr้้c้้dentes caract้้ris้้e en ce qu'elle contient en
poids - entre 4 et 10 % d'huiles v้้g้้tales de babassu et de rosier sauvage - entre 2 et 5 % de orizanol entre 2 et 5 % de c้้tyl phosphate de potassium - environ 0,1 % de sel de l'acide ้้thyl้่ne diamine
t้้trac้้tique- environ 1% d'acide 18 p glyccyrh้้tinique - environ 10 % d'extrait glycolique de
miel.Data supplied from the esp@cenet database - Worldwide
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52. JP55145789
- 13/11/1980
PRODUCTION OF FOOD* FAT AND OIL FROM WHICH GENERATION OF
DISAGREEABLE ODOR
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=JP55145789
Inventor(s):
(--)
SHIMIZU YASUHIRO (--); HAMASHIMA MORIO (--); FUJIKAWA TAKUMA
Applicant(s):
NISSHIN OIL MILLS LTD (--)
IP Class 4 Digits: C09K; A23D; C11B
IP Class:C09K15/34; A23D9/00; C11B5/00; C09K15/00; A23D5/00
Application Number:
JP19790053360 (19790502)
Priority Number: JP19790053360 (19790502)
Family: JP55145789
Abstract:
Abstract of JP55145789
PURPOSE:To produce foods, fats and oils from which the generation of soapy flavor is prevented, by a
method wherein a specified additive is added to fats and oils contg. lower fatty acids or to foods using
such fats and oils. CONSTITUTION:Crude rice bran oil is purified with an alkaline material. The
resulted neutral oil in alkali foots is saponified and then treated with dilute sulfuric acid to produce dark
oil which is then distilled under reduced pressure to obtain a distillation residue (A) of the rice bran
dark oil. The alkali foots of rice bran oil is extracted with a neutral monohydric lower alcohol. The
resulting extract is acidified to separate a viscous material (B). An additive selected from (A) the
residue and (B) the viscous material in an amount of 0.01-1.0% based on the weight of fats and oils is
added to fats and oils contg. lower fatty acids (e.g. hardened coconut oil, palm kernel oil, etc.) or foods
(e.g. chocolate, ice cream, etc.) using the fats and oils.
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53. JP57202266
- 11/12/1982
COMPOUNDED PASTY SEASONING AND ITS PREPARATION
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=JP57202266
Inventor(s):
KITA YASUO (--); SAKAGUCHI MAKOTO (--); EBISAWA TAIJI (--)
Applicant(s):
AJINOMOTO KK (--)
IP Class 4 Digits: A23L
IP Class:A23L1/22
Application Number:
JP19810084995 (19810604)
Priority Number: JP19810084995 (19810604)
Family: JP57202266
Abstract:
Abstract of JP57202266
PURPOSE:To obtain a pasty seasoning free of stickiness and stringiness and composed of extracts, oils
and fats, and crystalline seasonings, by dispersing fine particles of solid fat having a melting point
of ;=35 deg.C in the seasoning. CONSTITUTION:1-4pts.wt. of an extract (meat extract, fish and
shellfish extract, vegetable extract), 1-5pts. of an oil or fat at least a part of which is a solid oil or fat
having a melting point of ;=35 deg.C (e.g. hydrogenated rapeseed oil, hydrogenated soybean oil, palm
oil, coconut oil, lard, beef tallow, etc.) and 2-4pts. of a crystalline seasoning (e.g. MSG, IMP, GMP,
table salt, etc.) are heated at or above the melting point of the solid fat, mixed with each other, and
cooled under stirring to prevent the separation of the fat. The fat is solidified keeping the finely divided
state and retaining the fluidity of the whole system.
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54. JP61021098
- 29/1/1986
PREPARATION OF ENZYMIC REACTION PRODUCT
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=JP61021098
Inventor(s):
NAKAMURA KOUZOU (--); YANO TOSHIMASA (--)
Applicant(s):
AJINOMOTO KK (--)
IP Class 4 Digits: C12N; C11C; C12P; C12Q
IP Class:C12N11/00; C11C3/10; C12P7/64; C12Q1/00; C11C3/00
Application Number:
JP19840143138 (19840710)
Priority Number: JP19840143138 (19840710)
Family: JP61021098
Abstract:
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Abstract of JP61021098
PURPOSE:To advance a reaction in a homogeneous phase and carry out separation after the reaction
with ease, by carrying out an enzymic reaction in the presence of a substance capable of being a solvent
in the supercritical state. CONSTITUTION:For example, lipase, e.g. Rhizopus delemar, is used as an
enzyme, and a fat or oil, e.g. palm oil or beef tallow, is used as a substance subjected to the enzymic
reaction. The enzymic reaction is carried out using carbon dioxide as a substance capable of being a
solvent in the supercritical state. The lipase and the fat or oil are put into reaction vessels 1 and 1', and
gaseous carbon dioxide (critical temperature; 31.1 deg.C, critical pressure; 73atm) is boosted with a
liquid chromatographic pump 4, liquefied, fed to the reaction vessels 1 and 1' while controlling the
pressure with valves 5-8, and reacted at about 32 deg.C under about 100atm pressure with stirring.
After the reaction, the reaction vessels 1 and 1' are cooled with acetone-dry ice, and the reaction
product is recovered in the dry ice. The dry ice is sublimed to extract and separate the aimed lipid from
the residue.
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55. JP6133735
- 17/5/1994
ENTERIC-COATED LACTOBACILLUS GRANULE
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=JP6133735
Inventor(s):
HIZAKI SHIGERU (--); YAMAUCHI MASAAKI (--)
Applicant(s):
KANEBO LTD (--)
IP Class 4 Digits: A23L; A61K; C12N
IP Class:A23L1/00; A23L1/30; A61K9/50; A61K35/74; A61K36/18; A61K47/14; A61K47/42;
C12N1/04; A61K35/66; A61K35/78
Application Number:
JP19920309637 (19921023)
Priority Number: JP19920309637 (19921023)
Family: JP6133735
Abstract:
Abstract of JP6133735
PURPOSE:To obtain the subject granules insoluble in the mouth and stomach but soluble in the
intestinal tract, thus excellent in lactobacterial proliferation and contamination resistance by coating
lactobacillis and coffee leaves or extract thereof with specific two kinds of layers.
CONSTITUTION:The objective granules can be obtained by coating lactobacillis such as
Lactobacillus casei or Leuconostoc dextranicum (viable cell number: ;=10>;6;) and coffee leaves or
extract thereof with (A) a layer containing fatty oil (e.g. palm oil, coconut oil) and vehicle (potato
starch, egg, glucose) and (B) a layer containing hydrous alcohol-soluble protein (pref. zein, a glyceral
fatty acid ester is used as plasticizer).
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56. JP62108876
- 20/5/1987
PRODUCTION OF VITAMIN E
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=JP62108876
Inventor(s):
ARIKI SHIGEO (--); YAMAMOTO TAKUO (--); OZAWA YOSHIHISA (--);
SEIKE TAKASHI (--)
Applicant(s):
MITSUBISHI GAS CHEMICAL CO (--)
IP Class 4 Digits: C07D
IP Class:C07D311/72; C07D311/00
Application Number:
JP19850248061 (19851107)
Priority Number: JP19850248061 (19851107)
Family: JP62108876
Abstract:
Abstract of JP62108876
PURPOSE:To facilitate extraction of vitamin E and improve recovery ration without loss, by dipping a
plant tissual body containing vitamin E in an edible oil and dehydrating the plant tissual body while
heating in efficiently separating and concentrating the vitamin E from the above-mentioned plant
tissual body. CONSTITUTION:A plant tissual body containing vitamin E, particularly preferably leaf
of oil palm is directly or finely cut and dipped in a preheated or unheated vegetable oil and further heat
normally at 120-200 deg.C, preferably about 140-160 deg.C. The pressure in heating is preferably
reduced pressure thereby to remove water and give a dehydrated plant tissual body, which is then
subjected to a mechanical means, e.g. oil press, etc., or solvent extraction to give an extract containing
the vitamin E and fat or oil. The resultant extract is then steam distilled to afford the vitamin E and the
separation residue is effectively utilized as a feed.
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57. JP62195254
- 28/8/1987
FEED
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=JP62195254
Inventor(s):
SEIKE TAKASHI (--); ARIKI SHIGEO (--); OZAWA YOSHIHISA (--);
TSUKAMOTO MASAAKI (--)
Applicant(s):
MITSUBISHI GAS CHEMICAL CO (--)
IP Class 4 Digits: A23K
IP Class:A23K1/00
Application Number:
JP19860032800 (19860219)
Priority Number: JP19860032800 (19860219)
Family: JP62195254
Abstract:
Abstract of JP62195254
PURPOSE:To obtain a feed liked by domestic animal and poultry, having high feed value and
important from the viewpoint of resource utilization, by extracting physiologically active substance
from small leaf or whole leaf of oil palm and using the extraction residue as an essential component.
CONSTITUTION:Small leaves or whole leaves of oil palm are usually cut or crushed and extracted
with a solvent (preferably n-hexane) to extract a physiologically active substance such as vitamin E
from the leaves. The residue after the extraction of the physiologically active substance is mixed with a
feed raw material such as grains, oil cake, etc., to obtain the objective feed.
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58. JP6256142
- 13/9/1994
HAIR TONIC
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=JP6256142
Inventor(s):
NISHIDA YUICHI (--); MIYAZAKI MASATSUGU (--); IWAO SHUJI (--)
Applicant(s):
LION CORP (--)
IP Class 4 Digits: A61K; A61Q
IP Class:A61K8/00; A61K8/37; A61K8/97; A61Q5/00; A61Q7/00; A61K8/30; A61K8/96; A61K7/06
Application Number:
JP19930047070 (19930309)
Priority Number: JP19930047070 (19930309)
Family: JP6256142
Abstract:
Abstract of JP6256142
PURPOSE:To provide a hair tonic containing carotenes and a cell-activating ingredient, having
excellent hair growth-promoting activity. CONSTITUTION:The hair tonic containing (A) 1X10>;-5; to
1 (pref. 1X10>;-4; to 0.5) wt.% of carotenes (pref. a mixture of alpha-carotene, gamma-carotene and
lycopene, esp. carotenes found in palm oil) and (B) 0.1-30 (pref. 0.5-5) wt.% of a cell- activating
ingredient, pref. a mono or diglyceride of 9-21C (odd-numbered carbon chain) fatty acid (e.g.
undecanoic, pentadecanoic or nonadecanoic acid), esp. pentadecanoic monoglyceride. The carotenes
found in palm oil normally comprises a mixture of alpha-carotene, gamma-carotene and lycopene with
the weight ratio falling within the range given by the three points: A (95:5:5), B (20:75:5) and C
(20:5:75) in triangular diagram. This hair tonic is additionally formulated with 1-hydroxy-2-pyridone
(derivative) and a plant extract having anti- inflammatory, blood circulation-promoting and/or 5alphareductase-inhibitory activity.
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59. JP6263647
- 20/9/1994
INHIBITOR AGAINST LIPOPEROXIDE
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=JP6263647
Inventor(s):
SOMEYA KEITA (--); TOTSUKA YUKA (--); MIYAZAWA HARUO (--)
Applicant(s):
LION CORP (--)
IP Class 4 Digits: A61K; A61P
IP Class:A61K31/015; A61K36/18; A61P3/06; A61P43/00; A61K31/01; A61P3/00; A61K35/78
Application Number:
JP19930079095 (19930312)
Priority Number: JP19930079095 (19930312)
Family: JP6263647
Abstract:
Abstract of JP6263647
PURPOSE:To obtain an inhibitor against lipoperoxide having high safety to organisms having
excellent inhibiting effect on lipoperoxide, hardly having side effect, capable of being administered by
various methods. CONSTITUTION:An inhibitor against lipoperoxide comprises a carotene mixture
extracted from a palm oil as an active ingredient. The palm oil extract is obtained by subjecting a palm
oil to alcoholysis with a lower monoalcohol, diluting the prepared fatty acid lower alkyl ester with a
hydrophilic solvent (e.g. methanol, ethanol or acetone), adding water to give a precipitate and purifying
the precipitate by using distillation under reduced pressure and a column of silicic acid and is
composed of 30-40% alpha-carotene, 55-66% beta-carotene and 5-15% other components such as
carotenoids. The inhibitor is applicable by various administration methods such as oral medication,
intravenous injection, hypodermic injection, intermuscular injection or suppository.
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60. JP63014678
- 21/1/1988
SEASONING
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=JP63014678
Inventor(s):
ODERA NORIO (--); KANAMORI TAKESHI (--)
Applicant(s):
LION CORP (--)
IP Class 4 Digits: A23L
IP Class:A23L1/22; A23L1/304
Application Number:
JP19860160153 (19860708)
Priority Number: JP19860160153 (19860708)
Family: JP63014678
Abstract:
Abstract of JP63014678
PURPOSE:To make is possible to readily eliminate imbalance in nutritional aspects in dietary habits,
by blending a seasoning with vitamin consisting of natural carotene and natural mineral derived from
whey to enrich nutrients. CONSTITUTION:A seasoning obtained by blending a basic seasoning, e.g.
soy sauce, MISO (paste, made of fermented soybeans and used for preparing soup) or natural processed
seasoning, e.g. dressing, mayonnaise, etc., with natural carotene, e.g. palm oil extract, as a vitamin and
then natural mineral derived from whey as a mineral. Thereby almost the same nutriments as those in
ingesting green and yellow vegetables can be readily ingested simply by sprinkling the resultant
seasoning on, e.g. light yellow and green vegetables, etc., and eating the vegetables. The natural
mineral derived from whey is obtained by adding an acid to deproteinize the whey and contains not
only calcium but also much potassium. Thereby preventing effect on adult diseases, e.g. hypertension,
etc., caused by taking too much sodium can also be expected.
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61. JP7118137
- 9/5/1995
BEAUTIFYING AGENT
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=JP7118137
Inventor(s):
SOMEYA KEITA (--); TANAKA YOSHIRO (--); KOIKE YASUSHI (--)
Applicant(s):
LION CORP (--)
IP Class 4 Digits: A61K; A61P; A61Q
IP Class:A61K8/30; A61K8/00; A61K8/97; A61K31/015; A61P17/00; A61Q19/00; A61Q19/02;
A61K8/96; A61K31/01; A61K7/48; A61K7/00
Application Number:
JP19930284340 (19931019)
Priority Number: JP19930284340 (19931019)
Family: JP7118137
Abstract:
Abstract of JP7118137
PURPOSE:To obtain a beautifying agent having excellent effect on beauty culture of skin, high safety
and improved absorption in body free from fear of side effects, comprising a carotene mixture
extracted from a palm oil as an active ingredient. CONSTITUTION:For example, a palm oil is
subjected to alcoholysis with a lower alcohol, the prepared ester is diluted with a hydrophilic solvent
and water is added to the solution to give precipitate. Then the precipitate is purified by vacuum
distillation to give a carotene mixture. A beautifying agent comprises the carotene mixture extracted
from the palm oil as an active ingredient. The extract of the palm oil is a mixture usually comprising
30-40% of alpha-carotene, 55-66% of beta-carotene and 5-15% of other components such as
carotenoids. Since various administration methods of this beautifying agent can be applied, the
administration method and a does can be controlled depending upon the condition of a disease. Further
a large amount of the beautifying agent can be used, the agent is effective for preventing and treating
disorder in terms of health and beauty culture.
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62. JP8038062
- 13/2/1996
COMPOSITION FOR PICKLE
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=JP8038062
Inventor(s):
KANDA YOSHIHIRO (--)
Applicant(s):
AJINOMOTO KK (--)
IP Class 4 Digits: A23D; A23J; A23L
IP Class:A23D9/007; A23J3/16; A23L1/318; A23J3/00
Application Number:
JP19940172984 (19940726)
Priority Number: JP19940172984 (19940726)
Family: JP8038062
Abstract:
Abstract of JP8038062
PURPOSE:To obtain a composition for pickle causing no decline in the mechanical strength of foods
like ham through presenting stable defoaming effect during producing or using pickles therewith, by
mixing soybean protein powder with powdered oil and fat at specified proportions.
CONSTITUTION:This composition is obtained by mixing (A) soybean protein powder with (B)
powdered oil and fat at the weight ratio of (70:30) to (95:5) [pref. (80:20) to (90:10)]. The component
A is pref. prepared by subjecting separated soybean protein to protease treatment to bring its soluble
nitrogen index at 5 deg.C to ;=80. The component B is prepared, for example, by adding a saccharide
or milk casein and an emulsifier to palm oil or tallow to make an emulsion which is then put to spray
drying. It is recommended that the separated soybean protein be obtained by extracting protein together
with water-soluble carbohydrates from defatted soybean and then coagulating the protein from the
resultant aqueous solution of the extract.
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63. JP8092050
- 9/4/1996
DEODORIZING AGENT AND COMPOSITION FOR ORAL CAVITY
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=JP8092050
Inventor(s):
ISHIKAWA MASAO (--)
Applicant(s):
LION CORP (--)
IP Class 4 Digits: A61K; A61Q
IP Class:A61K8/00; A61Q11/00; A61Q15/00; A61K7/32; A61K7/16
Application Number:
JP19940257556 (19940927)
Priority Number: JP19940257556 (19940927)
Family: JP8092050
Abstract:
Abstract of JP8092050
PURPOSE: To obtain a tasteless and odorless deodorizing agent containing tocotrienol as an active
ingredient, having excellent deodorizing effect on a volatile sulfur compound of methyl mercaptane,
etc., having high safety and also excellent in retaining property in oral cavity. CONSTITUTION: This
deodorizing agent contains tocotrienol as an active ingredient. A substance obtained from an extract of
palm oil is preferably used as the tocotrienol. A method for obtaining tocotriphenol from palm oil
includes a method for subjecting palm oil to methyl-esterification, distilling and concentrating the
esterified product, adding acetone to the bottom, carrying out crystallization, removing an unnecessary
component by ion exchange absorption and carrying out molecular distillation. Furthermore, when the
deodorizing agent is blended with a composition for oral cavity, e.g. a dentifrice or food and drink, the
agent is preferably used in an amount of 0.02-2wt.% as tocotrienol based on total amount.
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64. JP8151324
- 11/6/1996
ANTIMICROBIAL PREPARATION
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=JP8151324
Inventor(s):
TSUNEMITSU AKIRA (--); SUIDOU HIROHISA (--)
Applicant(s):
SUNSTAR INC (--)
IP Class 4 Digits: A61K; A61P; A61Q
IP Class:A61K8/00; A61K8/21; A61K8/33; A61K8/44; A61K8/90; A61K8/96; A61K8/97; A61K8/98;
A61K31/045; A61K31/085; A61K31/14; A61K31/155; A61K31/195; A61K31/198; A61K31/22;
A61K31/44; A61K31/70; A61K31/77; A61K33/16; A61K33/24; A61K35/64; A61K36/23;
A61K36/48; A61K36/60; A61K36/896; A61K45/00; A61P1/02; A61P17/00; A61P31/04; A61P43/00;
A61Q11/00; A61K8/19; A61K8/30; A61K8/72; A61K31/075; A61K31/185; A61K31/21; A61K31/74;
A61K35/56; A61K36/185; A61K36/88; A61P1/00; A61P31/00; A61K7/16; A61K7/18; A61K7/26;
A61K35/78
Application Number:
JP19940319152 (19941128)
Priority Number: JP19940319152 (19941128)
Family: JP8151324
Abstract:
Abstract of JP8151324
PURPOSE: To obtain an antimicrobial preparation exhibiting excellent antimicrobial activity against
the aggregate and lump of microorganisms, such as a biofilm or plaque, which can substantially not be
controlled with an antimicrobial agent a lone. CONSTITUTION: The antimicrobial preparation
contains 0.001-10wt.% of arginine or its derivative and 0.001-10wt.% of a compound exhibiting
antimicrobial activity. The further addition of 0.005-5wt.% of at least a surfactant selected from a
nonionic surfactant and an amphoteric surfactant to the antimicrobial preparation gives the more
excellent antimicrobial effect. The compound exhibiting the antimicrobial activity includes cationic
antimicrobial agents (e.g. cetylpyridinium chloride), fluorides, natural antimicrobial agents (e.g. thymol,
oil-soluble glycyrrhiza extract, a polyphenol), trichlosan, and isopropylmethylphenol. The nonionic
surfactant is preferably a polyethylene oxide-polypropylene oxide block copolymer, and the
amphoteric surfactant is preferably a palm oil fatty acid amide propylbetaine.
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65. JP8151326
- 11/6/1996
ANTIMICROBIAL PREPARATION
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=JP8151326
Inventor(s):
TSUNEMITSU AKIRA (--); SUIDOU HIROHISA (--)
Applicant(s):
SUNSTAR INC (--)
IP Class 4 Digits: A61K; A61P; A61Q
IP Class:A61K8/00; A61K8/43; A61K8/73; A61K8/86; A61K8/96; A61K31/05; A61K31/085;
A61K31/155; A61K31/335; A61K31/415; A61K31/44; A61K31/70; A61K31/77; A61K35/64;
A61K36/00; A61K36/23; A61K36/48; A61K36/60; A61K36/896; A61P1/02; A61P31/04; A61P43/00;
A61Q11/00; A61K8/30; A61K8/72; A61K31/045; A61K31/075; A61K31/74; A61K35/56;
A61K36/185; A61K36/88; A61P1/00; A61P31/00; A61K7/16; A61K7/26; A61K35/78
Application Number:
JP19940319153 (19941128)
Priority Number: JP19940319153 (19941128)
Family: JP8151326
Abstract:
Abstract of JP8151326
PURPOSE: To obtain an antimicrobial preparation exhibiting excellent antimicrobial activity against
the aggregate and lump of microorganisms, such as a biofilm or plaque, which can substantially not be
controlled with an antimicrobial agent alone. CONSTITUTION: The antimicrobial preparation
contains 0.001-10wt.% of histidine or its derivative and 0.001-10wt.% of a compound exhibiting
antimicrobial activity. The further addition of 0.005-5wt.% of at least a surfactant selected from a
nonionic surfactant and an amphoteric surfactant to the antimicrobial preparation gives the more
excellent antimicrobial effect. The compound exhibiting the antimicrobial activity includes cationic
antimicrobial agents (e.g. chlorohexidine), natural antimicrobial agents (e.g. oil-soluble glycyrrhiza
extract, camomile, Mori cortex extract, tea extract), trichlosan, and isopropylmethylphenol. The
nonionic surfactant is preferably a polyethylene oxide-polypropylene oxide block copolymer, and the
amphoteric surfactant is preferably a palm oil fatty acid amide propylbetaine.
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66. JP9104864
- 22/4/1997
NATURAL ANTIOXIDANT
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=JP9104864
Inventor(s):
KATO YOSHIAKI (--)
Applicant(s):
SAN EI GEN FFI INC (--)
IP Class 4 Digits: A23G; A23L; A61K; A61Q; C09K; C11B
IP Class:A23G3/00; A23G3/34; A23L1/48; A61K8/00; A61K8/96; A61K8/97; A61Q19/00;
C09K15/34; C11B5/00; C09K15/00; A61K7/00; A61K7/48
Application Number:
JP19950262946 (19951011)
Priority Number: JP19950262946 (19951011)
Family: JP9104864
Abstract:
Abstract of JP9104864
PROBLEM TO BE SOLVED: To obtain a natural antioxidant containing an extract from the wood part
of Pterocarpus santaltinus L. f. as an active ingredient, capable of manifesting a potent antioxidant
effect compared with that of conventional products in (un)saturated-based oils and fats such as a palm
oil and a corn oil, and useful for a food, a medicine, a cosmetic, etc. SOLUTION: This natural
antioxidant contains (A) an extract from the wood part of Pterocarpus santaltinus L. f. belonging to
Leguminosae obtained by immersing 10 pts.wt. crushed material obtained by crushing the wood part
by a crusher, etc., into 100-200 pts.wt. organic solvent such as methanol, acetone and propylene glycol,
extracting under refluxing, and removing the organic solvent from the extract as an active ingredient.
The preparations of this agent are e.g. the (A) as it is, a solution obtained by dissolving the (A) in
ethanol, etc., or an emulsified composition obtained by emulsifying the (A) in an aqueous solution by
using an emulsifier such as a glycerol fatty acid ester.
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67. JP9227344
- 2/9/1997
HERB EXTRACT-CONTAINING SHAMPOO AND PRODUCTION THEREOF
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=JP9227344
Inventor(s):
YAMADA TOSHIO (--)
Applicant(s):
YAMADA TOSHIO (--)
IP Class 4 Digits: A61K; A61Q
IP Class:A61K8/30; A61K8/00; A61K8/33; A61K8/34; A61K8/40; A61K8/42; A61K8/44; A61K8/46;
A61K8/65; A61K8/66; A61K8/96; A61K8/97; A61Q5/02; A61K7/075; A61K7/00
Application Number:
JP19960056726 (19960220)
Priority Number: JP19960056726 (19960220)
Family: JP9227344
Abstract:
Abstract of JP9227344
PROBLEM TO BE SOLVED: To obtain a herb extract-containing shampoo capable of expressing
effects such that exhibit actions of the herb extract, bring hair to be glossy after washing the hair, easily
impart nutrients to hair roots and cause little depilation. SOLUTION: This production of a herb extractcontaining shampoo is to add an aqueous solution of lauroyl methyl-beta -alanine sodium, an aqueous
solution of 2-alkyl-N-carboxyl-N-hydroxylethylimidazolium betaine, a (1:1) lauric acid diethanol
amide: palm oil fatty acid hydrolyzing collagen potassium solution, an active amino acid, an oligomer
enzyme, propylene glycol, hydroxyethylcellulose-hydroxypropyltrimethylammmonium chloride ether,
methyl paraoxybenzoate and citric acid and further add purified water and polyoxyethylene lauryl ether
sulfate to a herb extract.
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68. JP9315956
- 9/12/1997
PREPARATION OF GRANULE
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=JP9315956
Inventor(s):
SONOBE KAZUNORI (--)
Applicant(s):
HOUSE FOODS CORP (--)
IP Class 4 Digits: A23P; A61K; B01J
IP Class:A23P1/02; A61K9/14; A61K47/44; B01J2/28
Application Number:
JP19960137811 (19960531)
Priority Number: JP19960137811 (19960531)
Family: JP9315956
Abstract:
Abstract of JP9315956
PROBLEM TO BE SOLVED: To prepare the granules of a food, a medicine, etc., capable of
emphasizing its flavor, fragrance, etc., excellent in texture, capable of being maintained in a good
shape from their preparation time to their handling time. SOLUTION: This method for preparing the
granules of a food, a medicine, etc., comprises mixing a powdery raw material with the powder of a
binder having a melting point of 40-130 deg.C, heating and stirring the mixture at a higher temperature
than the melting point of the binder powder or higher, simultaneously spraying the heated and melted
products of solid fats containing a solid fat having a melting point of 40-120 deg.C in an amount
of ;=70% on the heated and stirred mixture, and subsequently cooling the mixture at a lower
temperature than the melting point of the binder powder or lower. The powdery raw material includes
various kinds of flavor materials and fragrant materials and is used in an amount of 70-95wt.%. The
binder powder includes beef tallow and palm oil, and is used in an amount of 4-20wt.%. The solid fats
are used in an amount of 1-20wt.%. The solid fats are the extract fats of a flavor raw component and/or
a fragrant raw component, or the heated mixture of a raw material solid fat with the flavor raw material
and/or the fragrant raw material. The method for preparing the granules is effective for granulating the
powder of a single spice such as pepper, the powder of a mixed spice such as curry powder, etc.
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69. KR8902096B
- 19/6/1989
PROCESS FOR PREPARING CONTENTS OF SOFT CAPSULE CONTAINING
WATER SOLUBLE HERB EXTRACTS
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=KR8902096B
Inventor(s):
LIM SONG-KI (KR)
Applicant(s):
HANMI PHARM IND CO LTD (KR)
IP Class 4 Digits: A61K
IP Class:A61K9/48
Application Number:
KR19870003399 (19870409)
Priority Number: KR19870003399 (19870409)
Family: KR8902096B
Abstract:
Abstract of KR8902096B
For the mass production of soft capsule containing herb medicine extracts, the preparation of the
capsule contains 18% of ginseng extract, 33.7% of palm oil, 41.3% of soybean oil, 2.5% of beeswax,
2% of -tocopherol and 2.5% of hard silicic anhydride.
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70. KR9310382B
- 23/10/1993
DETERGENT COMPOSITION
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=KR9310382B
Inventor(s):
SONG KI-CHAN (KR); SO SUN-YONG (KR)
Applicant(s):
DONGBANG JANGUP CO LTD (KR)
IP Class 4 Digits: C11D
IP Class:C11D3/382; C11D7/44; C11D3/38; C11D7/22
Application Number:
KR19910010187 (19910619)
Priority Number: KR19910010187 (19910619)
Family: KR9310382B
Abstract:
Abstract of KR9310382B
A cosmetic soap compsn. contains ginko biloba leave extract 0.01- 1.0 wt.%, mixture of palm oil and
palm kernel oil 1.0:0.1-1.0 wt.% ratio or 1.0:0.3-0.7 wt.% ratio as a oil component ginkgo biloba leave
extract contains 1.0-30.0 % of ginkgoflavon glycoside. This soap suppress aging of skin and has a good
beauty effect by blood circulation stimulating effect of ginkgo biloba leave extract.
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71. KR9400320B
- 17/1/1994
METHOD OF MAKING FOOD CONTAINING OF NOKAREN
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=KR9400320B
Inventor(s):
LEE HYONG-SU (KR)
Applicant(s):
LEE HYONG SU (KR)
IP Class 4 Digits: A23J; A23L
IP Class:A23J3/12; A23L1/29; A23J3/00
Application Number:
KR19910013064 (19910730)
Priority Number: KR19910013064 (19910730); KR19900012290 (19900810)
Family: KR9400320B
Abstract:
Abstract of KR9400320B
A health food contg. deer blood is prepd. by (a) mixing 3-50 wt.% deer blood powder, 50-90 wt.%
squalene and 5-20 wt.% additives, e.g. vegetable oil, soybean, phospholipid, vitamin, palm oil, ginseng
powder, lecithin, tocopherol, Ganoderna extract, pollen, honey etc., and (b) packing the mixt. in a soft
or hard capsule, or making a pill to obtain the final product. The deer blood powder is obtd. by
lysophilization. Thus, fresh deer blood was sterilized by adding ethanol and freeze-dried to give
powdered deer blood. The obtd. health food preserves for a long period.
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72. NZ331816
- 23/6/2000
NUTRIENT MEDIUM COMPRISING PEPTONE, YEAST EXTRACT,
COTTONSEED FLOUR, GLUCOSE AND PALM OIL
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=NZ331816
Inventor(s):
HEINS SHERRY D (--); EWING DUANE D (--); MARRONE PAMELA G (--)
Applicant(s):
AGRAQUEST INC (--)
IP Class 4 Digits: C12N
IP Class:C12N1/14
Application Number:
NZ19970331816 (19970617)
Priority Number: NZ19970331816 (19970617); WO1997US10343 (19970617)
Family: NZ331816
Abstract:
Abstract of NZ331816
A nutrient medium used in fermentation for increasing the yield of cells or microorganism is provided.
The formulation provided increases the yield of the fungus Lagenidium giganteum two-to three-fold
over known media. The medium for use in fermentation comprised of peptone, autolyzed yeast extract,
cottonseed flour, glucose (dextrose), palm oil, cholesterol, CaCl2.2H2O, and MgCl2.6H2O.
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73. PT96158
- 31/10/1991
PROCESS FOR OBTAINING A FOOD PRODUCT WITH DIETETIC
PROPERTIES
URL EPO = http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=PT96158
Inventor(s):
GARCIA-MORENO SEGUNDO MARCHAN (ES)
Applicant(s):
GUDRUN MARIANNE SELL (ES)
IP Class 4 Digits: A23D; A23L
IP Class:A23D7/00; A23L1/00; A23L1/29
Application Number:
PT19900096158 (19901211)
Priority Number: ES19900001012 (19900406)
Family: PT96158
Equivalent:
ES2023544
Abstract:
Abstract of PT96158
It consists of palm oil in a percentage of 31.82%, previously melted to liquefaction, wheatgerm oil in a
percentage of 40.90% at a temperature of 70 degree C and, with continuous agitation, previously
melted virgin wax is added in a percentage of 6.36%. Next, the temperature is lowered to 40 degree C
and, with agitation, ginseng extract in a percentage of 12.73% and soya lecithin in a percentage of
4.55% are added. Subsequently, lyophilized royal jelly is added in a percentage of 3.64% via a fine
sieve and the mass obtained is passed through a colloid mill. Finally, the mixture is homogenized and
subjected to a vacuum, the product prepared being ready for encapsulation and/or bottling and
packaging.
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74. RU2119287
- 27/9/1998
COMPOSITION FOR PREPARING FERMENTED MILK PRODUCT FOR
CHILD'S AND DIETETIC ALIMENTATION AND METHOD OF ITS
PRODUCTION
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=RU2119287
Inventor(s):
TIMAKOVA G A (--); KORNEV JU F (--); KON I JA (--)
Applicant(s):
TIMAKOVA GALINA ALEKSANDROVNA (--); KON IGOR JAKOVLEVICH (-); ORLOV ALEKSANDR SERGEEVICH (--); GAZHEV ALEKSANDR IVANOVICH (--)
IP Class 4 Digits: A23C
IP Class:A23C9/12; A23C9/13; A23C9/20; A23C9/00
Application Number:
RU19960124737 (19961230)
Priority Number: RU19960124737 (19961230)
Family: RU2119287
Abstract:
Abstract of RU2119287
FIELD: dairy industry. SUBSTANCE: composition contains milk, cream, malt extract or dextrin syrup,
corn oil, palm oil, copra oil, soya or peanut oil, sweetener, sweet quark whey prepared by ultrafiltration,
or lactose, or demineralized dry whey, dry whey protein, sour, iron and taurine preparations, fat- and
water-soluble vitamins and water. Oil mixture is heated and introduced in milk simultaneously with fatsoluble vitamins, cream and dry whey protein preliminarily dissolved in heated up to 35-40 C water or
milk whey, cooled, aged for proteins swelling and corrected with citrates of sodium and potassium.
EFFECT: increased assimilability and biological value of product. 6 cly
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75. RU2161419
- 10/1/2001
METHOD OF PREPARING PALATABLE BASE, READY-TO-EAT PRODUCTS,
AND PALATABLE BASE
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=RU2161419
Inventor(s):
ZHAN-ZHAK DESZHARDEN (FR); FILIPP DJUBI (FR); P ERR DJUPAR (FR);
ROBERT DASTEN VUD (GB); UL RIKH TSURKHER (CH)
Applicant(s):
SOS ETE DE PRODJUI NESTLE S A (CH)
IP Class 4 Digits: A23G; A21D; A23L
IP Class:A23G3/00; A21D2/36; A23G3/34; A23L1/00; A23L1/10; A23L1/105; A23L1/164;
A23L1/18; A23L1/187; A23L1/22; A23L1/23; A23L1/39; A21D2/00; A23L1/226
E Class: A23L1/105B; A23L1/18B2; A23L1/187B; A23L1/23
Application Number:
RU19960121518 (19961105)
Priority Number: EP19950810696 (19951107)
Family: RU2161419
Equivalent:
EP0772980; US5789003; OA10333; JP9163953; FI964456; PL183706B;
CA2189787; AU705373
Abstract:
Abstract of RU2161419
food industry, particularly, production of palatable base and its using for preparation of food products.
SUBSTANCE: method involves preparation of mixture containing at least water and starch-containing
raw material. Mixture is liquefied by at least one carbonic hydrase, and enzyme treatment of mixture is
conducted by lipase or lipoxygenase. The mixture may contain, %: water, 50-70; starch-containing raw
material, 25-50; vegetable oil, 0-5%. Mixture is liquefied by alpha-amylase in the amount of 0.2-0.5%
at temperature 50-85 C for 70-90 min. Prepared palatable base is used for production of food product.
Method of preparation of ready-to-eat products involves introduction of palatable base into
composition, containing, %: water, 8-15; starch-containing raw-material, 70-90; sugar, 2-20; hydrated
palm oil, 2-4; malt extract, 2-3; salt, 2-3; calcium carbonate, 0-1. Then composition is subjected to
extrusion providing boiling. EFFECT: preparation of palatable additive with taste of steamed grains
and/or toasts, and/or biscuit. 11 cl, 12 exDescription:
Description of corresponding document: US5789003
TECHNICAL FIELD
The subject of the present invention is a method of preparing a flavoring base, as well as its use for the
manufacture of food products.
BACKGROUND ART
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The use of flavorings or coating syrups to strengthen the cooked-grain taste and/or the biscuity taste
and/or the toasted taste has been known for a long time in the preparation of food products, in
particular in the manufacture of breakfast cereals and desserts. However, these flavorings or these
syrups often do not make it possible to reproduce the basic characteristic taste of these food products
obtained by a traditional methods.
CA 2,004,149 describes in particular a method of preparing cooked breakfast cereals, in which a
mixture based on a starchy starting material having a water content of 14-22% by weight is prepared
and is then extrusion-cooked. The extrusion-cooked and puffed product thus obtained may then be
dried, and next ground and agglomerated so as to obtain granules which may readily be dissolved in a
liquid.
According to EP 0,606,505, another known method of preparing breakfast cereals consists in preparing
a composition comprising in particular a starchy starting material and sugar and in extrusion-cooking
this composition with a suitable amount of water so as to obtain puffed cereals of the required density.
These cereal pieces may then be coated with a syrup and dried.
However, although they have the advantage of being quick, such methods do not make it possible to
obtain cooked cereals with a cooked-grain taste and/or with a biscuity taste and/or with a toasted taste
since the cooking time, which is generally about a minute, is too short.
SUMMARY OF THE INVENTION
The object of the present invention is to propose a method of preparing an flavorings base with a
cooked-grain taste and/or toasted taste and/or biscuity taste.
To this end, in the method of preparing an flavoring base according to the present invention:
a mixture comprising at least water and a starchy starting material is prepared,
the mixture is liquefied with at least one carbohydrase,
it is then treated enzymatically with a lipase or a lipoxygenase.
It has been observed, surprisingly, that such a method, which has the advantage of being quick, makes
it possible effectively to obtain an flavoring base with a cooked-grain taste and/or with a toasted taste
and/or with a biscuity taste.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the following description, the expression "starchy starting material" will be employed to denote a
cereal semolina or flour, in particular one from durum wheat, Triticum aestivum wheat, rice, barley or
corn.
To carry out the present method, a mixture comprising at least water and a starchy starting material is
prepared. A mixture comprising 50-70% water, 25-50% starchy starting material and about 0-5%
vegetable oil may be prepared, for example.
The mixture is liquefied, so as to reduce its viscosity, with at least one carbohydrase. It may be
liquefied with about 0.2-0.5% .alpha.-amylase, in particular with that marketed under the name Dexlo P
by Gist-Brocades N. V., Food Ingredient division, P.B. 01, NL-260 MA DELFT at 50 DEG -85 DEG C.
for about 70-90 min, for example. An .alpha.-amylase whose enzymatic activity is 170,000 Amylase
Units per gram is preferably used. This enzymatic activity is measured on a starch modified by
attaching a dye which, on becoming released, colors the solution, whose intensity becomes measurable.
The mixture is then treated enzymatically, preferably with a lipase or a lipoxygenase, so as to promote
the formation of flavoring compounds which give a characteristic basic taste.
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The mixture may be treated enzymatically with 0.5-1.5% lipoxygenase, in particular that extracted
from garden pea meal marketed by Fluka A. G., Chemische Fabrik, CH-9470 BUCHS St GALL, at 40
DEG -60 DEG C. for 80-100 min, so as to oxidize the polyunsaturated fatty acids to hydroxyperoxides,
which are unstable molecules, forming flavoring compounds, for example. A lipoxygenase whose
enzymatic activity is 135,000 Lipoxygenase Units per gram is preferably used. This enzymatic activity
is measured by measuring the oxidation of linoleic acid by the lipoxygenase under UV light.
The mixture may also be treated enzymatically with 0.05-0.2% lipase, in particular that marketed by
Novo Ferment A. G., Neumatt, CH-4243 DITTINGEN, at 45 DEG -65 DEG C. for 110-130 min, so as
to facilitate the oxidation of the fatty acids and the formation of flavoring compounds, on account of
the hydrolysis of the lipids into fatty acids, for example. A lipase having an enzymatic activity of
184,000 Lipase Units per gram is preferably used. This enzymatic activity is measured by measuring
the fluorescent intensity of a specific fraction associated with heptanoic acid.
In a first preferred embodiment of the present method, the mixture is dried after the enzymatic
treatment and after an optional brief inactivation of the enzymes with steam, for example. It may, in
particular, be dried on a cylinder. To do this, a film of liquid or pasty material to be dried is formed on
at least one heated cylinder, and the dried film is detached from the cylinder and then reduced to flakes.
The dried flavoring base thus prepared may be used directly for the manufacture of a food product or it
may be packaged and stored for subsequent use, for example.
In a second preferred embodiment of the present method, the mixture is heat-treated at 90 DEG -120
DEG C. for 10-30 min after the enzymatic treatment step, so as to stabilize it and to inactivate the
enzymes. A liquid flavoring base is thus obtained, which may be used directly for the manufacture of a
food product, or which may be packaged and stored for subsequent use, for example.
The subject of the present invention is also the use of the flavoring base obtained according to the
present method for the manufacture of a food product. It may be used, in particular, for the
manufacture of instant desserts and soups, for example. Similarly, it may be used in a food composition
intended for baby food, for example.
The flavoring base is preferably used for the manufacture of ready-to-eat cereals. To do this, the
flavoring base is preferably incorporated into a composition comprising 8-15% water and, as % solids
by weight, 70-90% starchy starting material, 2-20% sugar, 1-5% hydrogenated palm oil, 2-4% malt
extract, 2-3% salt and 0-1% calcium carbonate, which may be extrusion-cooked at 150 DEG -190 DEG
C. for 20-60 s for example. If the flavoring base is dried, it may be incorporated into the said
composition at a proportion of 10-80% dried base per 20-90% composition.
On the other hand, if the flavoring base is liquid, it may be incorporated into the said composition at a
proportion of 5-25% liquid base per 75-95% composition.
For the extrusion-cooking, a twin-screw extruder-cooker may be used, for example.
EXAMPLES
The method of preparing an flavoring base according to the present invention, and its use for the
manufacture of food products, are described in greater detail in the non-limiting examples below. In
these examples, the percentages and parts are given by weight on a basis, except where otherwise
indicated.
EXAMPLE 1
A mixture comprising 700 g of cornflour and 1300 g of water is prepared and is liquefied with
0.3% .alpha.-amylase at 60 DEG C. for 80 min.
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The temperature is then lowered to 50 DEG C. and the mixture is treated enzymatically with 1%
lipoxygenase for 90 min.
The mixture is heat-treated with stirring for 20 min at 110 DEG C. so as to inactivate the enzymes and
to stabilize the mixture.
A liquid flavoring base with a cooked-grain taste and a toasted taste is thus obtained.
EXAMPLE 2
The method is performed as described in Example 1, except that the enzymatic treatment is carried out
with 0.1% lipase at 55 DEG C. for 100 min.
A liquid flavoring base with a cooked-grain taste and a biscuity taste is thus obtained.
EXAMPLE 3
A mixture comprising 49% corn semolina, 50% water and 1% corn oil is prepared. It is liquefied with
0.3% .alpha.-amylase at 70 DEG C. for 90 min.
The temperature is then lowered to 50 DEG C. and the mixture is treated enzymatically with 1%
lipoxygenase for 90 min.
The enzymes are inactivated by injection of steam at 140 DEG C. for 15 s. The mixture is then dried
on a cylinder. To do this, the mixture is placed, in the form of a film, on a cylinder heated with
saturated steam at 110 kPa and rotating at 4.2 rpm. The film is detached from the cylinder and is
reduced to flakes.
A dried flavoring base with very pronounced toasted and biscuity tastes is thus obtained.
EXAMPLE 4
A mixture comprising 37.5% barley flour, 60.6% water and 1.9% corn oil is prepared. It is liquefied
with 0.45% .alpha.-amylase at 85 DEG C. for 60 min.
The temperature is then lowered to 45 DEG C. and the mixture is treated enzymatically with 1.5%
lipoxygenase for 60 min.
The enzymes are inactivated by injection of steam at 140 DEG C. for 15 s. The mixture is then dried
on a cylinder. To do this, the mixture is placed, in the form of a film, on a cylinder heated with
saturated steam at 110 kPa and rotating at 4.2 rpm. The film is detached from the cylinder and is
reduced to flakes.
A dried flavoring base with a taste of barley, with a biscuity taste and with a toasted taste is thus
obtained.
EXAMPLE 5
The method is performed as described in Example 4, except that a mixture comprising 37.5% rice
flour, 60.6% water and 1.9% corn oil is prepared.
A dried flavoring base with a cooked-grain taste and with a slightly biscuity taste is thus obtained.
EXAMPLE 6
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The method is carried out as described in Example 4, except that a mixture comprising 37.5%
wholewheat flour, 60.6% water and 1.9% corn oil is prepared.
A dried flavoring base with a cooked-grain taste and with a slightly biscuity taste is thus obtained.
EXAMPLE 7
The flavoring base as obtained in Example 1 is used for the manufacture of ready-to-eat cereals.
To do this, a composition is prepared comprising 10% water and, as % solids by weight, 86% corn
semolina, 7.2% sugar, 2.8% malt extract, 1.7% salt, 1.8% hydrogenated palm oil and 0.5% calcium
carbonate.
18% flavoring base, as % solids by weight, is incorporated into this composition during an extrusioncooking operation, which is carried out in a twin-screw extruder-cooker at 165 DEG C. for 40 s.
Ready-to-eat cereals which have a cooked-grain taste and a toasted taste are thus obtained.
EXAMPLE 8
The flavoring base as obtained in Example 2 is used and the method is carried out as described in
Example 7, for the manufacture of ready-to-eat cereals.
Ready-to-eat cereals having a cooked-grain taste and a biscuity taste are thus obtained.
EXAMPLE 9
The flavoring base as obtained in Example 3 is used and the method is carried out as described in
Example 7, except that 25% of the flavoring base is incorporated into the composition during the
extrusion-cooking, for the manufacture of ready-to-eat cereals.
Ready-to-eat cereals having a cooked-grain taste and a toasted taste are thus obtained.
EXAMPLE 10
The flavoring base as obtained in Example 4 is used and the method is carried out as described in
Example 7, except that 25% of the flavoring base is incorporated into the composition during the
extrusion-cooking, for the manufacture of ready-to-eat cereals.
Ready-to-eat cereals having a biscuity taste and a toasted taste are thus obtained.
EXAMPLE 11
The flavoring base as obtained in Example 3 is used for the manufacture of a poultry soup.
To do this, a mixture is prepared comprising 0.01 part antioxidants, 1 part salt, 6 parts hydrogenated
palm oil, 2 parts chicken fat, 2.5 parts chicken flavoring, 2 parts dehydrated chicken meat, 25.8 parts
maltodextrin, 1 part mono sodiumglutamate so as to strengthen the taste, and 2.6 parts flavoring
substances, in particular celery, pepper, onion and garlic.
57 parts dried flavoring base are incorporated into this mixture.
A powdered poultry soup is thus obtained, which the consumer can reconstitute while hot by mixing
25% of the said powder with 75% water at 90 DEG C., so as to obtain a creamy poultry soup.
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EXAMPLE 12
The flavoring bases as obtained in Examples 3, 4, 5 and 6 are used for the preparation of a dessert
cream.
To do this, a mixture is prepared comprising 5.7 parts milk proteins, 15.5 parts vegetable fats, 0.2 part
xanthan gum, 1.1 parts vanilla essence, 12 parts semolina sugar and 37.5 parts rice flour, dried
beforehand on a cylinder.
7 parts of each of the flavoring bases obtained in Examples 3, 4, 5 and 6 are added to this mixture.
A powdered food composition is thus obtained, which the consumer can reconstitute by mixing, while
cold, 25% of the said composition with 75% whole milk, so as to obtain a creamy, vanilla-flavored
dessert.Data supplied from the esp@cenet database - Worldwide
Claims:
Claims of corresponding document: US5789003
What is claimed is:
1. A method for preparing a flavoring base, which comprises:
preparing a mixture comprising at least water and a starchy starting material comprising wheat
semolina or flour;
liquefying the mixture with at least one carbohydrase; and
enzymatically treating the liquefied mixture with a lipase or a lipoxygenase to form the flavoring base.
2. A method for preparing a flavoring base, which comprises:
preparing a mixture comprising 50-70% water, 25-50% of a starchy starting material, and 0-5%
vegetable oil;
liquefying the mixture with at least one carbohydrase; and
enzymatically treating the liquefied mixture with a lipase or a lipoxygenase to form the flavoring base.
3. A method for preparing a flavoring base which comprises:
preparing a mixture comprising at least water and a starchy starting material;
liquefying the mixture with 0.2-0.5% .alpha.-amylase at 50 DEG -85 DEG C. for 70-90 minutes; and
enzymatically treating the liquefied mixture with a lipase or a lipoxygenase to form the flavoring base.
4. A method for preparing a flavoring base, which comprises:
preparing a mixture comprising at least water and a starchy starting material;
liquefying the mixture with at least one carbohydrase; and
enzymatically treating the liquefied mixture with 0.5-1.5% lipoxygenase at 40 DEG -60 DEG C. for
80-100 minutes to form the flavoring base.
5. A method for preparing a flavoring base, which comprises:
preparing a mixture comprising at least water and a starchy starting material;
liquefying the mixture with at least one carbohydrase; and
enzymatically treating the liquefied mixture with 0.05-0.2% lipase at 45 DEG -65 DEG C. for 110-130
minutes to form the flavoring base.
6. The method according to one of claims 1-5, in which the mixture is dried after the enzymatic
treatment step.
7. The method according to one of claims 1-5, in which the mixture is heat-treated at 90 DEG -120
DEG C. for 10-30 minutes after the enzymatic treatment step.
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8. The method according to one of claims 1-5, which further comprises adding the flavoring base to a
food product.
9. A method, for preparing a flavoring base, which comprises:
preparing a mixture comprising at least water and a starchy starting material;
liquefying the mixture with at least one carbohydrase;
enzymatically treating the liquefied mixture with a lipase or a lipoxygenase to form the flavoring base;
incorporating the flavoring base into a composition comprising 8-15% water and, as % solids by
weight, 70-90% starchy starting material, 2-20% sugar, 1-5% hydrogenated palm oil, 2-4% malt extract,
2-3% salt and 0-1% calcium carbonate; and then
subjecting the resultant composition to extrusion-cooking to impart a desired taste to the composition.
10. The method of claim 9 which further comprises drying the flavoring base before incorporating the
dried flavoring base into the composition, wherein the dried flavoring base is added at a proportion of
10-80% dried base per 20-90% composition.
11. The method of claim 9 which further comprises incorporating the flavoring base in liquid form into
the composition at a proportion of 5-25% liquid base per 75-95% composition.
12. The method of claim 9 which further comprises conducting the extrusion-cooking at a temperature
of 150 DEG -190 DEG C. for 20-60 seconds.
13. The method according to claim 1 wherein the starchy starting material is present in the mixture in
an amount of 25 to 50%.Data supplied from the esp@cenet database - Worldwide
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76. TW411365B
- 11/11/2000
NUTRIENT MEDIUM FOR INCREASING CELL YIELD IN FERMENTATION
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=TW411365B
Inventor(s):
MARRONE PAMELA G (US); HEINS SHERRY D (US); EWING DUANE D (US)
Applicant(s):
AGRAQUEST INC (US)
IP Class 4 Digits: C12N
IP Class:C12N1/00; C12N1/14; C12N1/16; C12N1/18
Application Number:
TW19980117128 (19981015)
Priority Number: US19960616738 (19960315); WO1997US10343 (19970617)
Family: TW411365B
Abstract:
Abstract of TW411365B
A medium for use in fermentation for increasing the yield of cells or microorganisms, conststing
essentially of: (a)3.6 g per liter peptone; (b) 1.5 to 3 g per liter autolyzed yeast extract; (c) 1.6g per liter
cottonseed flour; (d) 2.0 to 7.75 g per liter glucose (dextrose); (e) 2.5 g per liter palm oil; (f) 0.2 g per
liter cholesterol; (g) 0.6 g per liter CaCl2 . 2H2O; and (h) 0.2 g per liter MgCl2 . 6H2O. The
formulation provided increases the yield of the fungus Lagenidium giganteum two-to three-fold over
known media.
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77. UA6986U - 15/6/2005
MARGARINE
URL EPO = http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=UA6986U
Inventor(s):
RUDAVSKA HANNA BOHDANIVNA (UA)
Applicant(s):
KYIV NAT COMMERCIAL AND ECONOM (UA)
IP Class 4 Digits: A23D
IP Class:A23D7/00
Application Number:
UA20040010413U (20040120)
Priority Number: UA20040010413U (20040120)
Family: UA6986U
Abstract:
Abstract of UA6986U
A margarine contains solid and liquid fat fractions, an emulgator, table salt, a sweet additive, a dry milk
product, citric acid, vanillin, water, iodocasein. As a liquid fat fraction, it contains a mixture of plant
oils: rape, soybean and sunflower, and as a solid fat fraction ๛ a palm oil. As a dry milk product the
margarine contains Chicorlact and, as a sweet additive it contains a dry stevia extract.
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78. US2001006671
- 5/7/2001
GEL SYSTEM FOR ORAL AND TOPICAL ADMINISTRATION OF WATER
INSOLUBLE AND/OR WATER INTOLERANT DRUGS AND SUPPLEMENTS
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=US2001006671
Inventor(s):
GOODMAN LOUIS P (US); BIZUB DENNIS (US)
IP Class 4 Digits: A23L; A61K
IP Class:A23L1/00; A23L1/059; A23L1/30; A23L1/302; A23L1/303; A23L1/304; A23L1/305;
A61K9/00; A61K35/74; A61K47/02; A61K47/44; A23L1/05; A61K35/66; A61K31/70; A61K31/16;
A61K31/195; A61K31/355; A61K31/715; A61K33/00; A61K35/12; A61K47/00
E Class: A23L1/00P4B; A23L1/059; A23L1/30B; A23L1/302; A23L1/303; A23L1/304; A23L1/305A;
A61K9/00M18D; A61K35/72; A61K35/74; A61K35/78; A61K47/02; A61K47/44
Application Number:
US20000476352 (20000103)
Priority Number: US20000476352 (20000103)
Family: US2001006671
Equivalent:
US6617356
Abstract:
Abstract of US2001006671
Suspensions, emulsions or dispersions of therapeutically active agents which are water insoluble or
water intolerant such as nutritional supplements, herbal products, drugs, bacteria, yeast, vitamins and
minerals are prepared as suspensions in edible vegetable oils such as orange, lemon, soybean, cotton
seed, peanut, canola corn oil, sunflower, safflower, palm kernel, palm and coconut. The active
therapeutic agent may be in crystalline or amorphous form, it may be a liquid as for example an oil
such as vitamin E or beta carotene, or a preparation of a comminuted plant structure such as flower,
parts, leaf, stem, root or tree bark, or an extract of a dried plant structure, or a freeze dried preparation
of a vital bacteria or yeast. The suspension is formed by active mixing of the active agent and oil. To
the suspension of the active agent in vegetable oil is added the silica dioxide while actively mixing at
2000-4000 rpm to provide a stable gel, the active agent being uniformly distributed throughout the gel
Two to 60 minutes of stirring is more than adequate for all systems. The compositions can be
administered orally, sublingually, buccally and topically. For topical administration the preparation of
the invention may be formulated as a cream or ointment.Description:
Description of US2001006671
[0001] The present invention relates to a new drug delivery system, a method for suspending both
water insoluble and water intolerant materials in edible oils and products based thereon which are
stable over prolonged periods of time and are well suited as for oral and topical administration. The
method of the invention has particular advantage when the material involved undergoes changes
disadvantageous to its intended application on direct exposure to water. Such materials include creatine,
various Lactobacillus species, herbal products, vitamins, etc. It is therefore desirable to have a product
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which can be delivered in its active state without the use of water in its preparation, which is stable,
readily taken up by the body and provided in practical concentrations.
[0002] The drug delivery system of the invention comprises an edible oil to which a gelling agent, such
as silica dioxide is added. This system allows for uniform suspensions of the active agent, facilitating
drug delivery as well as in some instances regulating the rate of drug delivery. The active agent is
incorporated into the oil-gelling agent preparation providing formulations for therapeutic use.
[0003] The method of the invention comprises a series of steps whose sequence can be varied. In
accordance with one embodiment of the invention, the active material is introduced into the vegetable
oil under conditions for forming a uniform dispersion, emulsion or suspension and then a silica product,
namely silicon dioxide is introduced to form a pourable gel again under conditions whereby a stable
uniform thickened suspension of the active material in the gel will result. Alternatively the silica
dioxide can be added to the oil, and the active material then introduced into the thickened mixture to
form the suspension of the active material in the carrier gel.
[0004] The edible vegetable oils suitable for use herein include soybean, corn, orange and citrus oils,
cottonseed, olive oil, peanut oil, sunflower oil, safflower oil, coconut oil, canola oil, palm kernel oil,
palm oil. Mineral oils of varied molecular weights can also be used for some preparations. Mineral oil
is a standard ingredient in commercially available creams, ointment-type bases, as for example
available from Schering and is frequently used in topical drug delivery systems. Mineral oil can also be
used for oral ingestion. It has the advantage of being non-caloric and is without toxicity unless taken in
large doses. The vegetable oils mentioned are known food, nutritional supplement and drug
components and are especially suitable for use in the invention. Natural gums such as acacia or
tragacanth can be added to the combination of oil, active ingredient and silica product primarily to aid
in suspension of the insoluble pharmacologically active or nutritional supplement substance in the oil.
Substances such as synthetic mucilagenous materials including polyvinyl alcohol, methyl cellulose and
carboxymethyl-cellulose can be used in a similar manner to the natural gums. The synthetic gums have
the advantage of not being glycogenetic. The colloidal character and viscosity of the gums contribute
further towards preventing sedimentation of the suspended agents.
[0005] The dispersions or suspensions of the invention can be prepared by dispersing the silicon
dioxide product in the oil. As a rule, the dispersal step, e.g., treatment with a high angular speed
agitator, and the active ingredient then dissolved or dispersed in the gel formed after the initial
dispersal step. The second dispersal step can be carried out using the same stirrer, or other conventional
type homogenizing or emulsifying equipment. A suspension of the active agent in the pourable gelled
oil is thus formed. This suspension has a suitably long shelf life and can be used directly for its
application. When administered perorally, this suspension is used in a manner consistent with the type
of effective substance present, the amount of effective substance present and the therapeutic dose
which is commonplace for such administration. It is also possible to reverse the sequence by forming
first the dispersion of active ingredient in the oil, followed by a second dispersal step in which the silica
dioxide is introduced and distributed forming the gelled product.
[0006] In accordance with one embodiment of the invention the silica product can be added in
increments so that a first amount is added to the oil suspension and then a second amount of silica
product, preferably silicon dioxide, introduced again under conditions for ensuring the formation of a
stable thickened suspension of the active material in the gel.
[0007] A thixotropic gel is formed through the mechanism of hydrogen bonding between the silica and
active materials added. The gel suspends the ingredients that would normally precipitate or settle out.
The resultant stable suspensions contain the active material in discrete amounts in unaltered form. The
gel suspensions are suitable for oral and topical administration and can be use per se or with the
addition of the conventional adjuvants, colorants, flavorants etc.
[0008] Silicon dioxide or fumed silica the preferred gelling agent is characterized by extremely small
particle size, its enormous surface, high purity and its chain forming tendencies. Silicon dioxide is
produced by the vapor phase hydrolysis of silicon tetrachloride in a hydrogen-oxygen flame. The
combustion process creates silicon dioxide molecules which condense to form particles. The particles
collide, attach and sinter together resulting in a three-dimensional branched chain aggregate. Once the
aggregates cool further collisions result in mechanical entanglement of the chains, termed
agglomeration. The resulting white powder is of agglomerate size of less than 325 US mesh (44
microns).
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[0009] The surface chemistry of silica dioxide is extremely important especially in relation to its ability
to thicken non-polar and semi-polar liquid systems. During the preparation of silica dioxide, hydroxyl
groups become attached to some of the silicon atoms of the particle surface making it hydrophilic and
capable of bonding with suitable molecules of material in vapor, liquid or solid form. The surface OH
groups are capable of forming H bonds between silica dioxide aggregates. This network increases the
viscosity of the system and produces thixotropic behavior. Thixotropic behavior is the time dependent
recovery of viscosity after shearing (shearing forces due to mixing). The viscosity decreases in
proportion to the length of time of mixing or the intensity of the mixing. Once the shearing force has
been removed, the bonds rebuild over time and the viscosity approaches its original value. The
presence of these OH groups is the key to the mechanism through which silica dioxide is able to
perform many of its functions. The most important and widespread use of silica dioxide in liquid
systems is for the control and increase of viscosity and thixotropy. A major determinant of the effect of
silica dioxide will produce in any system is the nature of the solvent or suspending material used.
Network formation is determined to a large degree by the capability of the solvent or suspending agent
to participate in the formation of hydrogen bonds. Heretofore this capacity of silica dioxide has not
been applied to the thickening of oils or for the purpose of producing stable suspensions of watersoluble, water insoluble and water intolerant drugs and supplements suitable for oral and topical
administration.
[0010] In accordance with the invention, the suspending medium can be grouped into three
classifications. It is in the non-hydrogen-bonding systems (class 11) that silicon dioxide displays its
greatest efficiency, the silica particle has no choice but to hydrogen bond with other silica particles and
the greatest degree of network formation is achieved at the lowest concentration of silica.
Concentrations of 3% to 6% silica dioxide by weight are usually sufficient to provide fairly thick gel
formations, smaller concentrations will provide any viscosity required up to the stage of gelation.
Examples of suspending agents suitable for use therein are the mineral oils, vegetable oils, etc.
[0011] In medium hydrogen bonding systems (class 11) silica dioxide is slightly less efficient than the
non-hydrogen-bonding systems. Usually the level of silica needed for gel formation is 5 to 10 weight
percent. Examples of solvents and suspending media in this class also include vegetable oils, including
peanut, corn, canola, olive, soy, orange and lemon oils, sunflower, safflower, coconut, palm and palm
kernel.
[0012] In highly hydrogen-bonding systems (class 1) a much higher concentration of silica dioxide will
be required to produce a given increase in viscosity and thixotropy. A silica load as much as 10 to 15
weight % may be required.
[0013] Maximum viscosity of silica dioxide, 2% by weight is obtained quickly after vigorous mixing
for example using a rotor stator high speed stirring apparatus, high angular speed agitator or blender.
[0014] The following is a comparison of viscosities characteristically obtained with the different
classes of suspending media:
[0015] Mineral Oil class 111-1-4% by weight of silicon dioxide produced a Brookfield viscosity of
1,000 to 70,000 cps.
[0016] Vegetable Oil class 11-1-4% by weight of silicon dioxide produced a Brookfield viscosity of
about 1000 cps, 6-8% about 10,000 cps.
[0017] Viscosity values are in centipoises (cps) as measured using a Brookfield viscometer at 6 rpm at
room temperature and in one minute. Viscosities then level off for group 11 and 111 agents and do not
change substantially with time. The viscosity is unchanged through pH 1 to 9 but will fall off with
higher pH values.
[0018] Silicon dioxide has been widely used in foods, pharmaceuticals, animal feeds, cosmetics, etc.
[0019] Extensive toxicological studies indicate that silicon dioxide does not possess the fibrogenic
potential of crystalline silicas. Tests for acute oral toxicity, primary dermal irritation, primary eye
irritation, and mutagenic tests indicate that silicon dioxide is inert.
[0020] Silica dioxide meets the USP National Formulary requirements for purity. It has been
authorized by the FDA for cosmetic applications. It has been approved by the FDA for food use up to 2
weight percent, for pharmaceutical use up to 3 weight per cent in internal applications and up to 8
weight percent in pharmaceutical products for use in topical applications. It is classified as a nonhazardous, non-restrictive substance under the provisions of the Hazardous Materials Act (P.L. 93-633).
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[0021] Silicon dioxide is a unique, amorphous, of extremely high purity, sub-micron size material. and
has been approved by the FDA. Some of its particularly important properties for use in medicinal
preparations intended for topical and oral use include silicon dioxide's fine particle size, high purity,
amorphous structure, chemically inertness, non-toxicity, that it is easily handled and dispersed, and is
colorless, odorless and tasteless.
[0022] In accordance with the invention silicon dioxide is used as a suspending or anti-settling agent
for many different types of applications including suspension of solids in liquids or for the suspension
of liquids in liquids (emulsions). The suspending ability of silicon dioxide is a result of the formation
of a network when it is dispersed in a liquid. The network serves to keep droplets of particles separated
from each other so that they cannot readily coalesce and undergo phase separation or settle out. The
increased viscosity of the system helps to impede the rate of movement of all the ingredients in the
mixture. Silicon dioxide is available in a number of grades which are suitable for use in the invention.
These grades vary with the surface area of the aggregates and the degree of compression of the final
product. The grade preferably used in the invention has a surface area (m 2/g) of 200+-25. Chemical
and physical analysis indicates that the percent silica dioxide present in the product is greater than
99.8% and that the average particle size (aggregate) is +-0.2 to 0.3 microns.
[0023] A large number of pharmacologically active preparations can be prepared by the method of this
invention; of particular interest are the following:
[0024] Creatine (C4H9N3O2) which is a normal constituent of muscle, brain and blood, is involved in
energy storage in skeletal muscle and other tissues. Creatine is synthesized in the liver from amino
acids and then transported by the blood to the muscle. There the enzyme creatine phosphokinase
catalyzes the reaction of creatine with ATP to form phosphocreatine. Phosphocreatine contains a high
energy PO4 bond and serves as an energy storage mechanism. Creatinine is a catabolic end product, an
anhydride of creatine (or phosphocreatine) produced by the loss of water (or phosphoric acid) from the
molecule in an irreversible reaction. Creatinine is not reutilized, but is excreted via the urine. It is
formed at a nearly constant rate which is proportional to the body muscle mass. Numerous studies have
shown that the use of oral creatine supplementation in doses of 20 grams creatine monohydrate per day
for five days produces an increase in muscle total creatine concentration as well as a cumulative
increase in both peak and total work production.
[0025] The propensity for creatine to convert to creatinine in a water based solution can be avoided by
the method of this invention, i.e., by forming in accordance with one embodiment of the invention is a
suspension of silicon dioxide in vegetable oil followed by addition of creatine monohydrate. The user
can use the liquid gelled suspension directly and does not have to suspend a powder in a liquid such as
water, juice or the like before utilization.
[0026] In accordance with another embodiment of the invention, creatine monohydrate is combined
with one of the 20 amino acids and/or sugars which can be a monosaccharide, disaccharide,
trisaccharide or polysaccharide.
[0027] Examples of the monosaccharides which are suitable are the pentoses including D-arabinose, Larabinose, D-ribose, 2 deoxyribose, D-xylose and D-erythropentulose.
[0028] Examples of monosaccharide hexoses which can be used in the invention are D-galactose, Lgalactose, D-glucose, D-mannose and D-fructose.
[0029] Examples of disaccharides include maltose, [alpha],[alpha] trehalose and sucrose.
[0030] An example of trisaccharide is raffinose which is found in sugar beets.
[0031] Polysaccharides which can be advantageously used are starch and glycogen.
[0032] Any of the amino acids which are conventionally used in food and nutritional supplements can
be used for combination with the creatine monohydrate. Combinations of creatine monohydrate with a
saccharide as above exemplified may be used in sports nutrition for achieving optimal performance.
[0033] It is well recognized by those versed in the art that the amino acids can be replaced by full
proteins or partially digested proteins such as peptides.
[0034] Lactobacillus This term generally designates catalase negative, gram positive, non-motile rods
that grow aerobically and ferment carbohydrates, either homofermentatively to lactic acid or
heterofermentatively into lactic acid and other products including carbon dioxide.
[0035] Four species of lactobacillus are preferred for use in the invention, namely Lactobacillus
acidophilus, Lactobacillus rhamnosus, Lactobacillus casei, SPP Para casei and Lactobacillus bulgarious.
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[0036] Lactobacillus acidophilus is an inhabitant of the small intestine in humans. Acidophilus
manufacture lactase to digest milk sugar and produces lactic acid, which serves to suppress undesirable
bacteria and yeasts. Some strains are reported to produce natural antibiotics, to lower cholesterol levels
and to kill yeasts such as Candida. Lactobacillus bulgaricus is a transient but very important bacterium
which by manufacturing lactic acid, in the gastrointestinal tract encourage a good environment for the
resident bacteria such as acidophilus.
[0037] Bifidobacterium bifidum and Bifidobacterium longum. These bacteria are the main inhabitants
of the large intestine and are also found in the lower part of the small intestine and vagina. They
produce a number of specialized acids, which act to prevent colonization of the large intestine by
invading bacteria, yeasts and viruses. They also prevent toxicity from nitrates in food and assist in the
manufacture of B vitamins.
[0038] Enterococcus. A genus of gram-positive bacteria which belong to the family Streptococcaceae.
Of the 12 species two are found in the human gastrointestinal tract. They are amphiobiotic without
clearly defined primary pathogenicity.
[0039] Yeasts. The yeast's are an effective food supplement. They produce B 1 and B 2 vitamins and
niacin and other B complex vitamins.
[0040] It is well recognized that it is advantageous to have these microflora in the intestine. These
microorganisms are available as freeze-dried powders that are generally and heretofore have been
ingested after first mixing with milk or juice at the time they are to be consumed. In some preparations
the organisms are dispensed in capsule form. They cannot be dispensed suspended in water and kept
for any length of time, as they will continue to divide and eventually die in their own waste products as
they become too numerous for the solution they are suspended in. The method of this invention,
suspension in oil of the silicon dioxide gelling agent and then the addition of the lyophilized bacteria
avoids the death of the organism and doesn't allow the organism to grow until it reaches the intestine.
[0041] The usual dose of organisms is about 20 million to 400 million organisms (CFU).
[0042] Any number of medicinal herb products can also be prepared by the method of the invention.
Among the preferred are:
[0043] Hypericum Perforatum (St.John's Wort). St.John's Wort consists of the dried above ground parts
of Hypericum perforatum gathered during flowering season. The active ingredients are anthracene
derivatives (0.1-0.15%), in particular hypericin flavonoids (2-4%), xanthenes, acylchloroglucinols,
volatile oils, oligomeric procyanidines, catechin tannins and caffein acid derivatives. It acts as a mild
antidepressant, sedative, and anxiolytic. It is also used for treatment of inflammation of the skin, and
for treatment of wound injuries and burns. Studies have demonstrated that the antidepressant effect
may be due to the presence of a monoamine oxidase inhibiting function in the active agents as well as
the ability of the herb to inhibit the re-uptake of serotonin. Oily Hypericum preparations demonstrate
an anti-inflammatory action due to their high flavonoid content.
[0044] The average daily dose of drug is 0.2 to 1.0 mg of total hypericin. This corresponds to 2 to 4
grams of herb powder. Standardized preparations of the dried herb product are calibrated to contain
0.15-0.3% hypericin; this would correspond to 1.5 to 3 grams of herb powder.
[0045] Ginkgo Biloba (Ginkgo). The medicinal parts are the leaves and the seeds separated from their
fleshy outer layer. The active compounds are flavonoids, biflavonoids, proanthocyanidins, trilactonic
diterpenes, and trilactonic sesquiterpene.
[0046] Ginkgo acts by inhibition of the development of traumatically or toxically induced cerebral
edema and inhibition of cellular lesions in the retina by inhibition of age related reduction of
muscarinergic cholinoceptors as well as stimulation of choline uptake in the hypo campus. Indications
and usage are for brain dysfunction, including memory loss, symptomatic relief of intermittent
claudication, vertigo of vascular origin, and tinnitus of vascular origin.
[0047] The average daily dose is 240-360 mg of dried extract. The dried extract is prepared from the
dried Ginkgo biloba leaf and is manufactured using acetone/water extraction and subsequent
purification steps. Generally ginkgo is taken in 2 or 3 doses, orally. Ginkgo preparations are available
standardized to contain 24% ginkgo flavones glycosides; and the recommended dose of this preparation
is 30-100 mg per dose.
[0048] Piper Methysticum (Kava-Kava). The medicinal parts are the peeled, dried cut rhizome with or
without roots. The active ingredient is Kava lactone (Kava pyrones 5-12%). Comminuted rhizome and
other galinic preparations are used in preparing pharmaceutical preparations.
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[0049] The drug has anti-anxiety effects. It is indicated and used for nervousness and insomnia. The
daily dose for herbs and extracts is the equivalent of 60 to 120 mg kava pyrones.
[0050] The method of this invention allows for combination of herbal products e.g., St.John's Wort and
Ginkgo. A daily dose would be 300 mg of St. John's Wort (0.3% hypericin) and 60 mg Ginkgo Biloba.
Another combination could be St. John's Wort and Kava Kava. A daily dose would be 300 mg St.
John's Wort (standardized to 0.3% hypericin) and 250 mg Kava Kava (root powder).
[0051] Vitamins and Minerals. Vitamins and minerals could readily be dispensed by the method of the
invention, either as a single vitamin or in combination with other vitamins and/or minerals. Listings of
such vitamins and minerals and the percent Daily Values which have been determined by the National
Research Council of the National Academy of Sciences are readily available in the literature along with
their pharmacological action.
[0052] In accordance with yet another embodiment of the invention water-soluble materials such as
creatine monohydrate, sugars, amino acids, water-soluble vitamins, etc., are combined with fat-soluble
materials such as Vitamins A, D, E and K, Co-Enzyme Q-10, etc., into a matrix containing soybean oil
and silicon dioxide.
[0053] A host of other biological active substances such as amino acids, melatonin, chitosan, other
herbal products, etc., could be prepared in combination or as a single entity.
[0054] Drug absorption is determined by physicochemical properties of drugs, their formulations and
method of administration. The actual dosage forms include liquid-liquid suspensions, liquid-solid
dispersions liquid-liquid emulsions and semi-solids (creams, ointments), in a gel form. These dosage
forms are formulated to be administered by various routes, including oral, buccal, sublingual, and,
topical.
[0055] For oral administration, the most common route, absorption refers to the transport of drugs
across the membranes of the epithelial cells in the gastrointestinal tract. The oral mucosa has a thin
epithelium and a rich vascularity that favors absorption, but contact is usually too brief, even for drugs
in solution, for appreciable absorption to occur. A drug administered by introduction between the gums
and cheek (buccal administration) or under the tongue (sublingual administration) is retained longer so
that absorption is more complete. Drugs given orally are subjected to numerous gastrointestinal
secretions and to be absorbed must survive encounters with low pH and potentially degrading enzymes.
[0056] The advantage of the suspensions (dispersions) of the invention is the physiological
composition of the system and the simple method of production thereof. An important advantage is that
due to the oil/active ingredient suspension the preparation can be persorbed to the digestive tract
through the intestinal wall. The mechanism of oral absorption provides a good distribution of the
effective substance into the tissues. The dissolution rate determines the availability of the drug for
absorption. Over all absorption can be controlled by manipulating the formulation, for example,
reducing the particle size increases the drug's surface area, thus increasing the rate and extent of
absorption. Controlled release dosage forms are designed to reduce dosage frequency, and to reduce
fluctuation in plasma drug concentrations, providing a more uniform therapeutic effect. Oral controlled
release forms are often designed to maintain therapeutic drug concentrations for about 12 hours. The
absorption rate in accordance with the invention is controlled by embedding the drug in a matrix from
which it is released slowly during transit through the gastrointestinal tract. Further the oil particles are
stored in the fat tissue and thereby provide a deposition effect for the effective substance. Due to the
enzymatic fat decay, the effective substance is released over a longer period of time than heretofore
possible with the conventional orally administered types of pharmacologically effective substances.
Again advantageously, the achieved deposition effect from the oil suspension of the invention restricts
the ingestion of the active agent to at most once daily, or contrary to conventional forms which are
administered several times a day. This assures improved therapeutic reliability.
[0057] Drugs for transdermal delivery must have suitable skin penetration characteristics and high
potency, because the penetration rate and area of application are limited.
[0058] The bioavailability or extent to which the active agent enters the systemic circulation is
determined by its physical and chemical properties, but the properties of the dosage form can also
largely determine drug bioavailability.
[0059] Absorption from the oral mucosa has special significance for certain drugs, despite the fact that
the surface area is small. Venous drainage from the mouth is to the superior vena cava. Significantly
the drug is protected from rapid first pass metabolism by the liver. The rate of absorption through the
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mucous membrane is rapid. Another advantage of absorption from the oral mucosal membrane is the
elimination of the effect of digestive enzymes, food intake on the rate and on the resulting
concentration of the pharmacological agent during the absorption process. The exposure of the active
agent to the low pHs of the stomach is also avoided.
[0060] The formulations for most types of dosage forms of the substances used in accordance with the
invention can contain several types of inert adjuvant ingredients which aid in their preparation and
therapeutic performance. In order to increase the patient acceptability of the product, colorants and
flavorants may be added.
[0061] An important advantage of the invention arises from the fact that the formulations of the present
invention contain an oil phase and are thus less apt to be colonized by bacteria, yeasts, molds or fungi.
A non-toxic, non-sensitizing preservative compatible with the formulation composition can however be
added. The addition of a preservative selected from the phenol or the para-hydroxybenzoate
compounds can be provided for. The gel formulation may be prepared to contain 0.1 to 0.2% by weight
chlorocresol, a phenol derivative or preferably 0.01 to 0.2% by weight parahydroxybenzoate as methyl,
ethyl, butyl or propyl-paraben.
[0062] Formulations of the present invention are administered by oral for example for absorption
through the oral mucosa or topical route by dispensing the suspension from a one milliliter calibrated
dropper or if desired a two ml calibrated dropper. The oral dose can be 0.5 to 2.0 ml of the suspension;
the topical dose from 0.1 to 0.5 ml. The thixotropic nature of the gel facilitates the application of small
volumes of medication. High viscosity preparations may not always be desirable and convenient for the
delivery of therapeutic materials. The characteristic thixotropy of the silicon dioxide stabilized oil
system is such that the shearing forces of shaking, pipetting and pouring make the product behave as a
mixture of much lower apparent viscosity thus facilitating oral ingestion as well as enabling the
administration of the oral and topical preparations. As noted earlier, the suspensions can be formulated
as creams, ointments or unguents. This can be accomplished by incorporating the suspension of active
agent into a suitable base or by suitably thickening the suspension by a second addition of silica
dioxide compound.
[0063] The formulation of the final dosage form of the gel for administration must respect the
following criteria: (i) all components of the preparation including suspension agent, gelling agent,
thickening agents, preservatives, coloring and flavoring agents should be non-toxic and compatible
with the therapeutic agents; (ii) the final product should promote optimal release of the active agent to
its site of action; (iii) be of adequate consistency to enhance contact time with the drug and (iv) have
good patient acceptability.
[0064] Thus, in accordance with the invention suspensions, emulsions or solutions of therapeutic active
agents which are water insoluble or water intolerant such as nutritional supplements, herbal products,
drugs, bacteria or yeast, vitamins and minerals are prepared in edible vegetable oils including without
limitation orange, lemon, soybean, cotton seed, peanut, canola, corn oil sunflower, safflower, coconut,
canola, palm kernel, palm but preferably soybean oil and in some instances in mineral oils of low
molecular weights. The active therapeutic agent may be in crystalline or amorphous form, it may be a
liquid, as for example, an oil such as vitamin E or beta carotene or a preparation of a comminuted plant
structure such as flower parts, leaf, stem, root or tree bark, or an extract of a dried plant structure, or a
freeze dried preparation of a vital bacteria or yeast. The oil solvent containing the active agent as a
suspension, emulsion or solution and depending on the physical and chemical characteristics and
stability of the solvent/solute, may contain adjuvant ingredients as necessary for proper preparation and
therapeutic performance. Colorants and flavorants may be added to increase the acceptability of the
product. If the addition of a preservative is desirable a preservative selected from the phenol or the para
hydroxybenzoate compounds can be added. Natural gums such as Acacin or Tragacanth can be added
primarily to aid in suspension of insoluble pharmacologically active substances in the oil. Other useful
synthetic mucilagenous substances including poly vinyl alcohol, methyl cellulose and
carboxymethylcellulose may also be used. To the suspension of the active agent in the vegetable oil
there is added the prescribed amount of silica dioxide, in proportioned amounts at the same time
actively mixing with a propeller stirrer (a high shear mixer at 2000-4000 rpm). Higher mixer speeds
can be utilized if the therapeutic moiety will not be denatured by the mixing action. Viscosity
measurements have shown that peak viscosities which remain stable are found after short periods of
vigorous mixing of silicon dioxide in the vegetable oil. Mixing to obtain a complete and uniform
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dispersion of the solute in the oil occurs quickly, again somewhat dependent on the physical and
chemical characteristics of the therapeutic agent being dispersed. Two to 5 minutes have been found to
be adequate for some systems while longer times of up to 60 minutes are required for other systems.
These procedures are carried out at room temperature. The dispensing of the suspension should take
advantage of the thixotropy property of the silicon dioxide. The physical and chemical characteristics
of the active agent, particle size, absorption rate, required amount of active agent per dose, and end use
will determine the route of administration, i.e., oral, topical or both. Generally a less viscous
preparation could be used for sublingual and buccal oral application, and a more viscous preparation
for oral ingestion. For topical administration the preparations of the invention may be formulated as the
suspension, or the suspension distributed in a cream or cream ointment.
[0065] The invention is additionally illustrated in connection with the following examples, which are to
be considered illustrative of the present invention.
EXAMPLE 1
[0066] Seven and one half grams of silicon dioxide (having a surface area of (m 2/g) of 200+-25)) is
added to soy bean oil in a vessel to achieve a final volume of 250 ml while mixing at a low speed of
1000-2000 rpm with a propeller stirrer high shear mixer, until all the silicon dioxide is completely
dispersed and suspended in the soy bean oil. 100 grams of creatine monohydrate are then introduced
under stirring into the suspension previously obtained and the stirring continued for 10 additional
minutes at 7000 rpm. An ultra-fine suspension of creatine in the thickened soybean oil is obtained. The
concentration of creatine monohydrate in the suspension is 40 grams per 100 ml; an oral dose of 50 ml,
the recommended dose, would contain 20 grams of creatine monohydrate.
EXAMPLE 2
[0067] A suspension of creatine monohydrate and taurine was prepared by introducing the silicon
dioxide, 3 grams into 85 ml of canola oil under stirring for 3-5 minutes in a commercial agitator at
1000-2000 rpm. This is followed by the introduction of 10 grams creatine monohydrate and 3 grams of
taurine and the latter mixture dispersed in the thickened canola oil for 3 minutes in the agitator
operating at 7000 rpm. An ultra-fine suspension of the creatinine monohydrate and taurine in the
thickened canola oil with a concentration of 10 grams creatine monohydrate per 100 ml and 3 grams of
taurine per 100 ml of canola oil silicon dioxide gel. The recommended oral dose is 50 ml and would
contain 5 grams of creatine and 1.5 grams of taurine respectively.
EXAMPLE 3
[0068] Seven and one-half grams of silicon dioxide are added to safflower oil in a vessel to achieve a
final volume of 250 ml while mixing at a low speed of 500-1000 rpm with a high shear mixer until all
the silicon dioxide is completely dispersed and suspended in the safflower oil. One hundred grams of
creatine monohydrate, 5 grams of L-glutamine and 12.5 grams of ribose are dry blended and then
introduced under continual stirring into the suspension previously obtained. The stirring is continued
for 35 minutes at 3000 rpm until an ultra-fine suspension of creatine, ribose and glutamine are obtained.
The concentration of creatine monohydrate in the suspension is 40 grams per 100 ml, 2 grams per 100
ml for the glutamine, and 5 grams per 100 ml for the ribose. A 50 ml dose would contain 20 grams of
creatine, 1 gram of glutamine and 2.5 grams of ribose.
EXAMPLE 4
[0069] Standardized dried ginkgo extract, 15 grams are added to a blender mixer vessel containing
soybean oil to give a final volume of 100 ml, and the contents mixed at high speed. Four grams of
silicon dioxide are added and the mixing continued. The concentration of Ginkgo in the suspension is
0.15 grams dried Ginkgo extract equivalent to 3.6 grams Ginkgo flavone glycosides per 100 ml of
soybean oil/silicon dioxide gel the resulting preparation is suitable for peroral administration the
suspension is characterized by its stability over long periods of time. The recommended dose is 150 mg
twice daily and would be administered sublingually with a calibrated dropper in a 1 ml volume.
EXAMPLE 5
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[0070] Seven and one half grams of silicon dioxide are added to soybean' oil in a vessel to achieve a
final volume of 250 ml while mixing at a low Speed of 500-1000 rpm with a high-shear mixer until all
of the silicon dioxide is completely dispersed and suspended in the soybean oil. One gram of Vitamin E
(1110 IU/gram) is added to the mix. Mixing is continued at 501000 rpm for an additional 2-3 minutes.
One hundred grams of Creatine monohydrate, 5 grams of L-glutamine and 12.5 grams of ribose are dry
blended together and then introduced under continual stirring into the suspension previously obtained.
The stirring is continued for 35 minutes at 3000 rpm until an ultra-fine suspension of creatine
monohydrate, ribose, glutamine and Vitamin E are obtained in the soybean oil.
[0071] The concentration of Creatine monohydrate in the suspension is 40 grams per 100 ml., 2 grams
per 100 ml for the glutamine, 5 grams per 100 ml for the ribose and 440 IU per 100 ml for the Vitamin
E. A 50 ml dose would contain 20 grams of creatine, 1 gram of 1 gram of glutamine, 2.5 grams of
ribose and 220 IU's of Vitamin E.
EXAMPLE 6
[0072] A stock suspension of 4 vitamins was prepared in mineral oil which had been gelled by addition
of silicon dioxide and stirring at 2000 rpm so that 5 ml contain the following: Vitamin A (Retinol)
200,000 IU, Vitamin C (Ascorbic Acid) 20,000 mg, Vitamin D (cholecalciferol) 8,000 IU, and Vitamin
E (alpha-tocopherol) 8,000 IU. This vitamin preparation was dispersed in 95 ml of a conventional and
readily available polyacrylic gel with a paddle type stirrer. After thorough mixing the resultant
dispersion was dispensed into appropriate containers. The resultant gel formulation is applied to the
skin in approximately 1 gram amounts daily.Data supplied from the esp@cenet database - Worldwide
Claims:
Claims of US2001006671
1. A carrier suitable for oral and topical administration of a drug or nutritional supplement which is
water insoluble or water intolerant comprising a stable suspension of silicon dioxide in a number
selected from the group consisting of food grade vegetable oils and mineral oils; said carrier being in
the form of a pourable gel.
2. A carrier according to
claim 1 wherein said food grade vegetable oil is a member selected from the group consisting of soy
bean, orange, citrus, cotton seed, corn, olive, peanut, safflower, sunflower, palm kernel, palm, canola
and coconut oil.
3. A carrier according to
claim 1 wherein said food grade vegetable oil is soy bean oil.
4. A carrier according to
claim 1 wherein the silicon dioxide is present in the amount of about 2%-15% by weight.
5. A carrier according to
claim 1 wherein said gel is dispersed in a member selected from the group consisting of creams,
unguents and ointments.
6. A composition comprising an effective dosage amount of a member selected from the group of water
insoluble and/or water intolerant drugs and nutritional supplements dispersed in the carrier of
claim 1.
7. A composition according to
claim 6 wherein said food grade vegetable oil is a member selected from the group consisting of soy
bean, orange, citrus, cotton seed, corn, olive, peanut, safflower, sunflower, palm kernel, palm, canola
and coconut oils.
8. A composition according to
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claim 7 wherein said food grade vegetable oil is soy bean oil.
9. A composition according to
claim 6 wherein the silicon dioxide is present in the amount of about 2%-15% by weight.
10. A composition according to
claim 6 wherein said water-insoluble or water intolerant drug or nutritional supplement is at least one
member selected from the group consisting of creatine, Lactobacillus, Bifidobacterium bifidum,
Bifidobacterium longum, Enterococcus, yeast, St. John's Wort, Ginkgo Biloba, Kava-Kava, vitamins
and minerals.
11. A composition according to
claim 10 additionally containing at least one member selected from the group consisting of creatine,
monohydrate, monosaccharides, disaccharides, trisaccharides, starch and glycogen.
12. A composition according to
claim 6 wherein said food grade oil is soy bean oil.
13. A composition according to
claim 6 wherein said group member is water intolerant.
14. A composition according to
claim 12 wherein said water intolerant group member is creatine.
15. A composition according to
claim 6 additionally containing at least one member selected from the group consisting of preservatives,
colorants, flavorants, natural gums and miscellaneous substances.
16. A composition according to
claim 6 suitable for oral administration.
17. A composition according to
claim 6 suitable for topical administration.
18. A composition according to
claim 10 wherein said nutritional supplement is Ginkgo Biloba.
19. A composition according to
claim 10 wherein said group member is at least one vitamin.
20. A composition according to
claim 18 dispersed in a member selected from the group consisting of creams, salves and unguents.
21. A composition according to
claim 6 wherein said vegetable oil is soy bean oil and said nutritional supplement is creatine
monohydrate.
22. A composition according to
claim 6 wherein said vegetable oil is canola oil and said nutritional supplement is a combination of
creatine monohydrate and taurine.
23. A composition according to
claim 6 wherein said vegetable oil is safflower oil and said nutritional supplement is a combination of
creatine monohydrate, [sigma]-glutamine and ribose.
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24. A composition according to
claim 6 wherein said vegetable oil is soy bean oil and said nutritional supplement is a combination of
creatine monohydrate, [sigma]-glutamine and ribose and Vitamin E.
25. Method for preparing a composition according to
claim 6 which comprises dispersing silica dioxide in a member selected from the group consisting of
food grade vegetable oils and food grade mineral oils under thorough mixing to form a gel and
thereafter introducing a member selected from the group consisting of drugs and nutritional
supplements into the gel formed in the preceding step under thorough mixing.
26. Method according to
claim 25 wherein said thorough mixing is carried out using a member selected from the group
consisting of high angular speed agitators, homogenizers, emulsifying equipment, blenders, high speed
propeller stirrer mixers and high speed paddle mixers.
27. Method according to
claim 25 wherein said gel formed in the first step has a viscosity of about 10,000 to 100,000 cps
(Brookfield).Data supplied from the esp@cenet database - Worldwide
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79. US2003031740
- 13/2/2003
TREATMENT OF VEGETATION LIQUORS DERIVED FROM OIL-BEARING
FRUIT
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=US2003031740
Inventor(s):
SAMBANTHAMURTHI RAVIGADEVI (MY); TAN YEW AI (MY); SUNDRAM
KALYANA (MY)
IP Class 4 Digits: A61K
IP Class:A61K35/78
E Class: A61K35/78
Application Number:
US20020269224 (20021011)
Priority Number: US20020269224 (20021011); MY19980004378 (19980924); US19990405206
(19990924)
Family: US2003031740
Abstract:
Abstract of US2003031740
The present invention relates to processes for the treatment of liquors derived from oil-bearing fruit, for
example from oil palm fruit, and to products therefrom. Typically a process involves removal of
undissolved solids, oleaginous parts, colloids and higher weight molecules from the vegetation liquor
to give an aqueous fraction containing phytochemicals, for example, flavonoids, phenolic acids and
hydroxy acids. Subsequently, pH adjustment and solvent extraction upon said aqueous fraction realise
an extract rich in hydroxy acids or phenolic acids or flavonoids or any combination thereof
Applications of the substances subject of this invention are to be found in drinks, edible products,
tonics, health supplements, antioxidant additives, cosmetics, soaps, shampoos, detergents, drugs or
medicinal products.Description:
Description of US2003031740
[0001] This application is a divisional of U.S. patent application Ser. No. 09/405,206, entitled
"TREATMENT OF VEGETATION LIQUORS DERIVED FROM OIL-BEARING FRUIT," by
Ravigadevi Sambanthamurthi, Yew Ai Tan, and Kalyana Sundram, filed Sep. 24, 1999; and claims the
benefit of Malaysian patent application number PI 9804378, filed Sep. 24, 1998, the entire contents of
which are incorporated herein by reference.
[0002] Throughout this application, various publications are referenced. These publications are
incorporated herein by reference to describe more fully the state of the art to which the invention
pertains.
TECHNICAL FIELD
[0003] The present invention relates to processes for the treatment of vegetation liquors derived from
oil-bearing fruit, for example from oil palm fruit, and to products therefrom.
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BACKGROUND ART
[0004] Vegetation liquors are obtainable, among other ways, either directly from plants for the purpose
of extracting useful components or as a waste stream in the processing of plant material which is often
the cause of environmental pollution leading to the degradation of waterways and sources of water. In
this invention, the vegetation liquors derived from oil-bearing fruit may be obtained from or using one
of the following:
[0005] a) oil-bearing fruit of any herbaceous or arboraceous plant or from a combination of such fruit,
[0006] b) fruit of the oil palm plant,
[0007] c) waste streams from oil mills that process oil-bearing fruit,
[0008] d) palm oil mill effluent or concentrated palm oil mill effluent,
[0009] e) steriliser condensate from a palm oil mill,
[0010] f)waste from any oil clarification stage at a palm oil mill,
[0011] g) waste from any centrifuge stage at a palm oil mill, or
[0012] h) waste from any oil trap at a palm oil mill.
[0013] The above list is not intended to exhaust the possible sources of vegetation liquors derived from
oil-bearing fruit and any other such sources not named explicitly, for example, olive flume wastewater,
are meant to be included as input material for the invention. It will be clear that the input material is not
restricted to pure fruit but also includes any ancillary vegetative matter collaterally processed with the
fruit.
[0014] In the case of oil palm fruit processing, the extraction of palm oil generates a waste stream of
vegetation liquor at more than twice the tonnage of the crude palm oil production. Currently there are
several treatments and uses for vegetation liquors like palm oil mill effluent. Among them are either
applying said effluent, with or without treatment, onto the crop growing area, or reduction of chemical
and biological oxygen demand before release of treated effluent into the environment, or generation of
feed for livestock, or generation of substrates for the growth of micro-organisms ("A novel treatment
process for palm oil mill effluent", Ma Ah Ngan et al, PORIM Technology No. 19, October 1996). The
use of membrane filtration in the treatment of such effluents, whether in research or in practice, has
hitherto been focussed upon one or more of the above objectives rather than those aims which are the
subject of this invention ("Palm oil mill effluent treatment by ultrafiltration: An economic analysis",
Mohd. Tusirin Nor et al, Second Asean Workshop on membrane technology, 1982). However, existing
treatments have not really provided a solution to the effluent problem, and proposed solutions do not
seem to have been widely adopted perhaps because of adverse economics.
[0015] Furthermore, it has hitherto been accepted palm oil mill practice that the recovery of any
remaining oil from effluent is not carried out despite the presence in said effluent of nominally one to
two per cent oil content, often more in reality. Similarly, palm oil mill effluent has hitherto been
ignored as a potential source of water-soluble biologically active compounds including, but not limited
to, flavonoids, phenolic acids and hydroxy acids. Neither has the oil palm fruit been used as a source
for such compounds nor as a source of a drink or tonic based upon its aqueous part.
SUMMARY OF THE INVENTION
[0016] As stated in the preceding section, in this invention, the vegetation liquors derived from oilbearing fruit may be obtained from or using one of the following:
[0017] a) oil-bearing fruit of any herbaceous or arboraceous plant or from a combination of such fruit,
[0018] b) fruit of the oil palm plant,
[0019] c) waste streams from oil mills that process oil-bearing fruit,
[0020] d) palm oil mill effluent or concentrated palm oil mill effluent,
[0021] e) steriliser condensate from a palm oil mill,
[0022] f) waste from any oil clarification stage at a palm oil mill,
[0023] g) waste from any centrifuge stage at a palm oil mill, or
[0024] h) waste from any oil trap at a palm oil mill.
[0025] The above list is not intended to exhaust the possible sources of vegetation liquors derived from
oil-bearing fruit and any other such sources not named explicitly, for example, olive flume wastewater,
are meant to be included as input material for the invention. It will be clear that the input material is not
restricted to pure fruit but also includes any ancillary vegetative matter collaterally processed with the
fruit.
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[0026] The present invention has as an object to provide improved treatments of vegetation liquors
derived from oil-bearing fruit, for example from oil palm fruit, that is economically attractive. A
further object of the present invention is to find new uses for, and better utilise the contents of, such
vegetation liquors by recovering fractions containing valuable components including, but not limited to,
flavonoids, phenolic acids and hydroxy acids. Another object of this invention is to put waste streams
from oil-bearing fruit processing plants to more useful ends. Yet another object of the invention is to
realise new and/or improved products through the use of aqueous substances derived from oil-bearing
fruit, including but not limited to drinks, edible products, tonics, health supplements, antioxidant
additives, cosmetics, soaps, shampoos, detergents, drugs or medicinal compositions. Concomitantly, an
object of the invention is to reduce pollution by making feasible better treatments of waste streams
from oil-bearing fruit processing plants.
[0027] There is herein disclosed, according to the invention, a method of obtaining a drink or an edible
product or a tonic or a health supplement or an antioxidant additive or a cosmetic or a soap or a
shampoo or a detergent or a drug or a medicinal product, characterised in that an aqueous fraction
separated from vegetation liquor derived from oil-bearing fruit, said aqueous fraction having
substantially no oleaginous parts, substantially no colloidal particles and substantially no undissolved
solids, and said aqueous fraction containing, among other phytochemicals, flavonoids, phenolic acids
and hydroxy acids, or a concentrate, a residue or an extract derived from said aqueous fraction, is
combined in any way, form or proportion, to any other substance or substances.
[0028] According to this invention, a process is disclosed for extraction of phytochemicals from
vegetation liquor derived from oil-bearing fruit characterised in that an aqueous fraction or a
concentrated aqueous fraction or a residue containing said phytochemicals is separated and recovered
from said vegetation liquor, said separation being adapted to remove, in one step or more, substantially
all oleaginous parts, substantially all undissolved solids, substantially all colloidal particles and
substantially all molecules above M Daltons in molecular weight, thereby giving said aqueous fraction
containing solutes substantially all of which molecules are below M Daltons in molecular weight,
where M, the molecular separation cut-off, is chosen to be less than 41,000 Daltons; some or
substantially all of the water content of said aqueous fraction being removed to give said concentrated
aqueous fraction or said residue. Further according to the present invention, a process for extraction of
phytochemicals from vegetation liquor derived from oil-bearing fruit comprises obtaining a colloidal
fraction and an aqueous fraction from said vegetation liquor by the steps of putting said vegetation
liquor in contact with a material that preferentially adsorbs or absorbs substantially all the oleaginous
parts and filtering out substantially all the undissolved solids to give, as filtrate, an essentially colloidal
aqueous substance, and separating said substance into two fractions by one or more membrane
filtrations, giving as retentate, said colloidal fraction containing substantially all the colloidal particles
and containing solutes substantially all of which molecules are above M Daltons in molecular weight,
where M, the molecular separation cutoff, is chosen to be less than 41,000 Daltons; and giving as
permeate, being substantially clear and containing solutes substantially all of which molecules are
below M Daltons in molecular weight, said aqueous fraction.
[0029] Also according to this invention, a process for extraction of phytochemicals from vegetation
liquor derived from oil-bearing fruit comprises obtaining an oleaginous fraction, a colloidal fraction
and an aqueous fraction from said vegetation liquor by the steps of centrifuging said vegetation liquor
to give a light phase, being essentially all the oleaginous parts, said light phase being recovered as said
oleaginous fraction, a sediment phase containing substantially all the undissolved solids, and an
aqueous phase which contains substantially all the colloidal particles and substantially all the solutes,
said aqueous phase being recovered to give an essentially colloidal aqueous substance, or if necessary,
filtered to remove out any remaining finer undissolved solids to give said essentially colloidal aqueous
substance; and separating said substance into two fractions by one or more membrane filtrations, giving
as retentate, said colloidal fraction containing substantially all the colloidal particles and containing
solutes substantially all of which molecules are above M Daltons in molecular weight, where M, the
molecular separation cut-off, is chosen to be less than 41,000 Daltons; and giving as permeate, being
substantially clear and containing solutes substantially all of which molecules are below M Daltons in
molecular weight, said aqueous fraction. An improvement is disclosed herein whereby the step of the
process involving centrifugation of the vegetation liquor is conducted at a temperature below 13
degrees Celsius to better effect separation.
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[0030] Alternatively, according to the present invention, a process for extraction of phytochemicals
from vegetation liquor derived from oil-bearing fruit comprises obtaining an oleaginous fraction, a
colloidal fraction and an aqueous fraction from said vegetation liquor by the steps of separating said
vegetation liquor by one or more membrane filtrations into two parts, the retentate containing
substantially all the oleaginous parts and substantially all the undissolved solids, said oleaginous
retentate being filtered to remove substantially all the undissolved solids to give, as filtrate, said
oleaginous fraction; and giving, as permeate, an aqueous fraction containing substantially all the
colloidal particles and substantially all the solutes, this being an essentially colloidal aqueous
substance; and separating said substance into two fractions by one or more membrane filtrations, giving
as another retentate, said colloidal fraction containing substantially all the colloidal particles and
containing solutes substantially all of which molecules are above M Daltons in molecular weight,
where M, the molecular separation cut-off, is chosen to be less than 41,000 Daltons; and giving as
another permeate, being substantially clear and containing solutes substantially all of which molecules
are below M Daltons in molecular weight, said aqueous fraction.
[0031] In addition, according to the present invention, a process for extraction of phytochemicals from
vegetation liquor derived from oil-bearing fruit comprises obtaining an oleaginous fraction, a colloidal
fraction and an aqueous fraction from said vegetation liquor by the steps of filtering from said
vegetation liquor substantially all of the undissolved solids contained in said vegetation liquor, and
separating the filtrate so obtained into two parts by one or more membrane filtrations, giving as
permeate, an aqueous substance containing substantially all the colloidal particles and substantially all
the solutes; and, as retentate, giving said oleaginous fraction containing substantially all the oleaginous
parts; and separating the permeate so obtained into two parts by one or more membrane filtrations,
giving as another retentate, said colloidal fraction containing substantially all the colloidal particles and
containing solutes substantially all of which molecules are above M Daltons in molecular weight,
where M, the molecular separation cut-off, is chosen to be less than 41,000 Daltons; and giving as
another permeate, being substantially clear and containing solutes substantially all of which molecules
are below M Daltons in molecular weight, said aqueous fraction.
[0032] According to the present invention, an improvement to the processes as described in the
preceding paragraphs is disclosed which comprises the additional step of removing from said aqueous
fraction, being the substantially clear permeate obtained as an end result of the processes of the
preceding paragraphs, some part of or substantially all the water content to give either a concentrated
aqueous fraction or a residue.
[0033] Another alternative according to the present invention is a process for extraction of
phytochemicals from vegetation liquor derived from oil-bearing fruit which comprises obtaining a
concentrated aqueous fraction or a residue from said vegetation liquor by the steps of separating said
vegetation liquor into two parts by one or more membrane filtrations, the retentate containing
substantially all the oleaginous parts, substantially all the colloidal particles and substantially all the
undissolved solids; and giving as permeate, being substantially clear and containing solutes
substantially all of which molecules are below M Daltons in molecular weight, an aqueous fraction,
where M, the molecular separation cutoff, is chosen to be less than 41,000 Daltons; and removing from
said aqueous fraction some or substantially all the water content therein to give either said concentrated
aqueous fraction or said residue. Furthermore, according to this invention, an oleaginous fraction is
recoverable from the retentate obtained in the first membrane filtration carried out in the process as
described above in this paragraph.
[0034] There are herein disclosed, according to the present invention, substances that are products of
the invented process as follows:
[0035] a) an aqueous fraction, being substantially clear and containing solutes substantially all of which
molecules are below M Daltons in molecular weight, where M is chosen to be less than 41,000 Daltons,
[0036] b) a concentrated aqueous fraction, being said aqueous fraction with some part of the water
content removed,
[0037] c) a residue, being said aqueous fraction or said concentrated aqueous fraction with substantially
all the water content removed,
[0038] d) an extract rich in hydroxy acids or phenolic acids or flavonoids or any combination thereof,
and
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[0039] e) a dried extract rich in hydroxy acids or phenolic acids or flavonoids or any combination
thereof.
[0040] The last two substances, namely said extract or said dried extract, according to the present
invention, are obtained by a process which involves one or more steps of pH adjustment and solvent
extraction upon either vegetation liquor derived from oil-bearing fruit or said aqueous fraction or said
concentrated aqueous fraction or said residue reconstituted into an aqueous form.
[0041] There is herein disclosed, according to the present invention, a method of extracting
phytochemicals by obtaining an aqueous fraction containing, among other phytochemicals, flavonoids,
phenolic acids and hydroxy acids, or obtaining a concentrated aqueous fraction containing, among
other phytochemicals, flavonoids, phenolic acids and hydroxy acids, or obtaining a residue containing,
among other phytochemicals, flavonoids, phenolic acids and hydroxy acids, or obtaining an extract rich
in hydroxy acids or phenolic acids or flavonoids or any combination thereof, or obtaining a dried
extract rich in hydroxy acids or phenolic acids or flavonoids or any combination thereof, through the
application of the invented process to vegetation liquor derived from oil-bearing fruit.
[0042] According to the present invention, the invented substances disclosed may be used to make, or
are contained in, drinks, edible products, tonics, health supplements, antioxidant additives, cosmetics,
soaps, shampoos, detergents, drugs or medicinal products. It is clear, according to this invention, that
products may be produced using or containing, in any way, form or proportion, a fraction extracted
from vegetation liquor derived from oil-bearing fruit, in particular from palm oil mill effluent or from
concentrated palm oil mill effluent, said fraction having substantially no oleaginous parts, substantially
no colloidal particles and substantially no undissolved solids, and said fraction containing, among other
phytochemicals, flavonoids, phenolic acids and hydroxy acids.
[0043] Low grade oil may be recovered for sale from the oleaginous fraction, and the colloidal fraction
may be sold as animal feed, as animal food supplement or as substrate for microbial growth. The water
from the invented process is substantially pure and is recyclable. The invention realises new products
which will enhance effluent treatment economics. The invention further provides an apparatus, or a
combination of devices, for extraction of phytochemicals from vegetation liquor derived from oilbearing fruit characterised in that means are provided in said apparatus, or in said combination of
devices, to perform the processes as described herein.
EXAMPLES
[0044] Specific embodiments of the invention will now be described by way of example only. While
the embodiments here deal with vegetation liquor derived from oil palm, it is intended that the
invention will find wider application to other sources of vegetation liquor derived from oil-bearing fruit.
[0045] As a preliminary example, vegetation liquor is derived from fifteen oil palm fruitlets by
autoclaving at 120 degrees Celsius at a gauge pressure of 103421 Pascals (15 psig) for 15 minutes
following addition of 5 millilitres of water. The liquor so derived is collected and filtered through a
Whatman number 4 filter paper. The filtrate is then transferred into a Centriprep 10 (Amicon) system
and is centrifuged to give a permeate containing solutes of molecular weight less than 10,000 Daltons,
this providing the aqueous fraction from the vegetation liquor, the presence of the phytochemicals
being confirmed by analysis (details below). A sample of the aqueous fraction is used to recover an
extract containing hydroxy acids and phenolic acids and flavonoids by extracting with ethyl acetate,
first at a neutral pH of 7 achieved by adding sodium hydroxide, and subsequently at a pH of 2 achieved
by adding hydrochloric acid, the presence of the hydroxy acids and phenolic acids and flavonoids being
confirmed by analysis (see below for details).
[0046] In a second example, vegetation liquor is derived from an oil palm fruit bunch, weighing
approximately 18 kilograms, by autoclaving at 120 degrees Celsius at a gauge pressure of 117211
Pascals (17 psig) for 40 minutes. The liquor so derived is collected and filtered through a Whatman
number 4 filter paper. The filtrate is then collected and is circulated through a pumped ultrafiltration
device with a hollow fibre cartridge with nominal molecular weight cut-off of 10,000 Daltons to give a
permeate containing solutes of molecular weight less than 10,000 Daltons, this providing the aqueous
fraction from the vegetation liquor, the presence of the phytochemicals being confirmed by analysis
(details below). A sample of the aqueous fraction is used to recover an extract containing hydroxy acids
and phenolic acids and flavonoids by extracting with ethyl acetate, first at a neutral pH of 7 achieved
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by adding sodium hydroxide, and subsequently at a pH of 2 achieved by adding hydrochloric acid, the
presence of the hydroxy acids and phenolic acids and flavonoids being confirmed by analysis (see
below for details).
[0047] As a third example, vegetation liquor in the form of hot steriliser condensate is collected
immediately on discharge from the horizontal sterilisers at a palm oil mill. After a short transport time
to the laboratory, this condensate is then cooled to between 8 and 10 degrees Celsius before
centrifuging in a refrigerated centrifuge at 10 degrees Celsius at 5000 g for 30 minutes. The light phase
so generated is then skimmed off to give an oleaginous fraction. The middle aqueous phase is then
decanted, thereby separating this phase from the now-pelleted solids, to give a colloidal aqueous
substance. This substance is then arranged to be circulated through a pumped ultrafiltration device with
a hollow fibre cartridge with nominal molecular weight cut-off of 10,000 Daltons to give a permeate
containing solutes of molecular weight less than 10,000 Daltons, this providing the aqueous fraction
from the vegetation liquor, the presence of the phytochemicals being confirmed by analysis (details
below). A sample of the aqueous fraction is used to recover an extract containing hydroxy acids and
phenolic acids and flavonoids by extracting with ethyl acetate, first at a neutral pH of 7 achieved by
adding sodium hydroxide, and subsequently at a pH of 2 achieved by adding hydrochloric acid, the
presence of the hydroxy acids and phenolic acids and flavonoids being confirmed by analysis (see
below for details).
[0048] In a fourth example, the same process as in the third example above is carried out with the
difference that, in the ultrafiltration device, the nominal molecular cut-off of the hollow fibre cartridge
is 30,000 Daltons. The permeate therefore contains solutes of molecular weight less than 30,000
Daltons, this providing the aqueous fraction from the vegetation liquor, the presence of the
phytochemicals being confirmed by analysis (details below). As before, a sample of the aqueous
fraction is used to recover an extract containing hydroxy acids and phenolic acids and flavonoids by
extracting with ethyl acetate, first at a neutral pH of 7 achieved by adding sodium hydroxide, and
subsequently at a pH of 2 achieved by adding hydrochloric acid, the presence of the hydroxy acids and
phenolic acids and flavonoids being confirmed by analysis (see below for details).
[0049] As a fifth example, vegetation liquor is collected immediately on discharge from the sludge
centrifuge at a palm oil mill, and after a short transport time to the laboratory, is then cooled to between
8 and 10 degrees Celsius before centrifuging in a refrigerated centrifuge at 10 degrees Celsius at 5000 g
for 30 minutes. The light phase so generated is then skimmed off to give an oleaginous fraction. The
middle aqueous phase is then decanted, thereby separating this phase from the now-pelleted solids, to
give a colloidal aqueous substance. This substance is then circulated through a pumped ultrafiltration
device with a hollow fibre cartridge with nominal molecular weight cut-off of 10,000 Daltons to give a
permeate containing solutes of molecular weight less than 10,000 Daltons, this providing the aqueous
fraction from the vegetation liquor, the presence of the phytochemicals being confirmed by analysis
(details below). A sample of the aqueous fraction is used to recover an extract containing hydroxy acids
and phenolic acids and flavonoids by extracting with ethyl acetate, first at a neutral pH of 7 achieved
by adding sodium hydroxide, and subsequently at a pH of 2 achieved by adding hydrochloric acid, the
presence of the hydroxy acids and phenolic acids and flavonoids being confirmed by analysis (see
below for details).
[0050] In a sixth example, the same process as in the fifth example above is carried out with the
difference that, in the ultrafiltration device, the nominal molecular cut-off of the hollow fibre cartridge
is 30,000 Daltons. The permeate therefore contains solutes of molecular weight less than 30,000
Daltons, this providing the aqueous fraction from the vegetation liquor, the presence of the
phytochemicals being confirmed by analysis (details below). As before, a sample of the aqueous
fraction is used to recover an extract containing hydroxy acids and phenolic acids and flavonoids by
extracting with ethyl acetate, first at a neutral pH of 7 achieved by adding sodium hydroxide, and
subsequently at a pH of 2 achieved by adding hydrochloric acid, the presence of the hydroxy acids and
phenolic acids and flavonoids being confirmed by analysis (see below for details).
[0051] The oleaginous fraction is found to comprise low grade crude palm oil with about a quarter of
its content as free fatty acids. The colloidal fraction is found to be proteinaceous. The aqueous fraction
is found to contain essential minerals (iron, phosphorus, calcium, magnesium), sugars (among which
are glucose, fructose, sucrose), vitamins (among which are vitamin C, the B-complex vitamins, folic
acid), flavonoids (among which are catechin, catechin gallate, epicatechin, epigallocatechin,
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epigallocatechin gallate, epicatechin gallate, quercetin), phenolic acids (among which are caffeic acid,
protocatechuic acid, vanillic acid, ferulic acid, syringic acid, chlorogenic acid, gallic acid, tannic acid,
coumaric acid) and hydroxy acids (among which are citric acid, ascorbic acid, lactic acid, glycolic acid,
fumaric acid, tartaric acid, salicyclic acid). Where the aqueous fraction is obtained using the membrane
with the higher (30,000 Dalton) molecular weight cut-off, the solutes contain more proteins and other
filtrates, which could reduce the purity depending on the eventual application. The residue obtained by
freeze drying the aqueous fraction is found to contain an average of about 40,000 parts per million of
flavonoids and other phenolic compounds, and antioxidant activity is indicated. The extract is found to
contain hydroxy acids (among which are citric acid, ascorbic acid, lactic acid, glycolic acid, fumaric
acid, tartaric acid, salicyclic acid), phenolic acids (among which are caffeic acid, protocatechuic acid,
vanillic acid, ferulic acid, syringic acid, chlorogenic acid, gallic acid, tannic acid, coumaric acid) and
flavonoids (among which are catechin, catechin gallate, epicatechin, epigallocatechin, epigallocatechin
gallate, epicatechin gallate, quercetin).
[0052] As a seventh example, fresh palm oil mill effluent is filtered to remove undissolved solids and
the filtrate is subject to membrane filtration using the Membrex Ultrafilic system with a molecular
weight cut-off of 100,000 Daltons. This gives the oleaginous fraction as retentate and , as permeate,
gives an essentially colloidal aqueous substance which is subject to another membrane filtration with
molecular weight cut-off of 10,000 Daltons. This gives the colloidal fraction as another retentate and,
as another permeate, gives the aqueous fraction containing, among other phytochemicals, flavonoids,
phenolic acids and hydroxy acids. This aqueous fraction is concentrated or dried and the water so
obtained is substantially pure.
[0053] While examples of the invention have been described in detail, it should be apparent that many
modifications and variations thereto are possible all of which fall within the true spirit and scope of the
invention.Data supplied from the esp@cenet database - Worldwide
Claims:
Claims of US2003031740
What is claimed is:
1. A method of obtaining a product comprising separating an aqueous fraction from vegetation liquor
derived from oil-bearing fruit, said aqueous fraction having substantially no oleaginous parts,
substantially no colloidal particles and substantially no undissolved solids, and said aqueous fraction
containing, among other phytochemicals, flavonoids, phenolic acids and hydroxy acids, or a
concentrate derived from said aqueous fraction, or a residue derived from said aqueous fraction, or an
extract derived from said aqueous fraction, is combined in any way, form or proportion, to any other
substance or substances.
2. A process for extraction of phytochemicals from vegetation liquor derived from oil-bearing fruit
characterised in that an aqueous fraction or a concentrated aqueous fraction or a residue containing said
phytochemicals is separated and recovered from said vegetation liquor, said separation being adapted
to remove, in one step or more, substantially all oleaginous parts, substantially all undissolved solids,
substantially all colloidal particles and substantially all molecules above M Daltons in molecular
weight, thereby giving said aqueous fraction containing solutes substantially all of which molecules are
below M Daltons in molecular weight, where M, the molecular separation cut-off, is chosen to be less
than 41,000 Daltons; some or substantially all of the water content of said aqueous fraction being
removed to give said concentrated aqueous fraction or said residue.
3. A process for extraction of phytochemicals from vegetation liquor derived from oil-bearing fruit as
in claim 2, wherein the separation comprises the steps of obtaining a colloidal fraction and an aqueous
fraction from said vegetation liquor by:
a) putting said vegetation liquor in contact with a material that preferentially adsorbs or absorbs
substantially all the oleaginous parts and filtering out substantially all the undissolved solids to give, as
filtrate, an essentially colloidal aqueous substance, and
b) separating said substance into two fractions by one or more membrane filtrations, giving as retentate,
said colloidal fraction containing substantially all the colloidal particles and containing solutes
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substantially all of which molecules are above M Daltons in molecular weight, where M, the molecular
separation cut-off, is chosen to be less than 41,000 Daltons; and giving as permeate, being substantially
clear and containing solutes substantially all of which molecules are below M Daltons in molecular
weight, said aqueous fraction.
4. A process for extraction of phytochemicals from vegetation liquor derived from oil-bearing fruit as
in claim 2, wherein the separation comprises the steps of obtaining an oleaginous fraction, a colloidal
fraction and an aqueous fraction from said vegetation liquor by:
a) centrifuging said vegetation liquor to give a light phase, being essentially all the oleaginous parts,
said light phase being recovered as said oleaginous fraction, a sediment phase containing substantially
all the undissolved solids, and an aqueous phase which contains substantially all the colloidal particles
and substantially all the solutes, said aqueous phase being recovered to give an essentially colloidal
aqueous substance, or if necessary, filtered to remove out any remaining finer undissolved solids to
give said essentially colloidal aqueous substance, and
b) separating said substance into two fractions by one or more membrane filtrations, giving as retentate,
said colloidal fraction containing substantially all the colloidal particles and containing solutes
substantially all of which molecules are above M Daltons in molecular weight, where M, the molecular
separation cut-off, is chosen to be less than 41,000 Daltons; and giving as permeate, being substantially
clear and containing solutes substantially all of which molecules are below M Daltons in molecular
weight, said aqueous fraction.
5. A process as in claim 4, wherein step (a) of the process is conducted at a temperature below 13
degrees Celsius.
6. A process for extraction of phytochemicals from vegetation liquor derived from oil-bearing fruit as
in claim 2, wherein the separation comprises the steps of obtaining an oleaginous fraction, a colloidal
fraction and an aqueous fraction from said vegetation liquor by:
a) separating said vegetation liquor by one or more membrane filtrations into two parts, the retentate
containing substantially all the oleaginous parts and substantially all the undissolved solids, said
oleaginous retentate being filtered to remove substantially all the undissolved solids to give, as filtrate,
said oleaginous fraction; and giving, as permeate, an aqueous fraction containing substantially all the
colloidal particles and substantially all the solutes, this being an essentially colloidal aqueous substance,
and
b) separating said substance into two fractions by one or more membrane filtrations, giving as retentate,
said colloidal fraction containing substantially all the colloidal particles and containing solutes
substantially all of which molecules are above M Daltons in molecular weight, where M, the molecular
separation cut-off, is chosen to be less than 41,000 Daltons; and giving as permeate, being substantially
clear and containing solutes substantially all of which molecules are below M Daltons in molecular
weight, said aqueous fraction.
7. A process for extraction of phytochemicals from vegetation liquor derived from oil-bearing fruit as
in claim 2, wherein the separation comprises the steps of obtaining an oleaginous fraction, a colloidal
fraction and an aqueous fraction from said vegetation liquor by:
a) removing by filtration from said vegetation liquor substantially all of the undissolved solids
contained in said vegetation liquor, and
b) separating the filtrate obtained from the process in the above step (a) into two parts by one or more
membrane filtrations, giving as permeate, an aqueous substance containing substantially all the
colloidal particles and substantially all the solutes; and, as retentate, giving said oleaginous fraction
containing substantially all the oleaginous parts, and
c) separating the permeate obtained from the process in the above step (b) into two parts by one or
more membrane filtrations, giving as retentate, said colloidal fraction containing substantially all the
colloidal particles and containing solutes substantially all of which molecules are above M Daltons in
molecular weight, where M, the molecular separation cut-off, is chosen to be less than 41,000 Daltons;
and giving as permeate, being substantially clear and containing solutes substantially all of which
molecules ate below M Daltons in molecular weight, said aqueous fraction.
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8. A process as in claim 3, comprising the additional step of removing from said aqueous fraction,
being the substantially clear permeate obtained as a result of the process, some part of the water content
or substantially all the water content to give either a concentrated aqueous fraction or a residue.
9. A process as in claim 4, comprising the additional step of removing from said aqueous fraction,
being the substantially clear permeate obtained as a result of the process, some part of the water content
or substantially all the water content to give either a concentrated aqueous fraction or a residue.
10. A process as in claim 6, comprising the additional step of removing from said aqueous fraction,
being the substantially clear permeate obtained as a result of the process, some part of the water content
or substantially all the water content to give either a concentrated aqueous fraction or a residue.
11. A process as in claim 7, comprising the additional step of removing from said aqueous fraction,
being the substantially clear permeate obtained as a result of the process, some part of the water content
or substantially all the water content to give either a concentrated aqueous fraction or a residue.
12. A process for extraction of phytochemicals from vegetation liquor derived from oil-bearing fruit as
in claim 2, wherein the separation comprises the steps of obtaining a concentrated aqueous fraction or a
residue from said vegetation liquor by:
a) separating said vegetation liquor by one or more membrane filtrations, into two parts, the retentate
containing substantially all the oleaginous parts, substantially all the colloidal particles and
substantially all the undissolved solids; and giving as permeate, being substantially clear and
containing solutes substantially all of which molecules are below M Daltons in molecular weight, an
aqueous fraction, where M, the molecular separation cut-off, is chosen to be less than 41,000 Daltons,
and
b) removing from said aqueous fraction some or substantially all the water content therein to give
either said concentrated aqueous fraction or said residue.
13. A process as in claim 12 comprising the additional step of recovering from the retentate obtained as
a result of step (a), substantially all of the oleaginous parts to give an oleaginous fraction.
14. A substance, being said aqueous fraction containing, among other phytochemicals, flavonoids,
phenolic acids and hydroxy acids, obtained as a product of the process in claim 2.
15. A substance, being said aqueous fraction containing, among other phytochemicals, flavonoids,
phenolic acids and hydroxy acids, obtained as a product of the process in claim 3.
16. A substance, being said aqueous fraction containing, among other phytochemicals, flavonoids,
phenolic acids and hydroxy acids, obtained as a product of the process in claim 4.
17. A substance, being said aqueous fraction containing, among other phytochemicals, flavonoids,
phenolic acids and hydroxy acids, obtained as a product of the process in claim 6.
18. A substance, being said aqueous fraction containing, among other phytochemicals, flavonoids,
phenolic acids and hydroxy acids, obtained as a product of the process in claim 7.
19. A substance, being said concentrated aqueous fraction or said residue containing, among other
phytochemicals, flavonoids, phenolic acids and hydroxy acids, obtained as a product of the process in
claim 2.
20. A substance, being said concentrated aqueous fraction or said residue containing, among other
phytochemicals, flavonoids, phenolic acids and hydroxy acids, obtained as a product of the process in
claim 12.
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21. A process for obtaining an extract rich in hydroxy acids or phenolic acids or flavonoids or any
combination thereof comprising one or more steps of extraction, by means of a solvent or solvents,
from vegetation liquor derived from oil-bearing fruit, being an aqueous fraction, a concentrated
aqueous fraction, or a residue reconstituted into an aqueous form, adjusting the hydrogen ion
concentration (pH), as necessary, of said vegetation liquor or said substances to effect separation of the
desired hydroxy acids or phenolic acids or flavonoids or any combination thereof into either the
aqueous phase or the solvent phase, and by recovering the phase containing said hydroxy acids or
phenolic acids or flavonoids or any combination thereof, thereby recovering said extract.
22. A substance, being an extract rich in hydroxy acids or phenolic acids or flavonoids or any
combination thereof, obtained as a product of the process in claim 21.
23. A substance, being a dried extract rich in hydroxy acids or phenolic acids or flavonoids or any
combination thereof, characterised in that said dried extract is produced by removing substantially all
of the water or substantially all of the solvent from the substance in the above claim 22.
24. A product characterised in that said product is produced using or containing, in any way, form or
proportion, a fraction extracted from vegetation liquor derived from oil-bearing fruit, said fraction
having substantially no oleaginous parts, substantially no colloidal particles and substantially no
undissolved solids, and said fraction containing, among other phytochemicals, flavonoids, phenolic
acids and hydroxy acids.
25. A product characterised in that said product is produced using or containing, in any way, form or
proportion, a fraction derived from palm oil mill effluent or from concentrated palm oil mill effluent,
said fraction having substantially no oleaginous parts, substantially no colloidal particles and
substantially no undissolved solids, and said fraction containing, among other phytochemicals,
flavonoids, phenolic acids and hydroxy acids.Data supplied from the esp@cenet database - Worldwide
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80. US4235889
- 25/11/1980
THERAPEUTIC AGENT FOR THE EXTERNAL TREATMENT OF PSORIASIS,
TINEA AND ECZEMAS
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=US4235889
Inventor(s):
EVERS WALTER (DE)
Applicant(s):
EVERS and CO PHARMA (DE)
IP Class 4 Digits: A61K; A61Q
IP Class:A61K8/92; A61K8/97; A61Q19/00; A61K8/96; A61K35/78
E Class: A61K8/92C; A61K8/97; A61K35/78; A61Q19/00
Application Number:
US19790033154 (19790425)
Priority Number: US19790033154 (19790425)
Family: US4235889
Abstract:
Abstract of US4235889
The subject of the invention is a pharmaceutical composition for the external treatment of psoriasis,
tinea and eczemas, comprising coconut oil, palm kernel oil, an extract of Laurus nobilis (Linn.) and an
emulsifier.Description:
Description of US4235889
BACKGROUND OF THE INVENTION
1. Field of the Invention
The object of the present invention is to provide a pharmaceutical composition for the external
treatment of psoriasis, tinea and eczemas, with which treatment on humans has proved very successful.
Even "hopeless cases" have shown distinct healing. A further object of the invention is that the
composition for topical application makes possible a therapy which is free from side effects.
2. Prior Art
Therapeutic agents which are known for the external treatment of psoriasis, tinea and eczemas have not
yet proved sufficiently effective, so that topical ointments based on tars have frequently been used in
combination with an X-ray treatment.
SUMMARY
The subject of the invention is a pharmaceutical composition for topical application for the external
treatment of psoriasis, tinea and eczemas, which comprises 30 to 50 percent by weight of coconut oil,
30 to 50 percent by weight of palm kernel oil, 5 to 15 percent by weight of laurel oil from Laurus
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nobilis (Linn.), and 5 to 15 percent by weight of an emulsifier, the percentages by weight summing up
to 100 percent by weight.
In one embodiment of the composition of the invention, it may contain wool fat as emulsifier.
In another embodiment, the composition may contain wool wax alcohols as the emulsifier.
In a further embodiment, the composition may contain salts of pharmacologically permissible metals of
aliphatic monocarboxylic acids with 10 to 22 carbon atoms as the emulsifier.
In an additional embodiment, the composition may contain mono- and/or di-glycerides of aliphatic
monocarboxylic acids with 10 to 22 carbon atoms as the emulsifier.
In still an additional embodiment, the composition may contain about 50 percent by weight of coconut
oil, 30 percent by weight of palm kernel oil, 10 percent by weight of laurel oil, and 10 percent by
weight of wool fat.
In a further embodiment, the composition contains about 40 percent by weight of coconut oil, 40
percent by weight of palm kernel oil, 10 percent by weight of laurel oil, and 10 percent by weight of
zinc stearate.
In a still further embodiment, the composition contains about 50 percent by weight of coconut oil, 30
percent by weight of palm kernel oil, 10 percent by weight of laurel oil, and 10 percent by weight of
zinc stearate.
In still an additional embodiment, the composition contains about 30 percent by weight of coconut oil,
50 percent by weight of palm kernel oil, 10 percent by weight of laurel oil, and 10 percent by weight of
zinc stearate.
In another embodiment, the pharmaceutical composition contains small amounts of antioxidants.
In yet another embodiment, the pharmaceutical composition contains small amounts of preservatives.
Coconut oil is isolated from the fruit of the coconut palm (Cocos nucifera) and contains, as the main
constituents, 50 to 60% of caprilolauromyristin and 15 to 20% of myristodilaurine. In addition it
contains small amounts of oleic acid glycerides, palmitodimyristine and stearodipalmitine. With
reference to the fatty acid composition (in percentage) of coconut oil, Ullmanns Encyklopadie der
technischen Chemie (Ullmans Encyclopedia of Technical Chemistry), 4th Edition, Volume 11 gives,
on pages 458 and 459, 13 percent of C10 and lower saturated fatty acids, 45 to 50 percent of C12
saturated fatty acids, 8 to 9 percent of C16 saturated fatty acids, and 2 to 3 percent of C18 saturated
fatty acids, traces of C14/1 unsaturated fatty acids, traces of C16/1 unsaturated fatty acids, 5 to 8
percent of C18/1 unsaturated fatty acids, and 1 to 3 percent of C18/2 unsaturated fatty acids. The
content of free fatty acids in coconut oil is 5 to 17 percent (calculated relative to oleic acid). Coconut
oil, as used in this specification, is also designated coconut fat or coconut butter, both in the literature
and in commerce. It is preferred that the coconut oil employed be natural, but synthetic coconut oil
prepared in accordance with foodstuff technology can also be used for the present invention.
According to the citation, in Ullmanns on pages 458 and 459, palm kernel oil contains, with reference
to the fatty acid composition (in percentage), 7 percent of C10 and lower saturated fatty acids, 47 to 52
percent of C12 saturated fatty acids, 16 percent of C14 saturated fatty acids, 6 to 9 percent of C16
saturated fatty acids, 2 to 3 percent of C18 saturated fatty acids, 10 to 18 percent of C18/1 unsaturated
fatty acids, and 1 to 3 percent of C18/2 unsaturated fatty acids. Palm kernel oil contains 0.4 to 9.8
percent of free acids.
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In its properties and characteristic values, palm kernel oil is very similar to coconut oil; however,
compared with the latter, it contains more oleic acid and only half as much C8 and C10 fatty acids in its
glycerides. The palm kernel oil glycerides consist of 60 to 65 percent of tri-saturated components,
about 25 percent of disaturated-monounsaturated components, and 10 to 15 percent of monosaturateddiunsaturated components. Palm kernel oil, as used in this specification, is also designated palm kernel
fat in the literature and in commerce. It is preferred to use natural palm kernel oil, but synthetic palm
kernel oil prepared in accordance with foodstuff technology can also be used for the present invention.
"Laurel oil", as used in this specification, is understood to be the product "Oleum Lauri" described on
pages 470 to 471 of the Deutsches Arzneibuch 6 (German Pharmacopoeia, 6th Edition), that is to say,
the yellow-to-green semi-solid mixture of fats and oils, and lipid compositions expressed from the
fruits of Laurus nobilis (Linn.) using heat or isolated by boiling. Laurel oil melts at approximately 36
DEG C. to give a dark green liquid which has a spicy odor and a bitter taste and mainly consists of
lauryl laurate, lauryl stearate, and the essential oils and lipid components.
The laurel oil described above is also occasionally known as "laurel tallow" in the literature and in
European commerce. It is a greenish fatty composition which is isolated from the fresh fruits of the
laurel (Laurus nobilis (Linn.)). The density is approximately 0.88, the melting point is about 40 DEG
C., the saponification number is 198-199, and the iodine number is 68-80. Each of "laurel oil" and
"laurel tallow", as defined in Deutsches Arzneibuch 6, and as defined above, may be used in the
practice of this invention.
Yet a further embodiment of the novel compositions of the invention comprises a composition in which
the laurel essential extract consists of a mixture of 50 to 100 percent by weight of "laurel tallow" and
50 to 0 percent by weight of "laurel oil", as the terms are used in literature and commerce.
As used in this specification, laurel oil is defined as a mixture of fats, oils, and lipid components which
is isolated from the leaves and berries of laurel, i.e., the plant Laurus nobilis (Linn.), and is a pale
yellow oil which has a spicy odor and contains about 50 percent of cineol, as well as .alpha.-pinene,
linalool, citral, geraniol, eugenol, and hitherto unidentified substances. In the Merck Index, 9th Edition
(1976), page 707, No. 5228, there is defined: "Laurel Oil. Laurel berry oil. Fixed oil from fresh fruit of
Laurus nobilis L., Lauraceae. Constit. Chiefly the lauryl alcohol esters of lauric, stearic, etc. acids and a
volatile oil, the so-called laurel camphor. Greenish, fatty solid; the green color due to presence of some
chlorophyll. d about 0.88. mp about 40 DEG. nD@25 1.4783. Sapon no. 198-199. Iodine no. 68-80.
Insol in water; sparingly sol in alcohol; sol in benzene, ether, carbon disulfide."
The term "laurel camphor" for the volatile oil defined in the Merck Index definition of "Laurel Oil" is
not identical with Camphor USP, which is a solid ketone of the formula C10 H16 O which is isolated
from the plant Cinnamomum camphora (Linn.), or the synthetic isomorph thereof defined in
Remington's Pharmaceutical Sciences, 13th Edition, page 813 (1965). The volatile oil defined as laurel
camphor in the Merck Index and the solid substance (Camphor USP) are very different things and are
not to be confused. In the practice of the invention of this specification, no Camphor USP is contained
in "laurel oil" or "laurel tallow". Camphor USP is neither found in nor contemplated as a component of
the instant novel compositions.
It is readily apparent that the "laurel oil" of the Merck Index definition is identical with the "laurel
tallow" of European literature and commerce, and that the "laurel oil" of European literature and
commerce is the "laurel oil" of the Merck Index definition enriched or more concentrated in the more
volatile, lower-melting fats, essential oils, and lipid components. As used in this specification, "laurel
oil" differs from "laurel tallow" in a composition sense solely in that the former contains somewhat
more of the volatile components than does the latter, which latter is somewhat richer in the highermelting lauryl alcohol esters of lauric and longer-chain fatty acids. Both "laurel oil" and "laurel tallow"
derive from the same biological source, i.e., the fruits and leaves of Laurus nobilis (Linn.).
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In the sense of this invention, emulsifiers are defined as those which are pharmacologically and
physiologically tolerated by the diseased skin surface to be treated and which impart a favorable
consistency to the compositions hereof for their topical application to the skin, and which facilitate the
taking up of the therapeutic agent by absorption and/or resorption and/or persorption.
Suitable emulsifiers and emulsifying mixtures which meet these requirements are known to those
skilled in the art and are set forth, for example, in the book Rompp, Chemie Lexikon (Chemical
Dictionary), 6th Edition, 1966, Volume I, columns 1799 to 1806, along with further literature
references and a list of suppliers.
Examples of emulsifiers which can be used are: wool fat, wool wax alcohols, salts of
pharmacologically permissible metals with aliphatic monocarboxylic acids with 10 to 22 carbon atoms,
such as calcium stearate, magnesium stearate, aluminium stearate or zinc stearate, and emulsifier
mixtures of mono- and/or diglycerides of aliphatic monocarboxylic acids with 10 to 22 carbon atoms.
The compositions of the invention can also contain small amounts of antioxidants to prevent oxidative
destruction of those components of the composition susceptible thereto. Antioxidants and their use are
described in the chapter "Antioxidantien" ("Antioxidants") in Volume 8 of Ullmanns Encyklopadie der
technischen Chemie (Ullmanns Encyclopedia of Technical Chemistry), 4th Edition. The compounds in
the table below have been found effective as antioxidants in the practice of this invention, and are listed
therein together with their customary range of incorporation, in percentage by weight, relative to the
total weight of the composition. In addition, compounds which function as synergists to the
antioxidants are also set forth in the table.
>;tb;______________________________________
>;tb;Antioxidants
% by weight
>;tb;______________________________________
>;tb;L-Ascorbic acid
0.03-0.20
>;tb;2-/3-tert.-butyl-4-hydroxy-anisole (BHA)
>;tb;
0.005-0.02
>;tb;2,6-di-tert.-butyl-4-hydroxy-toluene (BHT)
>;tb;
0.005-0.12
>;tb;alkyl gallates
>;tb;alkyl = C3 H7 (PG), C8 H17 (OG) or C12 H25
>;tb;(DG)
0.008-0.10
>;tb;nordihydroguaiaretic acid (NDGA)
>;tb;
0.005-0.025
>;tb;3,3'-thio-dipropionic acid
>;tb;
0.01-0.02
>;tb;3,3'-thio-bis-(propionic acid alkyl esters)
>;tb;alkyl = C12 H23 (DLTDP) or C18 H37 (DSTDP)
>;tb;
0.01-0.09
>;tb;Tocopherols
0.01-0.30
>;tb;
and more
>;tb;2,4,5-trihydroxy-butyrophenone (THBP)
>;tb;
0.01-0.02
>;tb;ascorbic acid esters, for example, ascorbic
>;tb;acid myristate, ascorbic acid palmitate or
>;tb;ascorbic acid stearate 0.01- 0.015
>;tb;Synergists:
>;tb;L-Ascorbic acid, lecithin, phosphoric acid,
>;tb;polyphosphoric
>;tb;acid, tartaric acid and citric acid
>;tb;______________________________________
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The pharmaceutical compositions of this invention can also contain small amounts of preservatives to
prevent microbiological degradation. Preservation by chemical agents is described on pages 440 to 461
in Volume 11, 1960, of Ullmanns Encyklopadie der technischen Chemie (Ullmanns Encyclopedia of
Technical Chemistry), 3rd Edition. Examples of preservatives effective in the practice of this invention
are methyl p-hydroxy benzoate, ethyl p-hydroxy benzoate, propyl p-hydroxy benzoate, and sorbic acid.
In general, the addition of about 0.01 to 0.2 percent by weight of preservative, relative to the weight of
the total composition, suffices to prevent growth of molds, yeasts and bacteria and consequent spoilage
and loss of efficacy of the compositions. A particularly useful preservative consists of seven parts of
methyl p-hydroxy benzoate and three parts of propyl p-hydroxy benzoate, which mixture is effective at
a total amount of 0.1 percent by weight, relative to the weight of the total composition.
The topical pharmaceutical compositions of this invention can be manufactured using customary
methods of the pharmaceutical compounding art. Thus, the components can be brought into the mobile
or fluid state by careful warming to about 35 DEG to 50 DEG C. and combined by stirring, the
emulsifier or emulsifier mixture then being added and finely dispersed.
If desired, a completely homogeneous spreadable product can be manufactured by processing the batch
produced in this way in a homogenizer, in which the batch is forced through nozzles under high
pressure.
If the product has become highly viscous due to storage at low temperatures, or if it should be found to
contain crystalline fractions, it can be restored to a state in which it is very readily spreadable by gentle
warming to about 30 DEG C.
Psoriasis is a disease for which there has been no satisfactory method of treatment to date. The cause of
psoriasis is unclear, but genetic factors appear to play a major role.
The therapeutic composition of the invention is a combination of active compounds which is novel for
the treatment of psoriasis and represents a therapy free from side effects. Excellent therapeutic results
have been achieved in preliminary medical tests, even in "hopeless cases".
By penetrating into the diseased tissue, the active components of the compositions herein apparently
produce necrosis of the infected cells, which is apparent in the form of dermal shedding around the
areas of erythematous development. The efficacy of the compositions is also demonstrated by the fact
that no punctiform hemorrhages occur. After topical application to the effected sites, a gratifying
alleviation of the irritating itching is noticeable after a few days.
In the initial stages of treatment, visible reddening of the skin areaswhich are regenerating usually
arises as a result of increased blood flow.
The treatment period varies from individual to individual. Diseases in the primary stages require a
considerably shorter period to demonstrate beneficial results (six to eight weeks). Despite reddening of
the skin, the treatment can be continued until a normal skin color and gross appearance have returned
to the affected site.
The fields of efficacy for the novel compositions comprise the topical treatment of psoriasis, tineas, and
eczemas; the treatment is indicated in particular in the case of chronic diseases.
Unless otherwise prescribed by the doctor, the composition of the invention may conveniently and
effectively be applied, or lightly rubbed into the affected areas of the skin three times a day. The
treatment can be continued for a prolonged period without hesitation, or the development of distressing
side effects.
After the composition has been topically applied, all contact with water should preferably be avoided
for a period of at least thirty minutes.
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It is appropriate to carry out the treatment with the compositions of the invention under medical
supervision.
No side effects, concomitant symptoms, contra-indications, or risks have become known to date.
The following tests have been carried out to prove the therapeutic effectiveness of the compositions of
the invention.
TEST 1
Skin compatibility of coconut oil, palm kernel oil, and emulsifier on the healthy skin
In the first instance, compatibility tests were carried out on the healthy skin of forty voluntary persons,
consisting of twenty men and twenty women of 21 to 70 years of age. By these investigations it was
confirmed that coconut oil, palm kernel oil, and the emulsifiers mentioned in this application, as sole
substance or in combination one with the other, are tolerated without irritation on the healthy skin.
These personal investigations and results are in agreement with the results of examinations of the
manufacturers.
TEST 2
Skin compatibility test of laurel oil, melting point 36 DEG C., and laurel oil (laurel tallow), melting
point 40 DEG C., on the healthy skin
The same forty persons were used for this test. Laurel oil (or laurel tallow) was applied and rubbed in
in the liquid state in small amounts of 50.+-.5 mg. After thirty minutes, the treated skin was observed.
In sixteen men and seventeen women slight reddening of skin with the feeling of slight manifestation
of irritation was observed.
After thirty minutes, 50.+-.5 mg laurel oil was again applied to the skin of fifteen men and sixty
minutes later, a very distinct itching irritation with reddening had occurred with nine men, and for six
men formation of pustules, reddening and itching irritation had set in.
After 24 hours, one man complained of allergic malady.
These investigations have shown that laurel oil (or laurel tallow) applied alone on the healthy skin
produces appearance of irritation.
TEST 3
Skin compatibility tests of therapeutic agents according to this application on the healthy skin
30 to 50 percent by weight of coconut oil,
30 to 50 percent by weight of palm kernel oil,
5 to 15 percent by weight of laurel oil,
5 to 15 percent by weight of emulsifier.
The agents used in these tests were manufactured according to Examples 1 to 77 following. The same
forty persons were used as in the previous tests. Surprisingly, good compatibility of the compositions
appeared with the healthy skin.
TEST 4
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Skin compatibility tests of laurel oil, melting point 36 DEG C., and laurel oil (laurel tallow), melting
point 40 DEG C., on the ill skin (psoriasis, tinea and eczemas)
These examinations were carried out as described under Test 2, but there was proved the reaction on
the ill skin of
(a) six men--illness: psoriasis
(b) two men and two women--illness: tinea
(c) four men and one woman--illness: eczema.
Four men of group (a), two men and one woman of group (b), and three men and one woman of group
(c) had noted a strong burning pain upon application. The four men of group (a) tried spontaneously to
wipe the test substance off their skin. Inflammation focus, perceived as point of pain and burning,
appeared at two men of group (a), one woman of group (b), and one man of group (c) in the course of
fifteen minutes.
These tests show that laurel oil and laurel tallow, with melting points of 36 DEG C. and 40 DEG C.
respectively, are not compatible on the skin diseased with psoriasis, tinea and eczemas; moreover, skin
irritation is produced. That is the reason that these substances cannot be used as therapeutic agents
alone.
TEST 5
Skin compatibility tests of therapeutic agents according to the present invention on the skin diseased
with psoriasis, tinea and eczemas
For these tests there were used agents, manufactured according to Examples 1 to 77. These
examinations were carried out as described under Test 2, evaluating the reaction on the ill skin of:
(a) six men and four women--illness: psoriasis
(b) four men and four women--illness: tinea
(c) four men and two women--illness: eczema.
In a completely concordant manner, no skin irritation or risk factor was determined.
TEST 6
Therapeutic examination on the skin, diseased with psoriasis, tinea and eczemas
The skin, diseased with psoriasis, tinea and eczemas of the test persons who placed themselves at the
disposal, for the skin compatibility tests of therapeutic agents according to the present invention, was
proved with the following combinations:
I.
45 percent by weight of coconut oil
45 percent by weight of palm kernel oil
10 percent by weight of emulsifier
II.
80 percent by weight of coconut oil
10 percent by weight of laurel oil
10 percent by weight of emulsifier
III.
80 percent by weight of palm kernel oil
10 percent by weight of laurel oil
10 percent by weight of emulsifier
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IV.
30 to 50 percent by weight of coconut oil
30 to 50 percent by weight of palm kernel oil
5 to 15 percent by weight of laurel oil
5 to 15 percent by weight of emulsifier.
The combination I, II, III, and IV were applied on and lightly rubbed into the skin at different sites of
the same person, three times daily.
Combination I did not show any effect after six weeks.
The combinations II and III, in comparison with combination I and with the untreated skin, showed a
small therapeutic, but not sufficient, effect after six weeks.
Upon examination of combination IV according to the invention, after six weeks, in all cases good
therapeutic results were confirmed.
As experience and the test results have shown, the therapeutic effects are obtainable only with a
composition made according to the present invention.
Further, the following additional tests were carried out to prove effectiveness of the therapeutic
combination of the present invention.
TEST GROUPS
(A)
Forty people, twenty male, twenty female, in the age group 21 to seventy, free from skin diseases.
(B)(a)
42 people, 22 male, twenty female, suffering from chronic psoriasis, age group 18 to 45.
(b)
Eight people, four male, four female, suffering from tinea, age group 30 to 42.
(c)
Twelve people, four male, eight female, suffering from eczema, age group 27 to 36.
(C)(a)
114 people, fifty male, 64 female, suffering from chronic psoriasis, age group 18 to 63.
(b)
Twenty people, ten male, ten female, suffering from tinea, age group 25 to 42.
(c)
Twenty people, eleven male, nine female, suffering from eczema, age group 26 to 36.
Group C partially contains Group B.
All test people volunteered for the tests.
TESTED PHARMACEUTICAL COMPOSITIONS ACCORDING TO THE INVENTION
(A) Forty percent coconut oil; forty percent palm kernel oil; ten percent laurel oil; 9.9 percent Castearate; 0.1 percent hydroxybenzoic acid ester.
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(B) Fifty percent coconut oil; fifty percent palm kernel oil; ten percent laurel oil; 0.08 percent
tocopherol; 9.92 percent lanolin.
(C) Thirty percent coconut oil; fifty percent palm kernel oil; 8.4 percent laurel tallow; 3.6 percent
etheral laurel oil; ten percent zinc stearate.
(D) 45 percent coconut oil; 45 percent palm kernel oil; five percent laurel oil; 0.05 percent sorbic acid;
0.015 percent ascorbic acid-palmitate; 4.935 percent wool wax alcohols.
TESTS CARRIED OUT ON HEALTHY PATIENTS
(1) Skin compatibility tests of coconut oil, palm kernel oil and emulsifying agents on healthy skin:
With Test Group A, first of all compatibility tests were carried out on the healthy skin. By means of
these tests it was confirmed that coconut oil, palm kernel oil and those emulsifiers named in this patent
application, either as sole substance tested or in combination applied to the healthy skin, were tolerated
without irritation.
Said tests and results correspond entirely with the results of the tests carried out by the various
manufacturers.
(2) Skin compatibility tests of laurel oil, melting point 36 DEG C. and laurel oil (laurel tallow), melting
point 40 DEG C., on the healthy skin.
The same forty people were used for this test.
Laurel oil or laurel tallow was applied in a liquid state in a small quantity of 50.+-.5 mg and rubbed in.
After thirty minutes the treated skin was observed. In the case of sixteen men and seventeen women,
slight skin reddening was observed along with the sensation of slight irritation.
In the case of fifteen men, a renewed quantity of 50.+-.5 mg laurel oil was applied after thirty minutes.
After sixty minutes, nine men experienced a very marked irritation together with reddening and six
men experienced the formation of blisters, reddening and irritation. After 24 hours one man
complained of allergic conditions.
These tests have shown that laurel oil or laurel tallow when applied alone to the healthy skin cause
irritation.
(3) Skin compatibility tests of therapeutic agents, according to the invention, on the healthy skin:
Test Group A; compositions A+C.
Surprisingly enough, there was a good compatibility of the preparations on the healthy skin in the case
of 39 test people. In one case (female), composition C produced a slight reddening, which was
subjective but not regarded as unpleasant.
(4) Skin compatibility tests of laurel oil, melting point 36 DEG C., and laurel oil (laurel tallow),
melting point 40 DEG C., on the diseased skin (psoriasis, tinea and eczemas).
These tests were carried out as described in Test 2.
Test Groups B(a), B(b), B(c).
Twelve men and twelve women from the Group B(a), four men and two women from the Group B(b)
and three men and eight women from the Group B(c) indicated a marked burning pain upon application.
The four people from the Group B(a) tried immediately to rub the test substance off the skin.
In the case of eight men and nine women from the Group B(a), two women from the Group B(b) and
two men from the Group B(c), focuses of inflammation occurred within the course of fifteen to thirty
minutes, which were experienced as areas of pain and burning.
These tests show that laurel oil with the melting point 36 DEG C. or 40 DEG C. is incompatible on the
skin diseased with psoriasis, tinea and eczemas, causes skin irritation and pain, and for this reason
alone cannot be used as a therapeutic agent.
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(5) Skin compatibility tests of therapeutic agents according to the present invention on skin diseased
with psoriasis, tinea and eczemas:
Test Groups B(a), B(b), B(c); compositions A+C.
Surprisingly enough, no skin irritations or other side effects were observed in this series of tests.
(6) Therapeutic tests on skin diseased with psoriasis, tinea and eczemas:
Test Groups C(a), C(b), C(c); compositions A, B, C, D.
The compositions were applied three times daily to the test subjects on various diseased areas of the
skin. For comparison, no treatment was undertaken on a fifth area of their skin, which was likewise
erythematic. The patients guaranteed in writing that they would give up any further therapeutic
treatment of their skin during the ten (10) week period of tests with the compositions according to the
invention.
The following results were evident after treatment:
>;tb;
TABLE I
>;tb;______________________________________
>;tb;Com>;tb;posi>;tb;tion Ca
Cb
Cc
>;tb;______________________________________
>;tb;
30 .male.
>;tb;
50 .female.
>;tb;
++ 2 .male.
>;tb;
4 .female.
>;tb;
++ 3 .male.
>;tb;
2 .female.
>;tb;
++
>;tb;A 18 .male.
>;tb;
14 .female.
>;tb;
+ 7 .male.
>;tb;
6 .female.
>;tb;
+ 7 .male.
>;tb;
6 .female.
>;tb;
+
>;tb;
2 .male. 0 1 .male. 0 1 .male. 0
>;tb;
1 .female.
>;tb;
>;tb;
30 .male.
>;tb;
48 .female.
>;tb;
++ 2 .male.
>;tb;
3 .female.
>;tb;
++ 3 .male.
>;tb;
2 .female.
>;tb;
++
>;tb;B 19 .male.
>;tb;
15 .female.
>;tb;
+ 7 .male.
>;tb;
6 .female.
>;tb;
+ 7 .male.
>;tb;
7 .female.
>;tb;
+
>;tb;
1 .male.
>;tb;
1 .female.
>;tb;
0 1 .male.
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>;tb;
1 .female.
>;tb;
0 1 .male. 0
>;tb;
>;tb;
30 .male.
>;tb;
48 .female.
>;tb;
++ 2 .male.
>;tb;
3 .female.
>;tb;
++ 3 .male.
>;tb;
2 .female.
>;tb;
++
>;tb;C 19 .male.
>;tb;
14 .female.
>;tb;
+ 7 .male.
>;tb;
7 .female.
>;tb;
+ 6 .male.
>;tb;
6 .female.
>;tb;
+
>;tb;
1 .male.
>;tb;
2 + 0 1 .male. 0 2 .male.
>;tb;
1 .female.
>;tb;
0
>;tb;
>;tb;
+.male.
>;tb;
45 .female.
>;tb;
++ 2 .male.
>;tb;
3 .female.
>;tb;
++ 3 .male.
>;tb;
2 .female.
>;tb;
++
>;tb;D 18 .male.
>;tb;
14 .female.
>;tb;
+ 7 .male.
>;tb;
6 .female.
>;tb;
+ 7 .male.
>;tb;
7 .female.
>;tb;
+
>;tb;
2 .male.
>;tb;
5 .female.
>;tb;
0 1 .male.
>;tb;
1 .female.
>;tb;
0 1 .male. 0
>;tb;
>;tb;______________________________________
>;tb; Key to symbols:
>;tb; ++ = very marked improvement
>;tb; + = still clear improvement
>;tb; 0 = no noticeable reaction
>;tb; - = Worsening effect.
>;tb;
TABLE II
>;tb;______________________________________
>;tb;
Good Effect No Effect
>;tb;Test Group ++and +
0 and >;tb;______________________________________
>;tb;C(a)
442
14
>;tb;C(b)
74
6
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>;tb;C(c)
73
7
>;tb;______________________________________
In none of the patients (except for one evident allergy to hydroxybenzoic acid esters) was there any
appearance of subjective or objective side effects.
The described test results show that the desired therapeutic effects can be achieved only with a
pharmaceutical composition according to the present invention.
ADDITIONAL CLINICAL EVALUATION
Further, comparative treatments of psoriatic lesions with customary therapeutic medicaments and with
topical application of the composition defined below were undertaken. That composition (I) was
composed of:
Coconut oil: 50 grams
Palm kernel oil: 30 grams
Laurel oil as defined in the German Pharmacopeia: 10 grams
Emulsifier of equal parts of zinc stearate and lanolin: 10 grams
This composition (I) was applied topically to sixty chronic clinical psoriasis patents for evaluation. To
fifteen patients, there were also applied for side-by-side comparison, preparations which, according to
the art, are customary antipsoriatically effective therapeutic medicaments. Those known medications
evaluated were (1) a preparation based upon corticosteroids (Triamcinolone) and (2) a tar preparation
based upon coal tar.
In none of the fifteen patients under evaluation with the above compositions (1) and (2) did there occur
a single exacerbation of the clinical condition compared with the control or comparative treatments.
In twelve of the fifteen patients treated for twelve to fourteen days with the above-identified inventive
composition (I), there occurred a surprising objectively visible lessening of the affliction, such that the
affected body areas (mostly of the elbows and in the scalp area) were rendered completely normal. This
was not thought possible by the patients, who for many years had used the customary medicaments for
psoriasis.
In the remaining 45 patients, no comparative therapeutic evaluation was undertaken. Each of these
patients had in earlier years sought medical treatment for their affliction without any substantial
improvement, although further advance of the affliction was delayed for some.
In 38 patients, there occurred within from two weeks to two months an exfoliation of the diseased
dermal tissue. Also, during the post-treatment period of three to eight months, there was no further
occurrence of psoriasis on the previously afflicted dermal parts of these 38 patients.
Thus the therapeutic efficacy of the compositions of the present invention has been established in
comparison with treatments heretofore known, in which comparison the compositions of the invention
were shown to be highly antipsoriatically effective.
The compositions of this invention are illustrated in more detail by the examples which follow by way
of illustration and not by limitation.
EXAMPLES 1 to 8
Table I gives the individual components, and the amount thereof, used for Examples 1 to 8. The
components were filled into a stirred kettle, the outer walls of which were heated to about 40 DEG to
50 DEG C. by warm water. With the aid of the stirrer, the resulting melt was mixed until completely
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homogeneous. After cooling to room temperature, the stirrer was switched off. The resulting
composition of the invention was filled into sealable tubes holding a net weight of 30 g.
>;tb;
TABLE I
>;tb;______________________________________
>;tb;
Palm* Laurel tallow
>;tb;Example Coconut* kernel Deutsches
>;tb;No. oil
oil Arzneibuch 6
>;tb;
Emulsifier
>;tb;______________________________________
>;tb;1
500 g 300 g 50 g 150 g wool fat
>;tb;2
350 g 450 g 75 g 125 g wool fat
>;tb;3
400 g 400 g 90 g 110 g wool fat
>;tb;4
450 g 350 g 100 g 100 g wool fat
>;tb;5
410 g 390 g 150 g 50 g wool fat
>;tb;6
450 g 300 g 150 g 100 g wool fat
>;tb;7
400 g 400 g 110 g 90 g wool fat
>;tb;8
300 g 500 g 100 g 100 g wool fat
>;tb;______________________________________
>;tb; *natural form
EXAMPLES 9 to 12
The procedure was as in Examples 1 to 8. However, the amounts and components indicated in Table II
were employed.
>;tb;
TABLE II
>;tb;______________________________________
>;tb;
Palm Laurel tallow
>;tb;Example Coconut kernel Deutsches
>;tb;No. oil
oil Arzneibuch 6
>;tb;
Emulsifier
>;tb;______________________________________
>;tb; 9
300 g 500 g 170 g 90 g zinc stearate
>;tb;10
400 g 400 g 100 g 100 g zinc stearate
>;tb;11
500 g 300 g 100 g 100 g zinc stearate
>;tb;12
300 g 500 g 100 g 100 g zinc stearate
>;tb;______________________________________
EXAMPLES 13 to 20
0.8 g of .alpha.-tocopherol was incorporated, as an antioxidant, into the formulations obtained
according to Example 1 to 8.
EXAMPLES 21 to 28
0.1 g of ascorbic acid myristate, as an antioxidant, and 0.1 g of L-ascorbic acid, as a synergist, were
incorporated into the formulations obtained according to Examples 1 to 8.
EXAMPLES 29 to 36
0.7 g of methyl p-hydroxy benzoate and 0.3 g of propyl p-hydroxy benzoate were incorporated, as a
preservative, into the formulations obtained according to Examples 1 to 8.
EXAMPLES 37 to 44
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0.7 g of methyl p-hydroxy benzoate and 0.3 g of propyl p-hydroxy benzoate were incorporated, as a
preservative, into the formulations obtained according to Examples 21 to 28.
EXAMPLES 45 to 52
The procedure employed was as indicated in Examples 1 to 8. However, the constituents indicated in
Table III were used.
>;tb;
TABLE III
>;tb;______________________________________
>;tb;Ex- Coco- Palm*
Laurel oil
>;tb;ample nut* kernel Laurel
>;tb;
Deutsches
>;tb;No. oil oil tallow
>;tb;
Arzneibuch 6
>;tb;
Emulsifier
>;tb;______________________________________
>;tb;45 500 g 300 g 25 g 25 g 150 g wool fat
>;tb;46 350 g 450 g 50 g 25 g 125 g wool fat
>;tb;47 400 g 400 g 80 g 10 g 110 g wool fat
>;tb;48 450 g 350 g 175 g 25 g 100 g wool fat
>;tb;49 500 g 300 g 100 g 50 g 50 g wool fat
>;tb;50 450 g 300 g 120 g 30 g 100 g wool fat
>;tb;51 400 g 400 g 100 g 10 g 90 g wool fat
>;tb;52 300 g 500 g 95 g 5 g 100 g wool fat
>;tb;______________________________________
>;tb; *natural form
EXAMPLES 53 to 60
The procedure followed was as indicated in Examples 45 to 52, but 0.6 g of .alpha.-tocopherol was
additionally incorporated as an antioxidant.
EXAMPLES 61 to 68
The procedure followed was as indicated in Examples 53 to 60, but 0.5 g of sorbic acid was
additionally incorporated as a preservative. The amount of antioxidant added to the therapeutic agent of
the invention can be between 0.005 and 0.4 percent by weight, depending on the nature of the
antioxidant used. Any synergist can be used in the same range.
EXAMPLES 69 to 76
The procedure was as in Examples 1 to 8. However, the amounts and substances indicated in Table IV
were employed.
>;tb;
TABLE IV
>;tb;______________________________________
>;tb;ExPalm* Laurel tallow
>;tb;ample Coconut* kernel Deutsches
>;tb;No. oil
oil Arzneibuch 6
>;tb;
Emulsifier
>;tb;______________________________________
>;tb;69 490 g 410 g 50 g 50 g wool wax alcohol
>;tb;70 420 g 450 g 75 g 55 g wool wax alcohol
>;tb;71 415 g 435 g 90 g 60 g wool wax alcohol
>;tb;72 470 g 380 g 100 g 50 g wool wax alcohol
>;tb;73 390 g 400 g 150 g 60 g wool wax alcohol
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>;tb;74 440 g 360 g 150 g 50 g wool wax alcohol
>;tb;75 415 g 425 g 110 g 50 g wool wax alcohol
>;tb;76 340 g 500 g 100 g 60 g wool wax alcohol
>;tb;______________________________________
>;tb; *natural form
EXAMPLE 77
A mixture consisting of 425 g of coconut oil (natural form), 425 g of palm kernel oil (natural form),
100 g of laurel tallow, as defined in Deutsches Arzneibuch 6, and 50 g of emulsifier (Tegin M.TM.)
based on a glycerol mono-/di-stearate which is related to natural fat, not self-emulsifying and has a
high monoglyceride content (compare Ullmann IV, 29 and 34), was processed in accordance with the
instructions in Examples 1 to 8 to give the composition of the invention.
It will be understood that while the invention has been described specifically with reference to certain
embodiments thereof, various changes and modifications may be made, all within the full and intended
scope of the claims which follow.Data supplied from the esp@cenet database - Worldwide
Claims:
Claims of US4235889
I claim:
1. A pharmaceutical composition for the external treatment of psoriasis, tinea and eczemas consisting
essentially of thirty to fifty percent by weight of coconut oil, thirty to fifty percent by weight of palm
kernel oil, five to fifteen percent by weight of an extract of the leaves and berries of laurel (Laurus
nobilis (Linn.)) and five to fifteen percent by weight of an emulsifier, the percentages by weight
summing up to 100 percent.
2. Pharmaceutical composition of claim 1 in which wool fat is the emulsifier.
3. Pharmaceutical composition of claim 1 in which wool wax alcohol is the emulsifier.
4. Pharmaceutical composition of claim 1 in which salts of pharmacologically permissible metals with
aliphatic monocarboxylic acids with ten to 22 carbon atoms is the emulsifier.
5. Pharmaceutical composition of claim 1 in which mono- and/or di-glycerides of aliphatic
monocarboxylic acids with ten to 22 carbon atoms are the emulsifier.
6. Pharmaceutical composition of claim 1 which consists essentially of about fifty percent by weight of
coconut oil, thirty percent by weight of palm kernel oil, ten percent by weight of laurel oil m.p.,
approximately 36 DEG C. and ten percent by weight of wool fat.
7. Pharmaceutical composition of claim 1 which consists essentially of about forty percent by weight of
coconut oil, forty percent by weight of palm kernel oil, ten percent by weight of laurel oil m.p.,
approximately 36 DEG C. and ten percent by weight of zinc stearate.
8. Pharmaceutical composition of claim 1 which consists essentially of about fifty percent by weight of
coconut oil, thirty percent by weight of palm kernel oil, ten percent by weight of laurel oil m.p.,
approximately 36 DEG C. and ten percent by weight of zinc stearate.
9. Pharmaceutical composition of claim 1 which consists essentially of about thirty percent by weight
of coconut oil, fifty percent by weight of palm kernel oil, ten percent by weight of laurel oil m.p.,
approximately 36 DEG C. and ten percent by weight of zinc stearate.
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10. Pharmaceutical composition of claim 1 which contains from 0.01 to 0.2 percent each by weight of a
preservative and an antioxidant, the percentages by weight summing up to 100 percent.
11. Pharmaceutical composition of claim 1 in which the extract of laurel (Laurus nobilis (Linn.))
consists of a mixture of fifty to 100 percent by weight of laurel tallow m.p. about 40 DEG C. and fifty
to 0 percent by weight of laurel oil m.p., approximately 36 DEG C., the percentages by weight
summing up to 100 percent.
12. A method for the external treatment of psoriasis, tinea and eczema, comprising the repeated topical
application, to the affected dermal site, of a therapeutically effective amount of a composition of claim
1.Data supplied from the esp@cenet database - Worldwide
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81. US5691191
- 25/11/1997
MEDIUM FOR THE CULTIVATION OF LAGENIDIUM GIGANTEUM
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=US5691191
Inventor(s):
HEINS SHERRY DARLENE (US); EWING DUANE DOUGLAS (US);
MARRONE PAMELA GAIL (US)
Applicant(s):
AGRAQUEST INC (US)
IP Class 4 Digits: C12N
IP Class:C12N1/14
E Class: C12N1/14
Application Number:
US19960616738 (19960315)
Priority Number: US19960616738 (19960315); WO1997US10343 (19970617)
Family: US5691191
Equivalent:
WO9858049
Abstract:
Abstract of US5691191
A nutrient medium used in fermentation for increasing the yield of cells or microorganisms is provided.
The formulation provided increases the yield of the fungus Lagenidium giganteum two- to three-fold
over known media. The medium contains peptone, yeast extract, Proflo TM cottonseed flour, glucose,
palm oil, cholesterol, CaCl2 and MgCl2.Description:
Description of US5691191
FIELD OF THE INVENTION
This invention relates to a novel medium for use in fermentation which provides an increased cell
yield compared to that of known media. More particularly, the present invention produces at least a two
to three-fold increase in the yield of the fungus Lagenidium giganteum compared to the yield obtained
with known media. In addition to increasing yield of cells, L. giganteum grown in novel medium
containing lecithin exhibits increased effectiveness against mosquitoes.
BACKGROUND OF THE INVENTION
Fermentation is the process of growing microorganisms or cells in specialized vessels. The cells or
organisms may then be purified and used for a variety of purposes. For instance, the fungus
Lagenidium giganteum grown in fermenters is used as a biocontrol agent for mosquitoes.
Optimal growth of the microorganism during fermentation depends on several factors including
available nutrients, oxygen concentration, pH, temperature, and degree of mixing. Nutrients necessary
for cell growth are provided in the medium used during the fermentation process. Accordingly, the
yield obtained from fermentation depends, in part, on the composition of the medium.
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There are several published nutrient media currently used in the fermentation of Lagenidium
giganteum. All use deionized water added to a final volume of 1L, and all are sterilized. One
formulation comprises 2.0 g Ardamine pH, 2.0 g glucose, 1 mL corn oil, 0.5 g cholesterol and 2 mM
Ca2+. (Kerwin, James L. and Washino, Robert K. (1986) "Ground and aerial application of the sexual
and asexual stages of Lagenidium giganteum (oomycetes: Lagenidiales) for mosquito control." J. Am.
Mos. Control Assoc. 2 (2): 182-189).
Another formulation comprises 2.0 g autolyzed yeast extract, 1.0 g proflo, 0.5 g fish meal, 2 mM -CaCl2 .multidot.2H2 O, 1 mM MgCl2 .multidot.6H2 O, 0.05 g cholesterol and 2 mL cottonseed oil.
(Kerwin, James L. and Washino, Robert K. (1988) "Field evaluation of Lagenidium giganteum
(Oomycetes: Lagenidiales) and description of a natural epizootic involving a new isolate of fungus." J.
Meal Entomol. 25 (6): 452-460) Yet another fermentation medium comprises 1.25 g glucose, 1.25 g
peptone, 1.25 g autolyzed yeast extract, 2 g corn oil, 1 g linseed oil, and 0.075 g CaCl2 .multidot.2H2
O (U.S. Pat. No. 4,687,744). The fourth published medium contains 1.25 g yeast extract, 1.2 g glucose,
3.2 g powdered wheat germ, hemp seed extract to provide 250 mg/L of soluble protein, 1.25 g
bactopeptone, 3 g glucose and 1.5 g corn oil. (Lord, Jeffrey C. and Roberts, Donald W. (1986) "The
effects of culture medium quality and host passage on zoosporogensis and infectivity of Lagenidium
giganteum (Oomycetes: Lagenidiales)," J. Invertebr. Pathol. 48:355-361)
When used in fermentation, the above-referenced published medium formulations all yield
approximately the same number of cells and infect susceptible mosquitoes at approximately the same
rate. Thus, in order to increase the yield and infectivity of biocontrol agents like Lagenidium giganteum,
there is a need for an improved fermentation medium.
SUMMARY OF THE INVENTION
A medium for use in fermentation consisting essentially of 3.6 g per liter peptone; 3.0 g per liter
autolyzed yeast extract; 3.6 g per liter peptone; 1.5 to 3.0 g per liter autolyzed yeast extract; 1.6 g per
liter Proflo.RTM. cottonseed flour (Traders Protein, Memphis, Tenn.), which is approximately 58%
protein (dry weight); 2.0 to 7.75 g per liter glucose (dextrose); 2.5 g per liter palm oil; 0.2 g per liter
cholesterol; 0.6 g per liter CaCl2 .multidot.2H2 O; 0.2 g per liter MgCl2 .multidot.6H2 O and,
optionally, 0.0 to 2.0 g per liter of lecithin. This medium provides increased yields of Lagenidium
giganteum compared to prior art media, and, yield and infectivity of the organism is further increased
when lecithin is included in the medium.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention relates to an improved medium for fermentation. The medium increases yield at
least approximately two to three fold over known media. The invention is useful in large scale
production of Lagenidium giganteum, a biocontrol agent for mosquitoes.
Definitions
As used herein, the term "fermentation" refers to the process of growing cells or microorganisms in
specialized vessels. "Nutrient medium" ("medium") refers to a solid or liquid substrate that will support
the growth of an organism.
In a preferred embodiment of this invention, the nutrient medium is prepared as
15 follows:
3.6 g per liter peptone;
1.5 to 3 g per liter autolyzed yeast extract;
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1.6 g per liter Proflo.RTM. cottonseed flour (Traders Protein, Memphis, Tenn.), which is
approximately 58% protein (dry weight);
2.0 to 7.75 g per liter glucose (dextrose);
2.5 g per liter palm oil;
0.2 g per liter cholesterol;
0.6 g per liter CaCl2 2H2 O; and
0.2 g per liter MgCl2 6H2 O.
Deionized water is added to a final volume of 1L and the pH is adjusted to 6.5. The constituents are
heated until dissolved and then the medium is sterilized by autoclaving at 121 DEG C., 15 p.s.i., for 30
minutes. When used in the fermentation of Lagenidium giganteum, this medium increases yield at least
two to three fold over known media.
In another preferred embodiment, the nutrient medium is prepared by adding up to 2.0 g per liter of
lecithin to the above formulation.
The following example is provided only for illustrative purposes, and is not to be construed as limiting
the invention in any way.
EXAMPLE 1
Shake flask comparison of growth rates of Lagenidium giganteum in different media
Growth rate in the novel nutrient medium was compared with two other media in side by side shake
flask experiments.
Medium #1:
1.25 g glucose (dextrose)
1.25 g peptone
1.25 g autolyzed yeast extract
2.0 g corn oil
1.0 g palm oil
0.03 g cholesterol
0.4 g CaCl2 2H2 O
0.2 g MgCl2 6H2 O
Medium #2:
1.2 g peptone
1.2 g autolyzed yeast extract
3.0 g glucose (dextrose)
0.5 g cholesterol
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Novel Nutrient Medium:
3.6 g peptone
3.0 g autolyzed yeast extract
1.6 g Proflo.RTM. cottonseed flour (Traders Protein, Memphis, Tenn.), which is approximately 58%
protein (dry weight) extract
2.0 g glucose (dextrose)
2.5 g palm oil
0.2 g cholesterol
0.6 g CaCl2 2H2 O
0.2 g MgCl2 6H2 O
When preparing each of the media, all ingredients were combined and deionized water was added to a
final volume of 1L. The pH was adjusted to 6.5. Contents were heated in a microwave until dissolved
and then sterilized at 121 DEG C., 15 psi for 30 minutes. For each medium, nine 250 mL flasks were
each filled with 50 mL of medium. A disk of Lagenidium giganteum (California strain) taken from a
petri dish was used to inoculate each flask. The flasks were shaken at 120 rpm, 29 DEG C. in an orbital
temperature controlled shaker for 7 days. Cells were harvested by centrifuging the fungal mass at 5,200
rpm for 20 minutes at 18 DEG C. The centrifuged cell mass was weighed and cell counts made with a
hemacytometer. Mean cell counts were recorded. Results are summarized in Table 1.
>;tb;
TABLE 1
>;tb;__________________________________________________________________________
>;tb;
Fold Increase in
>;tb;
cells/mL when
>;tb;
Novel Nutrient
>;tb;
Novel Medium
>;tb;Medium #1 Medium #2 Medium used
>;tb;__________________________________________________________________________
>;tb;Exp't #1
>;tb; 1.2-2.0 .times. 10@6
>;tb;
1.2-2.0 .times. 10@6 cells/mL
>;tb;
4.4 .times. 10@6 cells/mL
>;tb;
2.2 fold
>;tb; cells/mL
>;tb;Exp't #2
>;tb; 6.25 .times. 10@5 cells/mL
>;tb;
7.5 .times. 10@5 cells/mL
>;tb;
1.38 .times. 10@6 cells/mL
>;tb;
1.84-2.2 fold
>;tb;Exp't #3
>;tb; 2.97 .times. 10@5 cells/mL
>;tb;
3.3 .times. 10@5 cells/mL
>;tb;
4.75 .times. 10@5 cells/mL
>;tb;
1.4-1.6 fold
>;tb;Bxp't #7
>;tb; 9.77 .times. 10@4 cells/mL
>;tb;
not done 9.38 .times. 10@5 cells/mL
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>;tb;
9.6 fold
>;tb;Exp't #8
>;tb; 1.93 .times. 10@5 cells/mL
>;tb;
not done 7.30 .times. 10@5 cells/mL
>;tb;
3.7 fold
>;tb;__________________________________________________________________________
Medium #1 and Medium #2 yielded approximately the same number of cells per mL of medium in
each experiment. The novel nutrient medium consistently increased the number of cells/mL in
comparison to either Medium #1 or Medium #2. The average yield of Lagenidium giganteum was
increased approximately three and half fold when grown in the novel nutrient medium.
EXAMPLE 2
Shake flask comparison of novel medium with lecithin added
Having established that the novel medium formulation of Example 1 increases cell yield over known
media, the effect of varying amounts of dextrose and yeast extract and adding 1.0 g or 2.0 g lecithin to
the basal novel medium was examined. All media were homogenized with a large probe at 70% speed
for 10-15 seconds to ensure components were in solution. Using EmReagents color Phast.RTM., the
pH of all media was adjusted to 6.5 and sterilized as in Example 1. For each medium, three 250 mL
flasks were filled with 50 mL of medium, inoculated, cultured and harvested as described in Example 1.
Results are summarized in Table 2 and Table 3
>;tb;
TABLE 2
>;tb;______________________________________
>;tb;Dextrose
>;tb;
Yeast extract
>;tb;
Lecithin Cell Yield
>;tb;% Wt % Wt
% Wt (cells/mL)
>;tb;______________________________________
>;tb;0.8750 0.1250 0.0000 2.0 .times. 10@5
>;tb;
Average Cell
>;tb;0.8750 0.1250 0.0000 3.0 .times. 10@5
>;tb;
Yield (cells/mL)
>;tb;0.6875 0.3125 0.0000 4.8 .times. 10@5
>;tb;
without lecithin:
>;tb;0.5000 0.5000 0.0000 4.1 .times. 10@5
>;tb;
3.6 .times. 10@5
>;tb;0.5000 0.5000 0.0000 4.13 .times. 10@5
>;tb;0.5875 0.3125 0.1000 5.4 .times. 10@5
>;tb;
Average Cell
>;tb;0.5875 0.3125 0.1000 4.05 .times. 10@5
>;tb;
Yield (cells/mL)
>;tb;0.3000 0.5000 0.2000 7.4 .times. 10@5
>;tb;
with lecithin:
>;tb;0.3000 o.5000 0.2000 4.9 .times. 10@5
>;tb;
4.63 .times. 10@5
>;tb;0.6750 0.1250 0.2000 4.5 .times. 10@5
>;tb;0.6750 0.1250 0.2000 4.1 .times. 10@5
>;tb;0.4875 0.3125 0.2000 3.6 .times. 10@5
>;tb;______________________________________
As shown in Table 2, for media without lecithin, the average cells/mL yield is 3.6.times.10@5. With
lecithin, yield increases to 4.63.times.10@5 cells/mL.
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EXAMPLE 3
Infectivity of Lagenidium giganteum grown in various media
Lagenidium giganteum was grown in novel media described in Example 2 which contained no lecithin,
0.1000% by weight lecithin or 0.2000 % by weight lecithin. Culturing conditions were as described in
Example 1. The concentration of cells was calculated and their ability to kill mosquitoes measured at
concentrations of 5,000; 2,500; 1,250 and 675 cells/mL. Results summarized in Table 3 are averages of
duplicate experiments.
>;tb;
TABLE 3
>;tb;__________________________________________________________________________
>;tb;
% Mortality at
>;tb;
% Mortality at
>;tb;
% Mortality at
>;tb;
% Mortality at
>;tb;
5,000 cells/mL
>;tb;
2,500 cells/mL
>;tb;
1,250 cells/mL
>;tb;
675 cells/mL
>;tb;__________________________________________________________________________
>;tb;Medium without
>;tb;
66 67 61 51
>;tb;lecithin
>;tb;Medium with
>;tb;
87 87 89 74
>;tb;lecithin
>;tb;__________________________________________________________________________
These results illustrate that Lagenidium giganteum grown in the novel media killed more mosquitoes
than cells grown in media without added lecithin.Data supplied from the esp@cenet database Worldwide
Claims:
Claims of US5691191
We claim:
1. A medium for use in fermentation, consisting essentially of:
(a) 3.6 g per liter peptone;
(b) 1.5 to 3 g per liter autolyzed yeast extract;
(c) 1.6 g per liter Proflo.RTM. cottonseed flour;
(d) 2.0 to 7.75 g per liter dextrose;
(e) 2.5 g per liter palm oil;
(f) 0.2 g per liter cholesterol;
(g) 0.6 g per liter CaCl2 .multidot.2H2 O; and
(h) 0.2 g per liter MgCl2 .multidot.6H2 O.
2. A medium for use in fermentation, consisting essentially of:
(a) 3.6 g per liter peptone;
(b) 1.5 to 3 g per liter autolyzed yeast extract;
(c) 1.6 g per liter Proflo.RTM. cottonseed flour;
(d) 2.0 to 7.75 g per liter dextrose;
(e) 2.5 g per liter palm oil;
(f) 0.2 g per liter cholesterol;
(g) 0.6 g per liter CaCl2 .multidot.2H2 O;
(h) 0.2 g per liter MgCl2 .multidot.6H2 O; and
(i) lecithin up to 2.0 g per liter.
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3. The medium according to claim 1, for use in culturing Lagenidium giganteum.
4. The medium according to claim 2, for use in culturing Lagenidium giganteum.Data supplied from
the esp@cenet database - Worldwide
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82. US5902890
- 11/5/1999
PROCESS FOR OBTAINING CAROTENE FROM PALM OIL
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=US5902890
Inventor(s):
NITSCHE MICHAEL (DE); JOHANNISBAUER WILHELM (DE); JORDAN
VOLKMAR (DE)
Applicant(s):
HENKEL KGAA (DE)
IP Class 4 Digits: C07C; C09B; C11B
IP Class:C07C403/02; C07C403/24; C09B61/00; C11B7/00; C07C403/00
E Class: C07C175/00B
Application Number:
US19970913710 (19971022)
Priority Number: DE19951010098 (19950320); WO1996EP01040 (19960311)
Family: US5902890
Equivalent:
WO9629306; EP0819116; DE19510098
Abstract:
Abstract of US5902890
PCT No. PCT/EP96/01040 Sec. 371 Date Oct. 22, 1997 Sec. 102(e) Date Oct. 22, 1997 PCT Filed Mar.
11, 1996 PCT Pub. No. WO96/29306 PCT Pub. Date Sep. 26, 1996Carotene is recovered from a native
fat or oil in five process steps in an economical industrial process. The native fat or oil is catalytically
reacted in known manner with an alkanol containing up to 4 carbon atoms to form fatty acid alkyl ester
and glycerol. The ester phase of the reaction mixture is subjected to distillation to remove the fatty acid
alkyl ester. The distillation residue obtained in the second process step is saponified, carotene is
extracted from the product obtained in the third process step and the extract phase is concentrated by
evaporation. A yield of at least about 80% is achieved. At the same time, a fatty acid alkyl ester
suitable for further processing to fatty alcohol is provided.Description:
Description of US5902890
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a process for recovering carotene from a native fat or oil, more particularly
from palm oil.
Depending on its origin, crude palm oil contains between 500 and 3,000 ppm of carotinoids containing
a high proportion of beta-carotene and relatively low concentrations of tocopherols, tocotrienols and
sterols.
Among the carotinoids, there are the oxygen-containing derivatives (xanthophylls) and the carotenes.
The most well-known carotenes are alpha-, beta- and gamma-carotene and also lycopene. Beta-
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carotene occurs predominantly in nature and is the actual provitamin A. Since the carotenes are natural
compounds and since they all show pronounced provitamin A activity, they are widely used as
antioxidants or as dyes in commercial applications in the pharmaceutical industry, in the food industry
and in the manufacture of cosmetics. More recently, the tumor-inhibiting activity of beta-carotene has
been repeatedly demonstrated so that it is now also used in the prophylaxis of cancer.
2. Discussion of the Related Art
Several different processes for recovering carotene from palm oil or at least for concentrating carotene
are known from the prior art.
In some known processes, the palm oil is first transesterified and/or saponified and then concentrated
by extraction or distillation. Thus, according to U.S. Pat. No. 2,460,796, the palm oil is first
transesterified with methanol. After the reaction mixture has settled out, the upper phase consisting of
fatty acid methyl ester with dissolved carotene is washed with a mixture of alcohol and water and then
with water alone. The complete or partial removal of the fatty acid methyl ester, which may be used for
the production of soap, by distillation leaves a carotene concentrate. The distillation step is carried out
in vacuo at temperatures of up to 150 DEG C. The total distillation time mentioned in this document is
around 5 hours.
The disadvantage of this known process lies in the high temperatures to which the heat-sensitive
carotene is exposed and which rule out a high yield of carotene.
In another process known from U.S. Pat. No. 2,572,467, palm oil is first saponified (Examples I and
II). Dilute sulfuric acid is added to the reaction mixture to obtain the corresponding free fatty acids.
After settling, the fatty acid phase is dissolved in acetone and filtered. The filtrate is repeatedly cooled
and refiltered to obtain a residue consisting of fatty acids and a carotene-containing solution from
which carotene can be crystallized out at -70 DEG C.
In a variant of this known process, transesterification with methanol replaces saponification of the
palm oil with subsequent acid treatment (Examples III and IV of the same U.S. patent).
In a process described in U.S. Pat. No. 2,652,433, palm oil is subjected both to transesterification and
to saponification. After neutralization and filtration, the crude palm oil is transesterified with methanol.
Saponification of the ester phase is followed by an extraction step with petroleum ether or chloroform.
The residue obtained after removal of the petroleum ether by distillation contains around 3% of
carotene.
U.S. Pat. No. 5,157,132, which was published in 1992, discloses a process for concentrating carotene
from palm oil which also begins with a transesterification step. The ester-rich phase obtained after
settling is extracted with methanol and water to obtain a phase rich in carotene. Repeated extraction
with methanol leaves a concentrated methanol/carotene mixture from which the alcohol is removed by
evaporation in vacuo (Example I). In addition, the carotene-containing fatty acid methyl ester can be
saponified after the transesterification step before it is extracted with petroleum ether. In this process,
therefore, all the carotene-containing fatty acid methyl ester is saponified (Example II).
According to GB 2,218,989 A, the crude palm oil is subjected after transesterification with methanol
to liquid chromatography with methanol and a mixture of hexane and methanol or chloroform as
mobile solvent to obtain a fraction rich in carotene.
The disadvantage of extracting carotene from fatty acid methyl ester is that the fatty acid methyl ester
is contaminated with the extractant which prevents the ester from being further processed by
hydrogenation to fatty alcohol. In general, the ester obtained in this process cannot be put to any further
use and has to be disposed of. The same disadvantage attends the extraction processes which start
directly from palm oil without preliminary transesterification.
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A process without this disadvantage is described in U.S. Pat. No. 2,432,021 where carotene is obtained
in concentrated form by extraction with liquefied propane and subsequent rectification. Although, in
this case, the palm oil can be subsequently used for the production of fatty alcohol, the process cannot
be carried out economically on an industrial scale.
In addition, adsorptive processes for concentrating carotene are known from GB 691, 924, from GB
1,562,794 and from U.S. Pat. No. 2,484,040.
To summarize the prior art, it may be said that the known processes either cannot be economically
carried out on an industrial scale or the yield of carotene is too low as a result of thermal and/or
chemical decomposition or poor selectivity or that, after the process has been carried out the palm oil
or the palm oil derivative is no longer suitable for the production of fatty alcohols.
DESCRIPTION OF THE INVENTION
Accordingly, the problem addressed by the present invention was to achieve a yield of at least about
80% in an economically workable industrial process for recovering carotene from a native fat or oil,
more particularly palm oil, and at the same time to provide a native oil or oil derivative, for example an
alkyl ester, suitable for further processing to fatty alcohol. Accordingly, the palm oil used would not be
contaminated by the process according to the invention so that it would be suitable for further
processing.
According to the invention, the solution to this problem is characterized in that
1. the native fat or oil is catalytically reacted (transesterified) in known manner with an alkanol
containing up to 4 carbon atoms, more particularly methanol, to form fatty acid alkyl ester and glycerol,
2. the ester phase of the reaction mixture is subjected to distillation to remove the fatty acid alkyl ester,
3. the distillation residue obtained in the second stage of the process is reacted with a base, preferably
potassium or sodium hydroxide (saponification),
4. carotene is extracted with a suitable solvent from the product obtained in the third stage of the
process and, finally,
5. the extract phase is concentrated by evaporation.
It is possible by the process according to the invention to produce a carotene concentrate with a
carotene content of 4 to 100% by weight, preferably 10 to 90% by weight and, more preferably, 18 to
70% by weight from a native fat or oil with a carotene yield of at least about 80%, based on the fat or
oil used. At the same time, virtually the entire quantity of oil used is made available in the form of fatty
acid alkyl ester for subsequent hydrogenation to fatty alcohol. Accordingly, besides the carotene
concentrate and the glycerol obtained by transesterification, another useful material is obtained in the
process according to the invention.
This is achieved by the above-mentioned removal of the alkyl ester by distillation from a carotenecontaining residue and subsequent saponification and by limitation of the extraction step to the
hydrolyzed distillation residue. The carotene yield of around 80% mentioned above is achieved despite
the limitation of the extraction step to this part of the reaction mixture obtained from the
transesterification step and despite the high temperatures required for the distillation step. It is also
surprising that it is possible to remove up to 99% of the alkyl ester free from carotene despite the
minimal different in vapor pressure between the alkyl esters and the carotene. Accordingly, there is
also no need to purify the alkyl ester removed before it is hydrogenated to fatty alcohol.
Accordingly, the combination of removal of the ester phase by distillation and subsequent
saponification of the distillation residue before extraction is crucial to the invention.
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The free fatty acids present in the native fat or oil are preferably esterified before transesterification
with the short-chain alkanol mentioned or are saponified during the transesterification step which, to
this end, is carried out in the presence of a sufficiently large amount of alkaline catalyst.
The first step of the process according to the invention, i.e. the transesterification step, may be carried
out in batches or even continuously in reactors of different kinds, for example in stirred tank reactors or
tube reactors. One example of transesterification carried out in a tube reactor is described in DE 39 32
514 A1. Methanol, ethanol, n- or iso-propanol or -butanol may be used as the alcohol. Methanol is
preferably used.
If an alkaline catalyst is used, it is preferably sodium hydroxide, potassium hydroxide, sodium
methylate or potassium methylate.
Since carotene is extremely sensitive to heat, low reaction temperatures and short reaction times
during the transesterification step are advantageous. A reaction temperature of 30 to 110 DEG C. and,
more particularly, 50 to 70 DEG C. is proposed. The reaction time should be between 10 and 180
minutes and, more particularly, between 30 and 90 minutes.
A two-phase mixture is obtained on completion of the transesterification step. The lower phase
consists of glycerol and does not contain any carotene. The upper phase essentially contains fatty acid
alkyl ester, excess alcohol and the carotene present in the native oil used. The upper phase and lower
phase are separated by decantation.
In the second step of the process according to the invention, the fatty acid alkyl ester obtained in the
transesterification step is purified by distillation. To this end, it is proposed that 70 to 99.5% by weight
and, more particularly, 95 to 99% by weight of the fatty acid alkyl ester obtained in the
transesterification step be removed. Virtually all the fatty acid alkyl ester is separated from the
carotene-containing residue in this step. The alkyl ester obtained in pure form is unconditionally
available as a high-quality oleochemical starting material, for example for the production of fatty
alcohols or technical esters. Another advantage is that the carotene remains entirely in the distillation
residue and is considerably concentrated in this way. This results in a considerable reduction in the
effort involved in the subsequent steps for further concentration.
The fatty acids of palm oil which consist predominantly of palmitic acid, stearic acid, oleic acid and
linoleic acid have very long chains and require a low pressure, preferably a coarse or fine vacuum, and
a high temperature for the removal of the corresponding fatty acid alkyl ester by distillation. Despite
the high temperature, however, the heat-sensitive carotene does not undergo any significant
decomposition providing evaporators with brief residence times are used. In this way, a carotene yield
of 80 to 100% can be obtained in this step of the process.
In one advantageous embodiment of the invention, therefore, the distillation step is carried out in
falling film evaporators, in thin-layer evaporators with rotating wipers or in short-path evaporators
(molecular evaporators). The evaporation process may be carried out in a single stage. However, it is of
advantage to carry out the distillation step in two or more stages and to reduce the pressure from stage
to stage. Temperatures in the range from 100 to 250 DEG C. and, more particularly, in the range from
130 to 150 DEG C. are proposed as the distillation temperatures. The operating pressure of the (last)
evaporator stage should be in the range from 10@0 to 10@-4 mbar and, more particularly, in the range
from 10@-1 to 10@-3 mbar. Where the evaporation process is carried out in a single stage, these
pressures apply to that stage. Where evaporation is carried out in several stages, the operating pressure
of the first evaporator stage is advantageously in the range from 1 to 50 mbar and, more particularly, in
the range from 2 to 20 mbar.
Depending on the amount of distillate, high concentrations, i.e. up to 20% by weight, of carotene are
obtained in the distillation residue.
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This residue is saponified in the third step of the process. It is reacted with an alkali metal hydroxide,
preferably potassium or sodium hydroxide, under normal pressure and at temperatures of 80 DEG C. to
120 DEG C. Water in up to 5 times the quantity by weight of the distillation residue is preferably added
to the reaction mixture either directly or during the saponification reaction in order to improve
solubility behavior in the following extraction step.
The fourth and penultimate step of the process comprises extraction of the carotene.
For extraction, the saponified distillation residue is intensively mixed with a solvent mixture which
preferably consists of a polar component and a non-polar component. In selecting the solvent mixture,
it is important to bear in mind that, on the one hand, the saponified residue or the aqueous soap solution
should not be completely soluble whereas, on the other hand, the carotene present in the saponified
residue should be readily soluble in the solvent mixture. Linear or branched hydrocarbons containing 4
to 12 carbon atoms are suitable as the non-polar solvent while acetone or tetrahydrofuran is proposed
as the polar solvent component. However, other solvents are also possible.
It has surprisingly been found that the carotene can be completely extracted from the saponified
distillation residue in only a single extraction step. After the extraction step, a yellow colored lower
phase containing soap and water and an orange-red upper phase (extract phase) consisting of the
solvents and carotene are obtained.
In the last step of the process, the extract phase is concentrated by evaporation. The solvent is first
evaporated off under normal pressure. After about 80 to 95% of the solvent has been removed, the
process is preferably continued in a vacuum to achieve complete removal of the solvent.
The temperature of the residue should be kept at a low value during the concentration by evaporation.
A temperature of at most 120 DEG C. is proposed for concentration of the extract phase by evaporation
and should not be exceeded even on completion of this final step of the process.
The solvent evaporated off is carotene-free and may be reused for extraction. The evaporation residue
contains between 20 and 95% by weight of carotene and traces of tocopherols, tocotrienols and sterols.
The carotene obtained by the process according to the invention is suitable for use as a dye and
preservative in foods, cosmetics and pharmaceuticals. It may also be used in the prophylaxis of cancer.
For making-up, the carotene obtained after the evaporation step may be diluted with suitable oils, for
example sunflower oil, to a concentration of 1 to 50% by weight.
The following Example is intended to illustrate the invention without limiting it in any way.
EXAMPLE
In a 5 liter stirred-tank reactor, 3000 g of crude Malaysian palm oil with a carotene content of 900 ppm
and an acid value of 9.3 were reacted with 1200 g of methanol. 36.5 g of sodium methylate in the form
of a 30% solution in methanol were added to saponify the free fatty acids and as catalyst. The reaction
was carried out with stirring under normal pressure at 60 DEG C. After a reaction time of 1 hour, the
stirrer was switched off so that the separation of methyl ester phase and glycerol phase began. After a
settling time of 2 hours, the glycerol phase was decanted off. The methyl ester phase produced weighed
2719 g and contained 1000 ppm of carotene.
The methyl ester was then removed by distillation in two stages. A rotary evaporator was used for the
first stage and a short-path evaporator for the second stage. The first distillation step was started at 100
DEG C./normal pressure. During the distillation process, the pressure was first reduced to 3 mbar and
the temperature subsequently increased to 140 DEG C. The quantity of distillate amounted to 2403 g.
The distillate was carotene-free and water-clear. The quantity of residue amounted to 304 g. The
residue was further concentrated in a short-path evaporator at 160 DEG C./1.5.multidot.10@-2 mbar,
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226 g of yellowish colored methyl ester being obtained as distillate and 70.3 g with a carotene content
of 3.6% as residue.
210 g of water and 17 g of 50% sodium hydroxide were added to the residue, followed by refluxing for
4 hours at 105 DEG C./normal pressure. 295 g of soap solution were produced.
590 g of a solvent mixture of 1 part of n-hexane and 2 parts of acetone were added to this soap
solution, followed by stirring for 30 minutes. After a settling time of 2 hours, 542 g of a brown colored
lower phase were decanted off. The upper phase obtained weighed 341 g and contained 0.75% of
carotene. This upper phase was then concentrated by evaporation, initially under normal pressure and
at a temperature of the heating medium of 80 DEG C. In the further course of the evaporation process,
the pressure was lowered to 30 mbar and the temperature of the heating medium increased to 120 DEG
C. 4.5 g of a dark-red solid with a carotene content of 54.1% were obtained. Accordingly, the carotene
yield of the process as a whole is 90%. The material produced can be made up without any further
treatment for use in foods, cosmetics or pharmaceuticals.Data supplied from the esp@cenet database Worldwide
Claims:
Claims of US5902890
We claim:
1. A process for recovering a carotene from an oil that contains carotenes and free fatty acids
comprising the steps of:
a) transesterifying the oil with an alkanol having up to 4 carbon atoms to form a two-phase mixture
comprising a glycerol phase and an ester phase, said ester phase comprising fatty acid esters and the
carotene;
b) separating the fatty acid esters from the ester phase by distillation or evaporation to form a residue
containing the carotene;
c) saponifying the residue with an alkali metal hydroxide;
d) extracting the carotene from the saponified residue with an organic solvent to form an extract phase
containing the carotene; and
e) removing the solvent from the extract phase by evaporation.
2. A process according to claim 1, wherein the oil is palm oil.
3. A process according to claim 1, wherein prior to the transesterification step, the free fatty acids of
the oil are esterified.
4. A process according to claim 1, wherein the transesterification is carried out with an amount of an
alkaline catalyst sufficient to saponify the free fatty acids of the oil.
5. A process according to claim 3, wherein the transesterification is carried out in the presence of a
homogeneous alkaline catalyst.
6. A process according to claim 5, wherein the catalyst is sodium hydroxide, potassium hydroxide,
sodium methylate, or potassium methylate.
7. A process according to claim 1, wherein the temperature of the transesterification is 30 DEG C. to
110 DEG C.
8. A process according to claim 7, wherein the temperature of the transesterification is 30 DEG C. to
100 DEG C.
9. A process according to claim 8, wherein the temperature of the transesterification is 50 DEG C. to
70 DEG C.
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10. A process according to claim 1, wherein the time of the transesterification is 10 minutes to 180
minutes.
11. A process according to claim 10, wherein the time of the transesterification is 30 minutes to 90
minutes.
12. A process according to claim 1, wherein the separation step removes from the ester phase 70% to
99.5% by weight of the fatty acid esters formed in the transesterification step.
13. A process according to claim 12, wherein the separation step removes from the ester phase 95% to
99% by weight of the fatty acid esters formed in the transesterification step.
14. A process according to claim 1, wherein the separation step is carried out in a falling film
evaporator, a wipe film evaporator, or a molecular evaporator.
15. A process according to claim 1, wherein the distillation is carried out at a temperature of 100 DEG
C. to 250 DEG C.
16. A process according to claim 15, wherein the distillation is carried out at a temperature of 130
DEG C. to 150 DEG C.
17. A process according to claim 1, wherein the separation step comprises distillation and is carried
out in more than one stage wherein the distillation pressure is reduced from stage to stage.
18. A process according to claim 17, wherein the pressure in the final distillation stage is 10@0 mbar
to 10@-4 mbar.
19. A process according to claim 18, wherein the pressure in the final distillation stage is 10@-1 mbar
to 10@-3 mbar.
20. A process according to claim 17, wherein the pressure in the first distillation stage is 1 mbar to 50
mbar.
21. A process according to claim 20, wherein the pressure in the first distillation stage is 2 to 20 mbar.
22. A process according to claim 1, wherein the saponification step is carried out at a temperature of
80 DEG C. to 120 DEG C.
23. A process according to claim 1, wherein for the saponification step the residue is diluted with up to
five times by weight of water, based on the weight of the residue.
24. A process for recovering carotene from an oil that contains carotene and free fatty acids
comprising the steps of:
a) transesterifying the oil in the presence of an alkaline catalyst selected from the group consisting of
sodium hydroxide, potassium hydroxide, sodium methylate, and potassium methylate with an alkanol
selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, n-butanol, or
isobutanol at a temperature of 30 DEG C. to 110 DEG C. for 10 minutes to 180 minutes to form a twophase mixture comprising a glycerol phase and an ester phase comprising fatty acid esters and the
carotene;
b) distilling the ester phase at a temperature of 100 DEG C. to 250 DEG C. and a pressure of 10@0
mbar to 10@-4 mbar to separate 70% to 99.5% by weight of the esters obtained in the
transesterification step from the ester phase and to form a residue containing the carotene;
c) diluting the residue with up to 5 times by weight of water based on the weight of residue;
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d) saponifying the residue with an alkali metal hydroxide at a temperature of 80 DEG C. to 120 DEG
C.;
e) extracting the carotene from the saponified residue with a solvent mixture comprising a component
and a nonpolar component to form an extract phase containing the carotene; and
f) removing the solvent from the extract phase by evaporation.
25. A process for recovering carotene from an oil that contains carotene and free fatty acids
comprising the steps of:
a) transesterifying the oil in the presence of an alkaline catalyst selected from the group consisting of
sodium hydroxide, potassium hydroxide, sodium methylate, and potassium methylate with an alkanol
selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, n-butanol, or
isobutanol at a temperature of 50 DEG C. to 70 DEG C. for 30 minutes to 90 minutes to form a twophase mixture comprising a glycerol phase and an ester phase comprising fatty acid esters and the
carotene;
b) distilling the ester phase at a temperature of 130 DEG C. to 150 DEG C. and a pressure of 10@-1
mbar to 10@-3 mbar to separate 95% to 99% by weight of the esters obtained in the transesterification
step from the ester phase and to form a residue containing the carotene;
c) diluting the residue with up to 5 times by weight of water based on the weight of residue;
d) saponifying the residue with an alkali metal hydroxide at a temperature of 80 DEG C. to 120 DEG
C.;
e) extracting the carotene from the saponified residue with a solvent mixture comprising a nonpolar
solvent selected from the group consisting of linear or branched hydrocarbons containing 4 to 12
carbon atoms and a polar solvent selected from the group consisting of acetone and tetrahydrofuran to
form an extract phase containing the carotene; and
f) separating the solvents from the extract phase to form an evaporation residue comprising 20% to
95% by weight carotene.Data supplied from the esp@cenet database - Worldwide
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83. WO0152660
- 26/7/2001
COMPOSITION OF OILS
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=WO0152660
Inventor(s):
PUTRAMENTAS ALFRIDAS (LT); GRUZDIEN EDOT (LT)
Applicant(s):
PUTRAMENTAS ALFRIDAS (LT); GRUZDIEN and EDOT (LT)
IP Class 4 Digits: A23D
IP Class:A23D9/00; A23D9/007
E Class: A23D9/00; A23D9/007
Application Number:
WO2001LT00001 (20010119)
Priority Number: LT20000000005 (20000121)
Family: WO0152660
Equivalent:
LT4734
Cited Document(s):
US4721626; JP8231981; RU2059391; JP1265870
Abstract:
Abstract of WO0152660
This invention is attributed to the industry of fats and oils and may be utilised for production of quality
vitaminised and aromatised edible salad and baking oils. The essence of the invention - use of the new
refined red palm oil and its oleic and superoleic fractions, rich with natural carotenes (provitamin A),
tocopherols (vitamin E) and biologically active substances tocotrienols in the blends of oils which
contain low level of saturated acids and sufficient amount of mono- and poly-non-saturated acids and
natural tocopherols by adding garlic oily extract, such mixes enjoying organism strengthening features
and features stabilising oil blend. The new composition of oils is obtained by entering red palm oil or
its oleic and superoleic fractions and oily garlic extract at the chosen ratios of the components (% by
weight) into refined, bleached, deodorised rapeseed, soy and sunflower-seed oils or their blends chosen
taking into consideration the composition of fatty acids.Description:
Description of WO0152660
COMPOSITION OF OILS
This invention is attributed to the industry of fats and oils and may be utilised for production of quality
vitaminised and aromatised edible salad and baking oils.
In terms of technology, there are many oils and fats or their blends known which may be used for food.
The modern industry of oils must produce oils, which meet a range of requirements applied to edible
oils : -oils shall be of a relevant consistence suitable for use ; -oils shall have good taste and neutral
scent ; -oils shall have a good trading exterior, i. e. colour and clarity ; -the most important criterion for
the modern consumer is health-friendliness of oils, i. e. oils should be suitable for nutrition and
treatment purposes.
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The solutions to the above listed problems may be achieved in a number of ways. Description of salad
oil with good food and storage characteristics is provided in SU 936 689. Such oil is produced by
correct selection of oil blend components and their ratio as well as by specific mixing process.
There are solutions to produce oils of relevant consistence and suitable for production of certain food
products. One of such solutions is described in EP 0577371 : hardening-proof oil with 10% or higher
fatty acid trigliceride blend.
Especially good taste is characteristic to oil described in EP 0 600 539 which is even cheaper than the
traditional olive oil. This blend of olive oils consists of pure olive oil and oil produced from olives
washed with alcohol, the amount of the latter in the blend may vary from 5 to 95 weight %.
There are also known natural trigliceride fats (EP 0 719 091) contained in oil blends where oils are
produced from genetically modified soy, maize, olive, rape, sunflowers and other plants. Oils from
such plants are not chemically treated, except for the usual refinery.
EP 0 744 899 and EP 0 744 900 describe new fat composition in which adequate digliceride and
trigliceride ratio is chosen in order to achieve the desired composition of fats.
To solve health problems, as substitutes of fats with low calories, a fat composition described in EP 0
591 258 is offered. Such fat composition consists of sorbitol fatty acid ester with at least 4 fatty acids
changed, which are produced from soy, safflower, sesam, arachis, maize, olives, rice bran, rape, greasewood nuts, babassu nuts, coconuts, palm kernels, cotton seeds, palm oils. In addition to that, such fats
also contain animal fat.
Also there are fats with specific antisclerotic effect described in WO 98/19555.
These fats are in particular related to widely used fats, margarine, plant butter which have at least 25%
of the basic fat phase composed of oil ; in addition to that, it may contain animal fats and have
additives which reduce the level of cholesterol in the blood. The above additives consist of the main
hipolipidemics of the phospholipide group and/or of vitamin PP.
New edible phospholipidic products, which have antioxidation and cholesterolreducing features, are
described in RU 2 007 925, RU 2 031 589 and RU 2 052 946.
They consist of refined or refined-deodorised plant oil and plant phospholipide produced by hydration
of non-refined plant oil by means of alternate electromagnetic field. In patents there are different ratios
of oil and phospholipide chosen.
RU 2 031 590, RU 2 041 638 and RU 2 052 947 describe plant-origin fat products with characteristic
immunity stimulation features. These products are phospholipides of plant origin produced by
hydration of non-refined plant oil by means of alternate and constant electromagnetic fields. Different
products are produced by changing voltage of electromagnetic fields.
Vitaminised oil for salads enriched withp-carotene also enjoys features, which reduce the level of
cholesterol in the blood as described in SU 1 799251. This blend of oils is made of maize oil (33-35%)
and olive oil (64-66%). The blend contains 0, 015-0, 200% of-carotene and 0, 4-0, 8% of phosphatides.
Artificial entering of-carotene and phosphatides into the blend causes certain technological problems ;
in addition to that, the level of artificially enteredp-carotene is not organically related to the fatty acids
of the oil, therefore, its absorption and effect are not that efficient as in the cases where p-carotenes are
contained and preserved in oils naturally.
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Significant amount of natural carotenes,especially-carotene is contained in freshly pressed red palm
oil described in WO 98/18888. Minimal amount of carotenes in this refined palm oil comprises 500
mg/kg, whereas the amount of vitamin E
(tocopherols and tocotrienols)-800 mg/kg, free fatty acids-less than 0, 08%,
peroxide-approximately 0-1, 0 mekv/kg. The oil is scentless and tasteless.
Hence, the red palm oil, which contains large amount of carotenes and vitamin
E, is extremely suitable for healthy nutrition. However, certain physical characteristics
of the oil, especially hardening at the room temperature already, reduce comfort of its
use. Moreover, due to expensive primary raw oil, complex and expensive refinement
technology, the costs of pure palm oil are rather high.
The purpose of the invention-production of oil rich with vitamins A, E and
F, stabile in terms of oxidation and enjoying features which strengthen the organism.
The essence of the invention-use of the new refined red palm oil and its oleic
and superoleic fractions, rich with natural carotenes (provitamin A), tocopherols
(vitamin E) and biologically active substances tocotrienols in the blends of oils which
contain low level of saturated acids and sufficient amount of mono-and poly-non
saturated acids and natural tocopherols by adding garlic oily extract, such mixes
enjoying organism strengthening features and features stabilising oil blend.
The above purpose is achieved by entering red palm oil or its oleic and
superoleic fractions and oily garlic extract at the below ratios of the components (% by
weight) into refined, bleached, deodorised rapeseed, soy and sunflower-seed oils or
their blends chosen taking into consideration the composition of fatty acids :
red palm oil (RPA) or its oleic (RPO) or superoleic
(RPSO) fractions 5-50
rapeseed oil 40-95
or soy oil 40-95
or sunflower-seed oil 40-95
or rapeseed and sunflower-seed oils blend
(ratio 50 : 50, 40 : 60, etc.) 40-95
or rapeseed and soy oils blend 40-95
oily garlic extract 1-30.
Oily garlic extract is produced by extraction of fresh garlic cloves with -sunflower-seed or rapeseed oil.
It is known that in the course of refinement of plant oils, together with free fatty acids, colouring and
aromatic substances, physiologically important substances such as phospholipides,carotinoides,
tocopherols, etc., are fully removed, therefore, components the refinement technologies of which are
different, which enable to preserve up to 80% of vitamins and other biologically active substances and
which have a proper composition of fatty acids, sufficient amount in terms of nutrition of poly-nonsaturated fatty acids, are chosen.
Sunflower-seed and rapeseed oils contain a large amount of mono-and polynon-saturated fatty acids
(vitamin F), which by participating in circulation of cholesterol inhibit build-up of atheroscleroses in
heart coronal, brain, kidney, intestines and peripheral arteries. Sunflower-seed and rapeseed oils also
are rich with vitamin E (tocopherols), which has antioxidation features ; the red palm oil contains
carotenes (provitamin A) and biologically active anti-cancer substances tocotrienols, which together
with vitamin Eand-carotene are strong natural antioxidants.
Furthermore, as shown by the data of certain epidemiological researches, carotenes (provitamin A)
reduce the risk of hear coronary disease and resulting miocard infarct.
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The reduction of disease risk can be explained by the function performed by natural antioxidants
protecting from the cell-destruction effect caused by free radicals.
Increased formation of free radicals may be caused by a number of external and internal factors and
result in so called stress. When the latter continues, the risk of such diseases asatherosclerosis, sugar
diabetics, lung diseases(chronic bronchitis, asthma), rheumatoid diseases of joints, cataract, certain
cancer diseases the reason for which is the external factor, Parkinson's disease, ageing process as well
as a number of intoxications, occurs. In the food ration of population usually fats of animal origin
dominate, therefore the human organism lacks poly-non-saturated fatty acids (vitamin
F) which are not synthesised by a human organism and which have to be absorbed together with food.
Sufficiently large amount of poly-non-saturated fatty acids (linoleic, alinolenic) is contained in
rapeseed and sunflower-seed oil, whereas the blend of such oils (60 : 40) is the most ideal in terms of
the ratio of these acids.
These irreplaceable acids participate in the synthesis of poly-non-saturated fatty acids with long
chains :arachidone and eicozapentaene as well as docozahexaene.
As a result of lack of linol and a-linolene in the organism the syndrome of lack of irreplaceable fatty
acids is developed-reduction of energy, slow growth, dermatitis, degeneration of tissue structure, heart,
kidney and genitals. Moreover, poly-nonsaturated acids regulate the amount of cholesterol in the blood.
Table1. Composition of acids of plant origin, % by weight of the total amount of acids.
EMI5.1
>;SEP; Saturated >;SEP; Mono-non-Poly-non-saturated
>;tb; >;SEP; Oil >;SEP; fatty >;SEP; acids >;SEP; saturated >;SEP; fatty >;SEP; acids
>;tb; >;SEP; fatty >;SEP; acids >;SEP; Linoleic >;SEP; a-linolenic
>;tb; >;SEP; (oleinic >;SEP; acid)
>;tb; Rapeseed >;SEP; oil >;SEP; 6, >;SEP; 2 >;SEP; 59, >;SEP; 40 >;SEP; 20, >;SEP; 7 >;SEP; 10,
>;SEP; 1
>;tb; Sunflower-seed >;SEP; oil'11, >;SEP; 0 >;SEP; 21, >;SEP; 10 >;SEP; 66, >;SEP; 2
>;tb; Sunflower-seed >;SEP; oil2 >;SEP; 9,4 >;SEP; 79,9 >;SEP; 14,8 >;SEP;
>;tb; Red >;SEP; palm >;SEP; oil >;SEP; (RPA) >;SEP; 49, >;SEP; 9 >;SEP; 39, >;SEP; 2 >;SEP; 10,
>;SEP; 1 >;SEP; 0, >;SEP; 4
>;tb; Red >;SEP; palm >;SEP; olein >;SEP; (RPO) >;SEP; 45, >;SEP; 4 >;SEP; 42, >;SEP; 5 >;SEP;
11, >;SEP; 2 >;SEP; 0, >;SEP; 35
>;tb; Red >;SEP; palm >;SEP; superolein >;SEP; (RPSO) >;SEP; 34, >;SEP; 5 >;SEP; 47, >;SEP; 3
>;SEP; 14, >;SEP; 0 >;SEP; 0, >;SEP; 3
>;tb;
'-sunflower-seed oil, which contains large amount of linoleic acids-suitable for salads ;
2-sunflower-seed oil which has reduced amount of linoleic acid and increased amount of olein (special
species of sunflowers)-suitable for cooking and baking purposes.
The data presented in the Table 1 show that rapeseed and sunflower-seed oils have small amount of
saturated and sufficiently large amount of poly-non-saturated fatty acids (linoleic anda-linolenicvitamin F), whereas sunflower-seed and rapeseed oil blend at the ratio 40 : 60 is the most ideal option
for nutrition purposes.
Production of the red palm oil and its olein and superolein fractions was started in Malaysia in
accordance with the advanced patented technology offered by the Palm
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Oil Research Institute of Malaysia. With the help of such technology more than 80% of carotenes and
tocopheroles can be preserved. This oil is unique as it contains tocotrienols, tocopheroles and carotenes
(Table 2) as well as because it contains a large amount of saturated acids.
Table 2. Comparison of amounts of tocopherols, tocotrienols and carotenes in oils.
EMI6.1
>;tb;
>;SEP; Oil >;SEP; Carotenes, >;SEP; total >;SEP; Tocopheroles, >;SEP; Tocotrienols, >;SEP; T+
>;SEP; T3,
>;tb; >;SEP; mg/kg >;SEP; mg/kg >;SEP; mg/kg >;SEP; mg/kg
>;tb; >;SEP; aT, >;SEP; T, >;SEP; #T, >;SEP; #T >;SEP; ;T3, >;SEP; T3, >;SEP; #T3, >;SEP; #T3
>;tb; >;SEP; RPA >;SEP; 500 >;SEP; (47, >;SEP; 4%p, >;SEP; 152---205-439 >;SEP; 94 >;SEP; 890
>;tb; >;SEP; 37% >;SEP; a)
>;tb; RPA >;SEP; 500 >;SEP; 152---205-439 >;SEP; 94 >;SEP; 890
>;tb; RPSO >;SEP; 500 >;SEP; 152---205-439 >;SEP; 94 >;SEP; 890
>;tb; Sunflower-seed-487-51 >;SEP; 8----546
>;tb; oil
>;tb; Soy >;SEP; oil-101-593 >;SEP; 264----985
>;tb; Rapeseed >;SEP; oil-216-584-----800
>;tb;
The data of the most recent researches (Komyama K., Izuko, Yamaoko M., etc., 1989) showed that
tocotrienols are stronger as antioxidants than tocopherols.
Moreover, the red palm oil contains 47, 4% ofp-carotene and 37% ofa-carotene, therefore, addition of
this oil into oil blends for nutrition purposes may partly compensate shortage of the vitamin A.pcarotene (predecessor of the vitamin A) as a strong antioxidant participates in neutralisation of harmful
excess of oxygen and free radicals in the organism. It has been established (Carrolls, K. K., 1995) that
natural acarotene is important in anti-cancer prophylactics and thaty-tocotrienol is three times more
effective than the widely used anti-cancer medicineTomaxifin. The vitamin A produced from synthetic
sources may be poisonous if it is overdosed.P-carotenes contained in the red palm oil may be used
together with food without any restrictions.
In addition to that, antioxidants-vitamin E,p-carotene, tocotrienols-which are able to bind free radicals,
inhibit the ageing process.
Garlic has a feature of high antioxidation activity with regard to hyperoxidic radicals ; in particular,
the fresh garlic is active and rich with natural antioxidants (J.Valicek, R. Kubec, J. Davideh. Chemical
Composition and Classification of
Culinary and Pharmaceutical Garlic-Based Products. Lebensm Unters Forsh A (1997) 204 : 164-164).
Guohua Cao, Emin Sofic have confirmed by conducting researches that among 22 of the analysed
different vegetables the garlic acetone extract showed the highest antioxidation intensity inhibiting fat
oxidation processes (Guohua Cao,
Ermin Sofic and Ronald L. Prior, Antioxidant Capacity of Tea and Common
Vegetables, J. Agric. Food chem., (1996), 44, 3426-3431). In order to stabilise the rapeseed oil with the
natural antioxidants contained in the garlic and also to aromatise it, free garlic oil extract has been
added to rapeseed oil as an alternative to acetone extracts ; oil mix stability analysis has been carried
out at temperatures of40 C and75 C. The research has showed that a 30% additive of oily garlic
extract at the temperature of40 C has stabilised rapeseed oil by almost 1, 5 times when compared to
the reference. Moreover, it added to the oil a nice and not too strong garlic aroma, which is acceptable
to the users. The data of the research show that at the temperature of75 C, in terms of inhibition of
oxidation process, rapeseed oil(55%), garlic extract (30%) and red superolein (15%) blend is the most
efficient when compared to the pure rapeseed oil. In this case the stability of rapeseed oil at the
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temperature of75 C has increased by 2, 5 times. In addition to that, it has been established that
antioxidant combinations contained in garlic extract are more active at higher temperature ; therefore,
such combinations may be used for salads and for food preparation by baking.
Examples of oil blends as well as their optimal ratios (weight %) are presented below :
Example 1 :
Rapeseed oil 85
RPSO 15
Garlic extract in rapeseed oil 30
Example 2 :
Rapeseed oil 80
RPA 20
Example3 :
Rapeseed oil 48
Sunflower-seed oil 32
RPSO 20
Example 4 :
Sunflower-seed oil 90
RPSO 10
Example 5 :
Rapeseed oil 50
RPSO 50Table 3. Chemical composition of new structures and their components>;/RTI;
EMI9.1
Tocopherols, >;SEP; mg/100g >;SEP; Tocotrienols, >;SEP; Carotenes, >;SEP; Amount >;SEP; of
>;SEP; fatty >;SEP; acids >;SEP; in >;SEP; the >;SEP; total >;SEP; amoutn >;SEP; of >;SEP; acids,
>;SEP; %
>;tb; Oil >;SEP; Total >;SEP; ;-tocopherol >;SEP; mg/100g >;SEP; mg/100g >;SEP; Saturated >;SEP;
Mono-saturated >;SEP; Poly-non-saturated
>;tb; amount >;SEP; (oleic >;SEP; acid) >;SEP; Linoleic >;SEP; ;-linolenic
>;tb; Example >;SEP; 1 >;SEP; 53,3 >;SEP; 24,8 >;SEP; 16,2 >;SEP; 13,0 >;SEP; 10,85 >;SEP; 61,52
>;SEP; 17,99 >;SEP; 8,95
>;tb; Exmaple >;SEP; 2 >;SEP; 58,3 >;SEP; 26,1 >;SEP; 9,72 >;SEP; 8,1 >;SEP; 14,7 >;SEP; 59,17
>;SEP; 16,98 >;SEP; 8,08
>;tb; Exmaple >;SEP; 3 >;SEP; 54,1 >;SEP; 28,2 >;SEP; 12,96 >;SEP; 10,0 >;SEP; 14,06 >;SEP;
456,91 >;SEP; 34,87 >;SEP; 4,95
>;tb; Example >;SEP; 4 >;SEP; 50,66 >;SEP; 45,32 >;SEP; 6,48 >;SEP; 5,0 >;SEP; 8,63 >;SEP; 61,94
>;SEP; 14,24 >;SEP; 9,04
>;tb; Example >;SEP; 5 >;SEP; 34,9 >;SEP; 31.95 >;SEP; 32,4 >;SEP; 25 >;SEP; 22,5 >;SEP; 55,6
>;SEP; 16,35 >;SEP; 5,15
>;tb; RPA >;SEP; 15,2 >;SEP; 15,2 >;SEP; 64,8 >;SEP; 50 >;SEP; 49,9 >;SEP; 39,2 >;SEP; 10,1
>;SEP; 0,4
>;tb; RPO >;SEP; 15,2 >;SEP; 15,2 >;SEP; 64,8 >;SEP; 50 >;SEP; 45,4 >;SEP; 42,5 >;SEP; 11,2
>;SEP; 0,35
>;tb; RPSO >;SEP; 15,2 >;SEP; 15,2 >;SEP; 64,8 >;SEP; 50 >;SEP; 38,3 >;SEP; 47 >;SEP; 14 >;SEP;
0,3
>;tb; Rapeseed >;SEP; oil >;SEP; 66,80 >;SEP; 18-28 >;SEP; - >;SEP; - >;SEP; 6 >;SEP; 64,1 >;SEP;
18,7 >;SEP; 10
>;tb; Sunflower-seed >;SEP; oil1 >;SEP; 54,6 >;SEP; 48,7 >;SEP; - >;SEP; - >;SEP; 1,1 >;SEP; 21,1
>;SEP; 66,2 >;SEP;
Sunflower-seed >;SEP; oil2 >;SEP; 54,6 >;SEP; 48,7 >;SEP; - >;SEP; - >;SEP; 9,4 >;SEP; 79,9 >;SEP;
14,8 >;SEP;
Table 3 shows the most popular oils world-wide as well as in Lithuania.
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Sunflower-seed and rapeseed oils have been chosen since they contain the lowest amount of restricted
saturated and sufficient amount in terms of nutrition of mono and poly-non-saturated fatty acids.
Saturated acids contained in the red palm oil have positive influence on reduction of"bad"cholesterol in
the blood by 7-38% and thus is even useful to a human organism. The data of the research presented in
the Table show that taking into account the composition of fatty acids and amount of biologically
active substances, the compositions as shown in examples 1, 2 and 4 may be used as salad oils enriched
with vitamins A, E and with biologically active substances ; in addition to that, they contain sufficient
amount of poly-non-saturated fatty acids (vitamin F) and due to the contained natural substancesantioxidants they may be used for baking purposes using a small amount of oil, whereas the
composition 1 is additionally aromatised with garlic which has antioxidation and anti-microbe effects.
The third example of the composition is specific by the following feature : it has an ideal ratioof alinolenic and linoleic fatty acids in terms of nutrition, i. e. 1 : 7, and this oil may be used as a diet oil
enriched with natural vitamins-antioxidants which strengthen the general condition of the organism.
The composition given in the example 5 may be used for deep baking due to different amount of
certain fatty acids (increased oil stability with regard to oxidation), due to the ratio of saturated,
mononon-saturated and poly-non-saturated acids which is close to diet level (1 : 1 : 1) as well as due to
large amount of natural antioxidants (saturated-22, 5%,a-linolenic- 5, 15%).Data supplied from the
esp@cenet database - Worldwide
Claims:
Claims of WO0152660
Claims : 1. Composition of oils which contains rapeseed and/or soy, sunflower-seed oil,
characterised in that red palm oil(RPA) or its oleic(RPO) or superoleic (RPSO)
fractions are added and the components are taken at the following ratio, % by
weight :
red palm oil (RPA) or its oleic (RPO) or its
superoleic (RPSO) fractions 5-50
rapeseed oil40-95
or soy oil 40-95
or sunflower-seed oil 40-95
or rapeseed and sunflower-seed oils blend 40-95
or rapeseed and soy oils blend 40-95.
2. Composition of oils according to claim 1, characterised in that rapeseed and
sunflower-seed oils blend is formed of 50% of rapeseed oil and 50% of
sunflower-seed oil.
3. Composition of oils according to claim1, characterised in that rapeseed and
sunflower-seed oils blend is formed of 40% of rapeseed oil and 60% of
sunflower-seed oil.
4. Composition of oils according to claim1, characterised in that rapeseed and soy
oils blend is formed of 50% of rapeseed oil and 50% of soy oil.
5. Composition of oils according to claim 1, characterised in that rapeseed and soy
oils blend is formed of 60% of rapeseed oil and 40% of soy oil.
6. Composition of oils according to any one of claims 1 to 5, characterised in that a
part of rapeseed oil is replaced by oily garlic extract in the rapeseed oil, the
extract amount being 1-30 weight % of the total composition mass.
7. Composition of oils according to any one of claims 1 to 3, characterised in that a
part of sunflower-seed oil is replaced by oily garlic extract in the sunflower-seed
oil with the reduced amount of linoleic acid and increased amount of oleic acid,
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the extract amount being 1-30 weight % of the total composition mass.Data supplied from the
esp@cenet database - Worldwide
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84. WO2004061059
- 22/7/2004
RECOVERING OIL FROM PALM MESOCARP FIBRES
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=WO2004061059
Inventor(s):
GOH KEE SENG (MY); GOH CHENG HUAT (MY); MA ENG YAU (MY); LEE
LIANG (MY); NG CHEE HEONG (MY); TAN TIAM AIK (MY); SINGH TARAN TEJ (MY)
Applicant(s):
EONCHEM TECHNOLOGY SDN BHD (MY); LIM KIAN HIN (SG); GOH KEE
SENG (MY); GOH CHENG HUAT (MY); MA ENG YAU (MY); LEE LIANG (MY); NG CHEE
HEONG (MY); TAN TIAM AIK (MY); SINGH TARAN TEJ (MY)
IP Class 4 Digits: C11B; C11C
IP Class:C11B1/10; C11B1/00; C11C
E Class: C11B1/10; C11B1/10B; C11B1/10F
Application Number:
WO2004SG00002 (20040106)
Priority Number: MY20030000034 (20030106)
Family: WO2004061059
Equivalent:
WO2004061059
Cited Document(s):
US4325882; US4956125
Abstract:
Abstract of WO2004061059
The invention discloses a process and apparatus to extract remaining oil from mesocarp fibres of oil
palm after initial extraction of oil. The process includes the following steps: reducing the moisture
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content of the mesocarp fibres to below 10 % by weight; subjecting the mesocarp fibres to a solvent in
an enclosed chamber at a temperature between 45 to 55 DEG C to yield a miscella and deoiled
mesocarp fibres; removing the miscella containing oil, solvent and moisture; removing the solvent
from the deoiled mesocarp fibres produced; separating oil, solvent and moisture respectively from the
miscella. The solvent used is food grade hexane. Content of hexane in the extracted palm oil is below
0.1 % by weight. Remaining oil content of the deoiled mesocarp fibres is below 0.5 % by
weight.Description:
Description of WO2004061059
>;Desc/Clms Page number 1;
RECOVERING OIL FROM PALM MESOCARP FIBRES FIELD OF INVENTION
The present invention relates to a process of recovery of residual palm oil from palm fibres, more
particularly mesocarp palm fibres. More particularly, the invention is directed to a solvent extraction
process whereby residual palm oil in mesocarp fibres of palm fruits is recovered.
BACKGROUND ART
Among plants producing edible oils, the oil palm yields the most oil per hectare.
With the recent introduction of African Weevil Eloeidobiuss Kamerancius in 1981, especially in
Malaysia the yield per hectare has increased. A typical palm fruit is a drupe, oval in shape and contains
a kernel, which is the true seed. The kernel is surrounded by the fruit wall (pericarp) made up of the
hard shell (endocarp), oil bearing tissues (mesocarp) and the skin (exocarp).
The prior art process for the extraction of palm oil uses basic technology developed some 30 years ago
in Africa. The palm oil milling process known in the art comprises the major steps of digestion of fruit
bunches(FFB), oil extraction, oil clarification, sludge separation and kernel separation. There are two
main products derived from the palm oil milling process namely palm oil and kernels. There are several
methods of oil extraction which are known in the art. They are generally classified as the wet process,
using a wash liquid to free the oil in palm fruit and the dry process for example batch type hydraulic
press, a semi continuous type hydraulic press and a continuous type screw press, etc. Each
>;Desc/Clms Page number 2;
process has its advantages and disadvantages. The wet process ensures that there is no nut breakage
but results in the accumulation of unacceptably large quantities of fibres in the wash liquid/oil mixture.
Additional efforts have to be expanded to remove the fibres from the said mixture.
The continuous screw press (a dry process) gives high throughput, and operates at comparatively low
energy cost, but tends to result in a high amount of nut breakage when the operating conditions are not
ideal. Nut breakage in the screw press process is not desired as it would result in deterioration of crude
palm oil quality as well as higher costs of maintenance of presses. The kernel is obtained by separation
from the nut by a cracking process. Other by-products such as fibres, shells, and empty bunches are
also produced.
In the prior art, after crude palm oil is extracted from digested palm fruit by pressing, the mesocarp
fibre still contains about 5% oil, which cannot be ideally further extracted by increased pressure as the
excessive pressure would result in higher quantities of broken kernel, deterioration of crude palm oil
quality as well as higher cost of maintenance of presses. The fibres containing 5% oil is usually used as
fuel, burnt in the steam boilers in the palm oil mills, thereby losing useful palm oil. Any further excess
palm fibres from the mill are disposed off as mulches. Basically the mesocarp fibres will be produced
as by-products and used as fuel. If the quantities of broken kernel from pressing are intended to be
lower, a lower pressure in the oil presses must be used. But this approach results in higher (10-12%)
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residual oil in the fibres. There is a need to produce an efficient method of extracting the residual palm
oil in the mesocarp fibres without increasing the quantity of broken nuts.
>;Desc/Clms Page number 3;
Trials have been done using hexane extraction but it was not successful or commercially viable.
Typically the rate of usage of hexane was 22 litres per tonne FFB.
Such a rate of wastage of hexane is not commercially viable or economical. For this reason, no
attempts have been seriously made to extract the remaining 5% oil from the mesocarp fibres. Industry
did not know how to extract the residual palm oil from the mesocarp fibres with a minimum acceptable
loss of hexane in the extraction process.
SUMMARY OF INVENTION
The invention discloses a process and apparatus to extract remaining oil from mesocarp fibres of oil
palm after initial extraction of oil. The process includes the following steps: reducing the moisture
content of the mesocarp fibres to below 10% by weight; subjecting the mesocarp fibres to a solvent in
an enclosed chamber at a temperature between 45 to55 C to yield a miscella and deoiled mesocarp
fibres; removing the miscella containing oil, solvent and moisture; removing the solvent from the
deoiled mesocarp fibres produced; separating oil, solvent and moisture respectively from the miscella.
The deoiled mesocarp fibres contain bound moisture and oil. The mesocarp fibres are subjected to a
temperature between100 C to110 C and a pressure of 0.993 to 0.997 bar (absolute) in a fibre cooker to
reduce the moisture content to below 10%. Then the mesocarp fibres are cooled to a temperature
between50 C to60 C before introduction into a band extractor enclosed chamber. In the enclosed
chamber the mesocarp fibres are moved in a forward linear direction on a reticulated moving conveyor
and are subjected to a plurality of continous sprays of solvent and mixtures of solvent and palm oil in a
counter-current manner. The sprayer at forwardmost position sprays solvent and sprayer at the most
distal
>;Desc/Clms Page number 4;
position sprays a mixture of solvent and palm oil and the sprayers from the forwardmost position to
distal position spray an increasing ratio of oil to solvent.
Besides using the band extractor, a rotary cell extractor can be also used. In the rotary cell extractor,
the mesocarp fibres are moved in a forward rotary direction in a plurality of rotary cells which are
subjected to a plurality of continous sprays of solvent, and mixtures of solvent and palm oil in a
counter-current manner. During the forward rotary movement of cell, the fibres are washed
continuously with miscella of decreasing of oil content and finally with solvent in a counter-current
manner by means of a plurality of sprayers.
The miscella richest in oil from either the band extractor or the rotary cell extractor is sent to a
miscella holding tank. The rich miscella from the holding tank is pumped to the distillation section.
The distillated crude palm oil is then pumped to storage tank.
The deoiled mesocarp fibres obtained from the extractor are transported to an agitation chamber
known as toaster. Within the agitation chamber the deoiled mesocarp fibres are moved forward
preferably in a downward direction. The temperature within the chamber is maintained at100 C to110
C and is subjected to counter flow of open steam of107 C at 0.3 barg wherein the solvent in the doiled
mesocarp fibres is vapourised. This process is known as the desolventisation process. The
deoiled/desolventised fibre after oil the extraction is transported back to mill by means of chain
conveyor or other suitable to be used as boiler fuel. The solvent vapours formed in toaster as well as in
the distillation sections are to be condensed. Solvent and water vapours condensed in condensers are
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combined in a receiver and the solvent is separated from water by decantation and recycled to the
extractor. Uncondensed solvent from the condensers is led to a contact cooler in an
>;Desc/Clms Page number 5;
absorption section. Thereafter the uncondensed vapours are passed through an absorber.
The solvent gets absorbed in a spindle oil. Absorbed solvent is passed through evaporator and released
and taken to another condenser where it is condensed and combined with solvent recovered from other
sections. Uncondensed gasses are removed from the absorption section through a vent. The solvent
used is food grade hexane. Content of hexane in the extracted palm oil is below 0. 1% by weight.
Remaining oil content of the deoiled mesocarp fibres is below 0.5% by weight.
Further scope of applicability of the present invention will become apparent from the detailed
description given hereinafter. However, it should be understood that the detailed description and
specific examples, while indicating preferred embodiments of the above.
DETAILED DESCRIPTION The present invention will become more fully understood from the
detailed description given hereinbelow and the accompanying drawings which are given by way of
illustration only, and thus are not limitative of the present invention, wherein: Figure 1 shows the flow
chart of the solvent extraction plant.
Figure 2 shows the mass balance for 15 tons/hr or 360 tons/day (24 hours).
Figure 3A and B shows the flow sheet for solvent extraction plant.
Figure 4 shows a diagrammatic plan view of a rotary cell extractor.
Figure 5 shows a diagrammatic side sectional view of the rotary cell extractor.
The solvent extraction process consists of a first phase of preparing the palm fibres followed by second
phase of solvent extraction of the palm oil in the mesocarp fibres.
>;Desc/Clms Page number 6;
The first phase in general term involves the reduction of moisture content of palm fibres extruded from
the screw press. The mesocarp fibres produced by the palm oil mill after being subjected to the screw
press contains 30-40% moisture. For efficient solvent extraction the moisture content has to be reduced
to 8-10%. This is achieved by heating the fibres in a fibre cooker/dryer (10) at a temperature
between100-110 C under reduced pressure, using jacketed steam. The reduced pressure in the dryer
(10) is preferably maintained 0.995bar absolute. The steam pressure in the jacket is maintained at8lObarg and at a temperature of175-184 C. The temperature of the incoming fibres before feeding onto
the fibre cooker/dryer (10) is approximately45 C. The heated fibres are then cooled in a cooler (12) to a
temperature of55 C. The heating of the mesocarp fibres also facilitates the rupture of the oil bearing
cells within the fibres. This rupture of cells is desired as it enables the solvent to penetrate the oil
bearing cells for better extraction of oil.
The dried fibres now containing 10% or less oil are then transferred to the second phase.
The solvent extraction which is the second phase consists of 5 main processes: i) Extraction process ii)
Miscella Distillation process iii) De-oiled FibreDe-solventisation process iv) Condensation process v)
Absorption process
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The dried fibres from the preparatory section are conveyed by Redler conveyor to a band extractor (14).
Other types of material handling equipment can be easily adapted. A rotary valve regulates the feed
rate of material. Level indicators are provided on receiving hopper (16) to control low and high level of
the materials in the hopper (12). The extractor
>;Desc/Clms Page number 7;
(14) operates at temperature of45-55 C and pressure between 0.993-0. 997bar absolute.
The extractor (14) has a slow moving reticulated band conveyor (18) inside a totally enclosed chamber
(20). The band conveyor (18) is lined with perforated sheet, covered with stainless steel wire mesh for
easy percolation of miscella. The band conveyor (18) moves on a rail provided inside the extractor (14).
A series of sprayers (22) are located above the band conveyor (18) for spraying miscella and hexane on
top of the moving material bed of fibres (30) in the extractor (14). The solvent is sprayed in 8-11 stages.
Each stage of sprayer has a trough (24), heaters (26) and pumps (28) underneath. The heaters (26)
consist of circulating steam jackets. The jacket steam in heaters (26) is at a pressure of up to 5 barg and
temperature of159 C. During the movement of the material bed through the extractor (14) the fibres are
washed continuously with miscella of decreasing concentration and finally with fresh solvent in a
counter-current manner by means of sprayers (22) arranged in a line over the bed (30). The miscella
percolates through the bed (30), passes through the perforated screen of the conveyor (18) and collects
in various troughs (24) located underneath the band conveyor which ultimately flows to the miscella
holding tank (32). By the end of extraction cycle, oil in the fibres is reduced to less than 0.5% by
weight. The fibres after the extraction process from the band conveyor (18) fall into a de-oiled fibre
hopper (34) and conveyed to the desolventising section by an air tight de-oiled fibre conveyor (36).
Instead of using a band extractor, a rotary cell extractor (100) can be used to extract the remaining oil
in the mesocarp fibres. The detail description of the rotary cell extractor (100) is described below.
>;Desc/Clms Page number 8;
The dried palm fibres from the preparatory section are conveyed by Redler conveyor to an rotary cell
extractor (100). A rotary valve regulates the feed rate of material through a receiving hopper (102). The
extractor(100) operates at temperature of45-55 C and pressure of 0.995bar absolute. The extractor
(100) has a slow moving rotary conveyor consisting of number of stages of moving compartments, a of
stationary stainless steel grating (104) fitted between the compartments and miscella troughs (106),
inside a totally enclosed chamber (108). The feed (124) consisting dried palm fibres from the fibre
cooker are fed to an empty compartment which is positioned underneath the feed hopper during the
rotary motion of the conveyor. Miscella that is richest in oil is sprayed into the compartment
immediately adjacent to the compartment into which the palm fibres are fed.
A series of progessively leaner miscella sprays (110) is sprayed counter-currently into the
compartments filled with fibres, via a plurality of sprayers. The miscella circulated in each
compartment percolates through the fibres and then passes through the grating (104) acting as a screen,
into trough beneath and recycled back to the top of preceding compartments with the help of pumps
(112) fixed under each trough (106). Each sprayer has a heater (114) consisting of steam jackets. The
jacket steam in the heaters (114) is at a pressure of up to 5 barg and temperature of159 C. During the
forward rotary movement of the compartments filled with fibres, within the chamber (108), the fibres
are washed continuously with miscella of decreasing concentration of oil and finally with fresh solvent
(122) in a counter-current manner by means of sprayers (110). The miscella at each stage percolates
through the fibres (116), passes through the perforated grating (104) and collects in respective troughs
(106) located underneath the grating. The miscella richest in oil concentration flows to a miscella
holding tank (118). By the end of extraction cycle which
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is one revolution of rotary compartments, oil in the fibres is reduced to less than 0.5% by weight. The
fibres after the extraction process from extractor (100) fall into a de-oiled fibre hopper (120) and are
conveyed to the desolventising section by an air tight de-oiled fibre conveyor (126) as explained in the
embodiment for utilizing the band extractor (14).
The extracted fibres retain solvent and this solvent has to be recovered. The retention varies from 25%
to 30% of weight of fibre. The basic principles involved in desolventisation includes indirect/direct
heating of fibres with steam to a temperature well above the boiling point of solvent and and removal
of the solvent in vapour phase. Vapour of solvent is then sent to condensers via scrubber (40) where
solvent is condensed and recycled to the extractor (14) together with solvent recovered from miscella
distillation further down the process line. The equipment used in the desolventisation is known as the
de-solventiser-toaster or an agitation chamber (38). The operating temperature is between100-110 C
and the operating pressure is between 0.993-0. 997 bar (absolute). The temperature of the jacket steam
is between170 C-184 C and the steam pressure is between 8-10 barg. The
extracteddeoiled/desolventised fibre is transported back to the mill section by means of chain conveyor,
to be used as boiler fuel or for other downstream uses.
The mixture of oil and solvent obtained from the extractor (14) is known as miscella and it normally
contains 10% to 15% of oil in solvent. The rich miscella from the extractor is collected in a tank from
where it is pumped to the distillation section. It is kept under vacuum by means of a series of steam
ejector. The miscella is sent to a economizer (42) where the miscella is heated to80 C. Then the heated
miscella is passed through evaporator (44) and thus a part of the solvent in the miscella vaporizes
immediately. The
>;Desc/Clms Page number 10;
solvent vapour is led to the condensers (46,48). The concentrated miscella is sent to a first miscella
heater (50), heated between90-100 C and sent to a first evaporator (54) for flashing solvent from
miscella. The miscella from 1st evaporator is then passed through a second heater (52), heated
between100-110 C and sent to a second evaporator (56) for further separation of solvent by flashing.
The oil from evaporator (56) is atomized in a stripping column (58), for final removal of the last traces
of solvent from oil. Stripped crude palm oil is then pumped to storage tank and vapour from the
equipments is condensed in a condenser (60).
The solvent vapours formed both in the toaster (38) as well as in the distillation sections are to be
condensed. This condensation section consists of three shell and tube condensers (46,48, 60). The
miscella distillation, desolventisation and solvent absorption sections are appropriately connected to
respective condensers depending on the pressure required in each section. Solvent and water vapours
condensed in all the condensers are combined in a receiver (62). The solvent is separated from water by
decantation and recycled to the extractor (14).
To minimize solvent losses due to economical and fire hazard reasons the uncondensed solvent from
the condensers (46,48, 60) is led to a contact cooler (64) in the absorption section, which is sprayed
with cooling tower water counter-currently. Thereafter the uncondensed vapours are passed through an
absorber (66) packed with pall rings sprayed counter-currently with spindle oil which absorbs the
solvent. The operating temperature of the absorber is25 C and the pressure is 0.985bar (absolute). The
solvent gets absorbed in the spindle oil and the spindle oil is then passed through an evaporator (68)
maintained at90 C. Absorbed solvent from the spindle oil is thus released and taken to the condenser
>;Desc/Clms Page number 11;
(60) where it is condensed and combined with solvent recovered from other sections.
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Uncondensed gases are removed from the absorption section through a vent.
The preferred parameters for the present invention are shown in Table1. These parameters include all
the equipment in the solvent extraction plant. Table 2 shows the range of parameters for the present
invention.
The solvent used in this present invention is hexane (extraction grade) suitable for food industry and
commercially available from Shell Chemicals. Hexane (extraction grade) is manufactured to the high
standards required by the oil-seed extraction industry. Its composition complies with FAO/WHO and
UK MAFF specifications for polycylic aromatics and heavy metals. It does not contain detectable
quantities of chlorinated compounds.
The invention being thus described, it will be obvious that the same may be varied in many ways. Such
variations are not be regarded as a departure from the spirit and scope of the invention, and all such
modifications as would be obvious to one skilled in the art are intended to be included within the scope
of the following claims.
>;Desc/Clms Page number 12;
TABLE 1 : PREFERRED PARAMETERS FOR THE PRESENT INVENTION
EMI12.1
Section ! Item Vessel Steam Coo (in Water Tein
Temp Pressure Pressure deg C bar (abs) barg ! n put A Preparatory Section :
1. feed-Wet Palm Fibre 45 e : 2. FibreCooker/Dryer Cto) 105 0. 995
3. Fibre Cooker (steam) 184-10
Open Steam 107 0. 3
4. Fibre Cooler C 12) 55 0. 995 8. Main Plant :
1. Extractor C i-, t 50 0. 995 -Circulation Heaters steam 159-5
2. De-Solventiser (Fibre outlet) 3 9) 110 0. 995 10
De-Solventiser (Steam) 184-10
Open Steam 107 0. 3
3. D. T. Vapour Scrubber (-4-0') 90 0. 9954 Distillation Section a) Miscelta Tank C 3 Z 55 0. 995 b) Economiser C. .)
Shelf side : - Vapour inlet 105 0. 995 - Vapour outlet 70 0. 990
Tube side : - Miscella inlet 55 2. 5 -Miscelia outlet 80 2. 2 c) I st Miscella Heater C 50
Shell side : - Steam 159-5
Tube side : - Misoetta inlet 80 2. 2- - Miscella outlet 95 2. 0 d) 1st Miscelta Evaporator CS 95 0. 600 e)
2nd Miscella Heater C55)
Shelf side : - Steam t59-5-5
Tube side : - Misceftainfet 95 0. 600 - MisceAa outlet 110 0. 400
0 2nd MisceKa Evaporator (56) 110 0. 400, g) Final Oil Stripper C69) 115 0. 130
Steam Limpets 184-10
>;Desc/Clms Page number 13;
CONTINUATION OF TABLE 1
EMI13.1
~ Section t Item Vessel Steam Cooling Water Temp
Temp Pressure Pressure de C ~ deg C bartabs) barg. In Out 5. Condesation Section a) Prime
Condensor-1
Shell side :
Vapours inlet 95 0. 130
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Tube side :
Cooling Water b) Second Condensor-2 C4-9')
Shell side :
Vapours inlet 85 0. 400
Tube side : cooling Water c) DexCondenso (-3 Coo)
Shell side :
Vapours inlet
Tube side :
Cooling Water a) Receiver >; 40 0. 260.
6. Recuperation Section : a) Contact Cooler (64) 34 0. 990-30 33 b) Atisorber 25 0. 985. c) Evaporatoroil outlet 90 0. 400
Evaporator Limpet heatef 159-5
>;Desc/Clms Page number 14;
TABLE 2: RANGE OF PARAMETERS FOR THE PRESENT INVENTION
EMI14.1
~ Sectlon {Rem Vessel Steam Cooling Water Temp
Temp Pressure Pressure deg C bar (abs) barg In Out
A. Preparatory Section :
1. Feed-Wet Palm Fibre 40-50
2. Fibre Cooker/Dryer Cto) 100-110 0. 993-0. 997
3. Fibre Cooker (steam) 175-184 8-t0
Open Steam 105-115 02-0. 5
4. Fibre Cooler C s ? 5040 0. 993-0. 997
B. Main Plant :
1. Extrador Cl4, toO) 45-55 0. 993-0. 997 - Circulation Heaters steam 152-159-4-5-2. De-Solventiser (Fibre outlet) CX8 ? 100-110 0. 993-0. 997
De-Solventiser (Jacket Steam) 17o184 & 10
Open Steam 105-115 0. 2-0. 5
3. D. T. Vapour Scrubber C4o) 85-95 0. 993-0. 997
4 Distillation Section a) Miscella Tank C 3 Z7 50-55 0. 993-0. 997 b) Economiser C4-L)
Shelf side :
Vapour inlet 100-110 0. 993-0. 997 - Vapour outlet 65-75 0. 988-0. 992
Tube side : -Miscella inlet 5040 2. 3-2. 7 - Miscella outlet. 75-85 2. 0-2. 4--- c) 1 st Miscelta Heater
CSO)
Shelf side : - Steam 152-159-4-5
Tube side : - Misceffainfet 75-85 2. 0-2. 4
Miscelia outlet 90-100 1. 8-2. 2 d) 1st Miscella Evaporator CS4) 90 100 0. 575-0. 625 e)
2ndMiscelbHeater CSX)
Shell side : - Steam 152-159 4-5
Tube side : - ; scelia Wet 90 100 0. 550-0. 650- -Miscei'laodet 10s110 0. 375-0. 425 f) 2nd Misceib
Evaporator C56) 10s110 0. 375-0. 425 g) FinalOUStripper 150) lDS-115 0. 1000. 150 -Steam Limpets
175-184-8-10 I I
>;Desc/Clms Page number 15;
CONTINUATION OF TABLE2
EMI15.1
Section ltem Vessel Steam Cooffng Water Temp
Temp Pressure Pressure deg C deg C bar (abs) barg In Out
5. Condesation Section a) PrirneCondensor-1 C44,)
Shelf side :
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Vapours inlet 90-100 0. 10o0. 1S0
Tube side :
Cooling Water. 2 S3 2. 29-31 34-36 b) Second Condensor-2 C+ia
Shell side :
Vapours inlet 80 90 0. 375-0. 425
Tube side :
Cooling Water-2. 8-32-29-31 34-36 c) DexCondensor-3 C6O)
Shelf side :
Vapours inlet 65-75 0. 988-0. 992
Tube side :
Cooling Water 2 S-3. 2. 29-31 34-36 a) Receiver (6z) 40-45 0. 240-0. 280 6. Recuperation Section : a)
Contact Cooler 33-35 0. 988-0. 992 29-31 32-33 b) Absorber c) 23-26 0. 983-0. 987 c) Evaporator-oiJ
outlet C6g') 85-95 0. 375-0. 425
Evaporator Limpet heater 152-159-4-5-. f I IData supplied from the esp@cenet database - Worldwide
Claims:
Claims of WO2004061059
CLAIMS1. A process to extract remaining oil from mesocarp fibres of oil palm after initial extraction
of oil characterised in that the process includes the steps of i) reducing the moisture content of the
mesocarp fibres to below 10% by weight; ii) subjecting the mesocarp fibres from step (i) to a solvent in
an enclosed chamber (20,108) at a temperature between 45 to55 C to yield a miscella and deoiled
mesocarp fibres; iii) removing the miscella containing oil, solvent and moisture from step (ii); iv)
removing the solvent from the deoiled mesocarp fibres produced in step (ii); v) separating oil, solvent
and moisture respectively from the miscella in step (iii); and wherein the deoiled mesocarp fibres
contain bound moisture and residual oil.
2. A process to extract remaining oil from mesocarp fibres of oil palm as claimed in claim 1 wherein in
step (i) the mesocarp fibres are subjected to a temperature between100 C to110 C and a pressure of
0.933 to 0.997bar absolute.
3. A process to extract remaining oil from mesocarp fibres of oil palm as claimed in claims 1 and 2
wherein the mesocarp fibres are cooled to a temperature between50 C-60 C before introduction into the
enclosed chamber (20,108).
>;Desc/Clms Page number 17;
4. A process to extract remaining oil from mesocarp fibres of oil palm as claimed in claim 1 wherein in
step (ii) the mesocarp fibres are moved in a forward linear direction on a reticulated moving conveyor
(18) and are subjected to a plurality of continous sprays of solvent, and mixtures of solvent and palm
oil in a counter-current manner wherein the said palm oil is that which is extracted by the solvent.
5. A process to extract remaining oil from mesocarp fibres of oil palm as claimed in claim 4 wherein
sprayer (22) at forwardmost position sprays solvent and sprayer (22) at the most distal position sprays a
mixture of solvent and palm oil and the sprayers (22) from the forwardmost position to distal position
spray an increasing ratio of oil to solvent.
6. A process to extract remaining oil from mesocarp fibres of oil palm as claimed in claim 1 wherein in
step (ii) the mesocarp fibres are moved in a forward rotary direction in a plurality of rotary cells and are
subjected to a plurality of continous sprays of solvent, mixtures of solvent and palm oil in a countercurrent manner wherein the said palm oil is that is extracted by the solvent.
310/321
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7. A process to extract remaining oil from mesocarp fibres of oil palm as claimed in claim 6 wherein
during the forward rotary movement of cell compartments filled with fibres, the fibres are washed
continuously with miscella of decreasing concentration of oil and finally with solvent in a countercurrent manner by means of a plurality of sprayers (110).
>;Desc/Clms Page number 18;
8. A process to extract remaining oil from mesocarp fibres of oil palm as claimed in claim 1 wherein in
step (iv) the deoiled mesocarp fibres are moved forward in an agitation chamber (38) wherein the
solvent in the deoiled mesocarp fibres is vapourised while simultaneously the temperature within the
chamber (38) is maintained at100 C to110 C and are subjected to counter flow of open steam of107 C
at 0.3barg.
9. A process to extract remaining oil from mesocarp fibres of oil palm as claimed in claims 1 to 8
wherein the solvent is food grade hexane.
10. An assembly of apparatus to extract remaining oil from mesocarp fibres of oil palm after the initial
extraction of oil characterised in that the assembly of apparatus includes i) an apparatus to reduce
moisture content of the mesocarp fibres from
35% to a maximum of 10 % by weight; ii) an extractor comprising of an enclosed chamber (20,108),
either an endless reticulate conveyor (18), or a plurality of rotary cells and a plurality of troughs,
heaters, pumps and sprayers; iii) an enclosed agitation chamber (38) with an upward flow of open
steam at107 C at 0.3barg and a plurality of steam jackets within and outside the enclosed chamber
where the steam is at a temperature of between175 C to184 C and a pressure of 8 to 10 barg.
11. An assembly of apparatus as claimed in claim 10 wherein the apparatus to reduce moisture content
of the mesocarp fibres includes a chamber (10) with a
>;Desc/Clms Page number 19;
plurality of internal and external steam jackets and wherein the steam within the steam jackets is
between 175 C-184 C and at a pressure of8-lObarg.
12. An apparatus as claimed in claim 1 wherein the solvent is food grade hexane.
13. Palm oil extracted utilizing the process as claimed in any of the claims1 to 8.
14. Palm oil extracted from mesocarp fibres wherein the content of hexane in the extracted palm oil is
below 0.1 % by weight.
15. Mesocarp fibres from oil palm produced utilizing the process as claimed in any of the claims 1 to 8
wherein the remaining oil content of the fibres is below
0.5% by weight.
16. Mesocarp fibres from oil palm utilizing the assembly of apparatus as claimed in any of the claims
10 to 12 wherein the remaining oil content of the fibres is below 0.5% by weight.Data supplied from
the esp@cenet database - Worldwide
311/321
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85. WO9845018
- 15/10/1998
PROCESS FOR SORBING LIQUIDS USING TROPICAL FIBERS
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=WO9845018
Inventor(s):
HONDROULIS DIMITRIOS GEORGE (US); KINGHAM NEVILLE WILLIAM
(US); BERGQUIST-KINGHAM KATHERINE T (US)
Applicant(s):
FYBX ENVIRONMENTAL INC (US)
IP Class 4 Digits: C02F; B01D
IP Class:C02F1/68; B01D15/00; C02F1/28; C02F1/40
E Class: C02F1/68C
Application Number:
WO1998US06697 (19980403)
Priority Number: US19970832753 (19970404)
Family: WO9845018
Equivalent:
EP0973594; US6027652
Cited Document(s):
US4172039; US4072794; US4925343
Abstract:
Abstract of WO9845018
A process is described for using tropical fibers to recover spilled oil, gasoline, kerosene, hydrocarbons,
pentachlorophenol, creosote or other hazardous liquids from land or water. The sorbent fiber material is
produced from agricultural byproducts from cultivation of banana, plantain, cavendish plant, pineapple,
coconut, palm, or other tropical fruit bearing plants. The sorbent fibers are produced by separating the
raw plant materials; washing the separated fibers in a solution of 1 % alum; pressing the fibers to
extract liquids and natural juices; further separating the fibers by beating or agitating; and drying the
fibers. The sorbent fibers have a water and natural liquid content of less than 10 % by weight and may
be applied to the surface or periphery of an oil or chemical spill, whereupon they will sorb the oil or
chemical. Once the oil or chemical is sorbed the fibers may be collected and the oil or chemical may be
partially recovered by compressing the fibers. The fibers may be disposed of by landfilling or may be
thermally treated. When thermally treated in a boiler or furnace, the liquid laden fibers may also be a
valuable source of fuel.Description:
Description of WO9845018
PROCESS FOR SORBING LIQUIDS USING TROPICAL FIBERS
BACKGROUND OF THE INVENTION
Technical Field
This invention relates generally to the use of a sorbent material to sorb liquids. Particularly, this
invention relates to the use of processed tropical fibers, such as banana, plantain, cavendish plant,
pineapple, coconut, and palm, to recover spilled oil, gasoline, kerosene, solvents, hydrocarbons,
pentachlorophenol (PCP), creosote or other liquids.
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Descrintion of the Prior Art
Spills of oil, solvents and hazardous materials are a continuing problem having serious environmental
consequences, including damage to the oceans, beaches, inland rivers, streams and creeks, as well as
detrimental effects upon the health of wildlife and humans. The need for oil and chemical products has
created consistent growth in the chemical industry, including the transport and manufacturing of these
compounds, resulting in increasing environmental problems associated with spills, accidents and
improper disposal.
Sorbent materials, including both materials that absorb and materials that adsorb, have been used for
many years in the cleanup of oil and hazardous materials by private industry and the federal
government. Sorbent clay materials are currently the material of choice for absorbing or recovering oil
or other hazardous chemicals on land. In industrial applications, these materials have the
disadvantages of low sorbent capacity and a high density which make them both heavy and difficult to
transport. Additionally, the abrasiveness and friability of these products may lead to increased wear of
nearby industrial machinery. These clay based sorbents are not biodegradable and, therefore, pose an
additional environmental problem because they must be disposed of in the limited space available in
landfills. Peat, diatomaceous earth and vermiculite are sometimes used as alternatives to the clay based
sorbents.
The primary sorbents used in remediation of spills of oil or other hazardous substances on water
consist of synthetic materials such as polypropylene, which is currently the product of choice for
industry and remediation specialists. However, since polypropylene is itself a synthetic chemical, its
production handling can be the source of other environmental problems. Additionally, because these
synthetic sorbents are not biodegradable and currently must be disposed of in landfills, they increase
the load on the limited available landfill capacity. Therefore, a need exists for an efficient natural
sorbent material which is not a source of environmental problems.
One process for alleviating the environmental problems associated with the production of oil or
chemical sorbent materials is to use a sorbent system based on natural fibers.
Over the last several decades, a wide variety of treated natural fibers have been used as sorbents of
hazardous materials. These have included tree bark, peat, wood fiber, dealginate kelp, powdered lily,
kenaf cores, puffed cereals, and a variety of other cellulosic materials. Each of these fiber types has
disadvantages which have prevented them from becoming the material of choice for remediation of oil
and chemical spills on land or in water.
The primary disadvantage of most of these fiber types is that they are naturally hydrophilic and,
therefore, tend to sorb large quantities of water. Sorption of water increases the weight of these
materials and can seriously decrease their ability to sorb the oil or hazardous chemical which these
materials are intended to recover. It is possible to reduce or eliminate the tendency of some of these
materials to sorb water by treatment with chemical additives to increase their hydrophobicity.
For example, in U.S. patent No. 5,021,390, Hatton teaches a composition for sorbing liquids consisting
of various fibrous plant materials treated with the waterproofing agent sodium methyl silicate. In U.S.
patent No. 5,492,881, Diamond teaches a sorbent system using finely ground cellulose treated with a
hydrophobic agent such as paraffin, other waxes, polyvinyl alcohol, hydroxyethyl cellulose or the like.
These additives add to the manufacturing expense of the sorbent and may themselves be the source of
further harm to the environment.
Another disadvantage of previously disclosed natural fiber based sorbents is that most are generally
only capable of sorbing 5-10 times their mass in oil or other chemicals.
Additionally, most of these natural fiber compositions have a tendency to sink as they become
saturated with oil, water or other chemicals, making recovery of these materials and sorbed chemical
from a body of water extremely difficult or impossible.
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Several of the previously disclosed fiber compositions are not readily biodegradable which poses a
potential environmental problem since these fibers will not easily degrade when disposed of in a
landfill. For example, in U.S. patent No.
3,791,990, Fischer et al. teach an oil sorbent material composed of peat fibers dried to less than 10% by
weight water.
These fibers are believed not to be biodegradable, which, although beneficial from the stand point of
reducing leaching of the liquids, results in a long lifetime in landfills.
Overuse of the limited landfill capacity is a major environmental problem, and it is therefore desirable
to provide a sorbent material which is readily biodegradable after use and recovery of the oil, solvent or
other liquids.
Presently, banana stalks, plantain stalks, cavendish plant stalks, pineapple crowns, palm, palmetto and
coconut fronds, and a variety of other tropical plant portions are thought of as waste agricultural
byproducts in the countries in which they are produced. Currently these byproducts are disposed of in
landfills, where they can attract insects and contribute to landfill capacity problems. Additionally, they
may be discarded into rivers, where they oxidize and can cause potential environmental problems. In
other instances, the byproducts are left on the ground to act as a natural fertilizer.
SUMMARY OF THE INVENTION
The present invention recognizes and addresses the abovediscussed shortcomings and disadvantages,
as well as others, of prior sorbent materials. In accordance with the teachings of the present invention, a
novel process for using processed tropical fibers in the remediation of spills of oil or other liquids is
disclosed.
More specifically, the present invention comprises a process for sorption of spilled oil, kerosene,
gasoline, solvents, hydrocarbons, PCP, creosote or other liquids. This process includes the general
steps of conversion of the raw tropical plant materials to useful sorbent fibers; application of the
sorbent fibers to a body of spilled liquid; collection or recovery of the fibers; and disposal of the fibers
either by thermal treatment or landfilling. Additionally, a step may be included wherein the oil, solvent
or other hazardous material is extracted from the fibers before disposal.
The sorbent fibers are produced from tropical fibers, such as banana, plantain or cavendish plant stalks,
pineapple crowns, coconut palm or palmetto fronds, or the pinzote (fruit bearing body) of palm. In
general, these plant materials have a high content of water and natural latex, of which a substantial
portion must be removed to produce useful sorbent fibers. In order to convert them into sorbent fibers,
the raw plant materials are cut, ground, shredded or otherwise separated into a mass of separated fibers;
the fibers are washed; the fibers are pressed to extract natural liquids; the fibers are further separated by
beating or agitating; and the fibers are dried. This process may be fully or partially automated.
In a preferred embodiment, the processed tropical fibers are processed to have a final water and natural
liquid content of less than 10% by weight. Approximately 50% of the naturally occurring latex is also
removed by this processing. Once dried to this point the processed fibers become substantially
hydrophobic, without requiring the addition of additives.
The processed tropical fibers may be applied to the liquid on water or land in a variety of forms,
including as loose fibers or packaged in booms, pillows, socks, dikes, mats, pads and the like. When
the material is applied to a waterborne spill it will sorb the oil, solvent or hazardous chemical. The
hydrophobic nature of the fibers will cause them to aggregate, facilitating their recovery. If the fibers
have been applied in packaged form, then it is a simple matter to recover the packages.
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After recovery of the fibers, the oil or other liquid may be recovered from the fibers by compressing
the collected fiber mass. The fibers may then be simply disposed of in a landfill since they are
biodegradable and help reduce leaching of the sorbed liquids. Alternately, the fibers can be easily
disposed of by thermal treatment and, in fact, may serve as a valuable source of fuel since they have a
high BTU content and produce a low amount of ash residue.
The loose sorbent fibers are also useful in the stabilization or solidification of chemical contaminants
in contaminated soils, sludges or other semi-solids. In this application, the fibers are mixed directly into
the soil or may be mixed with cement-based stabilization agents to reduce the leachability of
contaminants from solidified soil.
The present invention provides several advantages over the prior art processes of sorbing oil or other
hazardous chemicals. Of primary importance, the tropical fiber sorbent material is biodegradable and
not harmful to the environment either in its production, use or disposal. Furthermore, use of this
material provides a use for tropical agricultural byproducts which would otherwise be disposed of as
waste material in potentially environmentally harmful ways. The tropical fiber material is also
relatively inexpensive since it may be produced from plentiful agricultural byproducts which are
currently largely unused. The tropical fiber material is neither abrasive nor friable, and therefore is not
a source of wear for industrial machinery. The tropical fiber sorbent material will also sorb up to 15
times its own weight in petroleum products, does not significantly sorb water, will float indefinitely
and will aggregate on open water making recovery both simple and inexpensive.
The aforementioned and other aspects of the present invention are described in the detailed description
and attached illustrations which follow.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG 1 is a diagram illustrating several processes whereby the tropical fiber sorbent product may be
applied to a body of liquid.
FIG 2 is a diagram illustrating the steps used in processing the raw tropical plant materials into useful
sorbent fibers.
FIG 3 is a diagram illustrating the steps for remediation of a spilled liquid.
FIG 4 is a diagram illustrating the steps used in remediation and recovery of a spilled liquid.
FIG 5 is a diagram illustrating both the steps used to produce the fibers and the steps for remediation
and recovery of a spilled liquid.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENT
Referring now to the figures in which like reference numerals indicate like or corresponding features,
FIG 1 shows several processes whereby the tropical fiber sorbent product may be applied to a body of
liquid 100, including as loose fiber 110, booms 120, socks 130, dikes 140, pillows 150, mats 160 or
pads 170.
The critical element in the present process is the use of dewatered, partially delatexed sorbent fibers
from tropical plants. These sorbent fibers 110 may be from any of a variety of tropical agricultural byproducts including, but not limited to, banana stalks, plantain stalks, cavendish plant stalks, pineapple
crowns, palm fronds and pinzote, palmetto fronds and coconut fronds. The raw tropical plant materials
fibers may be processed in any of a variety of ways to convert them into sorbent fibers, including, but
not limited to the subsequently described processes.
In the preferred embodiment, the sorbent fibers 110 are produced from banana, plantain or cavendish
plant stalks, pineapple crowns or other similar high liquid content plant materials. These materials are
byproducts of the cultivation of these crops, and are produced in large quantities on a yearly basis since
315/321
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these plants generally produce fruit only one time before they are harvested and cut back. The stalks or
crowns may be transported to the processing site after harvesting. In general, these plant materials have
a water and natural latex content of approximately 80% by weight.
Referring to FIG 2 and FIGS, once at the processing site, the raw plant materials are subjected to an
initial reducing step 210 wherein they are cut, ground, shredded or otherwise converted into a mass of
separated fibers; the fibers are subjected to a washing step 220 wherein they are washed in a solution of
1% alum; the fibers are subjected to a pressing step 230 wherein they are pressed to extract liquids and
natural juices; and the fibers are then subjected to a drying step 240. This procedure may be automated.
In the preferred embodiment the raw plant materials are first reduced 210 in a roller with blades that
draws the stalks or crowns into a series of rotating" steel knives or blades.
These blades cut the stalks into fibers ranging fromlitt to111 in length and serve to separate the fibers.
The separated fibers are then propelled through the neck of the grinder into the awaiting washer.
The fibers are washed 220 in a solution of 1% alum in water for a period ranging from 15 min. to 45
min. During this wash step 220 the fibers are constantly subjected to the action of bladed paddles
which act to agitate the fibers and further separate them. The fibers are then pumped out of the washer
by a common sewer pump which also serves to further separate the fibers. The fibers are then deposited
onto a steel mesh screen to separate the water from the fibers. Excess water can then be recycled back
into the washing system.
This washing step 220 is of critical importance in the fiber preparation process. Washing the raw plant
material in a mild alum (aluminum sulfate) solution results in the extraction of a substantial portion of
the latex and other resinous natural juices found in the stalk. Removal of a portion of the latex and
other plant natural juices is necessary to obtain useable fibers which are not initially aggregated into a
relatively non-sorbent mass upon drying, however, it is also necessary that a portion of these materials
be retained to contribute to the hydrophobicity of the fiber product. It is likewise important that the
wash step not be carried out by boiling at high temperature, since this can lead to degradation of the
fibers.
After washing, the fibers are subjected to a pressing step 230 for removal of a significant portion of the
remaining water, latex and other natural juices. The press exerts a high tonnage, and may consist of a
hydraulic press, a screw press or a belt press. The resulting compressed fiber mass has a water and
natural liquid content or approximately 25-30% by weight.
It is important to note that this relatively low liquid content is easily achieved by performing the
pressing step 230 after the initial separating 210 and washing 220 steps and drying step 240. This
results in a reduction in the time and energy required to dry the fibers and a substantial improvement of
the workability of the fibers during the following steps.
After pressing 230, the fibers are subjected to a drying step 240 in which industrial strength dryer
circulates hot air from an incinerator through the fibers to dry them to a liquid content of approximately
1-15%. Once dry, the fibers may optionally be subjected to further reducing steps to pulverize the
fibers to1/811 toN in length. The fibers may then be baled by a conventional hay baler or bagged for
transport and storage.
One skilled in the art will recognize that many variations of this embodiment are practical including
conversion of this system to a continuous flow system wherein raw plant material is constantly being
reduced to fibers and washed followed by pressing in a screw press or other means to constantly
squeeze out moisture, and by further continuous flow separating steps similar to those previously
described.
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เกี่ยวกับ น้ามันปาล์ ม สกัด (Palm oil Extract)
In an alternate embodiment, fibers may be prepared from fronds and stems or pinzote from palm,
palmetto, and coconut, which are again common agricultural byproducts in certain tropical countries.
These plant materials may be converted into sorbent fibers by cutting, grinding or otherwise reducing
the raw plant material into a fibrous mass, separating out the fibers from the non-fibrous materials, and
packaging the fibers.
Referring now to FIG 3, FIG 4 and FIG 5, the sorbent tropical fiber material may be applied 250
directly to the surface of an oil spill on land or water by dropping the loose sorbent fibers 110 over the
body of liquid 100. Alternatively, the loose fibers 110 may be applied 250 by being blown out over the
spill by a blower such as those used to blow fibrous insulation into a wall or ceiling. If the loose fibers
110 are used on land, they may be swept up and collected 270 once they have sorbed the spilled liquid.
Since the loose fibers 110 are naturally hydrophobic they will sorb hydrophobic liquids and
additionally will tend to aggregate if dispersed over the surface of a body of water.
Once aggregated, the loose fibers 110 will float indefinitely and may be easily collected 270 from the
body of water.
The tropical fiber material may be packaged into a wide variety of forms including booms 120, socks
130, dikes 140, pillows 150 and the like. Generally this is accomplished by filling a porous package
with a quantity of the loose tropical fiber material 110. The packaging material may be made of
polypropylene, nylon, cotton or other similar materials, and ideally should be permeable to oil while
excluding water.
Booms 120, as commonly recognized in the art, are large sausage-shaped containers which are stitched
on one side to contain the fiber material and may be attached end to end to contain a waterborne spill of
oil or other hazardous liquid.
Booms 120 usually range in size from a 4" to 8" diameter and form 3' to 6' in length. Socks 130 and
dikes 140 are smaller than booms, but similar in structure. Pillows 150 are sealed pouches containing
the loose fiber and can be any shape.
Typically, the booms 120 will be used on open water by joining together the booms to form a ring
encircling the spilled liquid 100. Alternatively, the booms 120 may be strung together just offshore to
sorb as much of the oil or other hazardous liquid 100 as possible before it can be deposited on the
beach or shoreline where it is likely to cause the most significant environmental damage. The socks
130, dikes 140 and pillows 150 may be used in a similar fashion, or may be placed directly on the site
of a smaller body of liquid 100 to sorb the liquid.
Alternatively, mats 160 and pads 170 made of compressed fiber with no outer covering may be used.
In a preferred embodiment, these mats 160 have a thickness of1S -M inch and may range in size from
2' x 2' to 4' x 4'. These mats 160 or pads 170 may be used to sorb spilled oil, solvents or other
hazardous chemicals on land by simply bringing the packaged fibers into contact with the spill and
allowing sorption to occur. The fiber mats 160 and pads 170 are particularly useful for sorbing spills of
oil and other automotive liquids from a garage floor or driveway, and may be placed under a work area
in anticipation of spills occurring during automotive or industrial repairs. When the packaged fibers,
mats 160 or pads 170 are saturated with liquid, or the user decides enough of the liquid has been sorbed
the packages, mats or pads may be collected and, if necessary, replaced with new packages, mats or
pads.
The fibers 110 may also be applied to a contaminated liquid as a filtration medium through which the
contaminated liquid is passed. When used as a filter, the fibers may be included in-line in a forced flow
fluid system, wherein the contaminated liquid is pumped through the filtration material to more quickly
treat high liquid volumes.
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เกี่ยวกับ น้ามันปาล์ ม สกัด (Palm oil Extract)
It is possible to include a recovery step 280 wherein a significant portion of a spilled liquid may be
recovered after sorption by the tropical fiber material by pressing the fibers to squeeze out the liquid.
The fibers may then be either disposed 290 of or reused at the owners discretion.
Alternatively, if the liquid is combustible, the disposal step 290 may include thermally treating (e.g.
incinerating) the fibers. Fibers saturated with combustible liquid may also serve as a valuable fuel
source if thermally treated by burning in an appropriate furnace or boiler. For less hazardous liquids
such as vegetable oil or animal waste the disposal step 290 may include disposal of the fibers in a
landfill.
The loose sorbent fibers 110 are also useful in the stabilization or solidification of chemical
contaminants in contaminated soil, sludge, sand, clay, gravel, dust or other semi-solids. In this
application, the loose fibers 110 are mixed directly with the into the semi-solid or may be mixed with
cement-based stabilization agents to reduce the leachability of contaminants from solidified soil. It is
not necessary to recover the loose fibers 110 in this application as they may serve to reduce
leachability of the chemicals until either the fibers or chemicals degrade over time.
When mixed with a semisolid, the loose sorbent fibers 110 also provide a source of organic material to
encourage the growth of bacteria and other microscopic organisms, thereby enhancing the
biodegradation of the contaminating liquid.
Additionally, since bacteria and other microscopic organisms are initially present in the fibers 110, the
fibers 110 may serve as a source of organisms to enhance bioremediation of the contaminated liquid.
What has been described above are preferred embodiments of the present invention. It is, of course,
not possible to describe every conceivable combination of methodologies for purposes of describing
the present invention. However, one of ordinary skill in the art will recognize that any further
combinations, permutations and modifications of the present invention are possible. Therefore, all such
possible combinations, permutations and modifications are to be included within the scope of the
claimed invention, as defined by the claims below.Data supplied from the esp@cenet database Worldwide
Claims:
Claims of WO9845018
CLAIMS
1. A process for sorbing a liquid comprising the steps of:
applying to a body containing the liquid a sorbent composition formed of a plurality of partially
deliquefied tropical fibers; and
sorbing the liquid from the body with said sorbent composition.
2. The process of claim 1, wherein the sorbent composition consists of a plurality of processed tropical
fibers with a water and natural liquid composition not greater than 30% by weight.
3. The process of claim 1, wherein the sorbent composition consists of a plurality of processed tropical
fibers with a water composition not greater than 10% by weight.
4. The process of claim 1, wherein said plurality of partially deliquefied tropical fibers are selected
from the group consisting of: banana, plantain, Cavendish plant, pineapple, coconut, palmetto and palm.
5. The process of claim 1, further comprising the initial step of packaging the sorbent composition.
6. The process of claim 5, wherein said packaging step includes packaging the sorbent composition
into porous containers.
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เกี่ยวกับ น้ามันปาล์ ม สกัด (Palm oil Extract)
7. The process of claim 5, wherein said packaging step includes packaging the sorbent composition as
loose fibers.
8. The process of claim 1, further comprising the initial step of compressing the sorbent composition to
a solid mass.
9. The process of claim 1, wherein said applying step includes the step of placing the sorbent
composition into contact with the liquid containing body at the periphery of the liquid containing body.
10. The process of claim 1, wherein said applying step includes the step of placing the sorbent
composition into contact with an interior surface of said body of liquid.
11. The process of claim 1, wherein said applying step includes the step of applying the sorbent
composition to a body of contaminated liquid on a solid surface.
12. The process of claim 1, wherein said applying step includes the step of applying the sorbent
composition to a body of contaminating liquid floating in a body of water.
13. The process of claim 1, wherein said applying step includes the step of applying the sorbent
composition to a semi-solid body.
14. The process of claim 13, wherein the semi-solid body is selected from the group consisting of: soil,
sand, sludge, clay, gravel and dust.
15. The process of claim 13, further comprising the step of allowing the sorbent composition to
biodegrade while in contact with the semi-solid body to enhance biodegradation of the liquid.
16. The process of claim 1, wherein said applying step includes the step of applying the sorbent
composition as a filtration medium through which the liquid containing body is passed.
17. The process of claim 1, further comprising the step of collecting the sorbent composition following
sorption of the liquid.
18. The process of claim 17, further comprising the step of disposing of the sorbent composition.
19. The process of claim 18, wherein said disposing step includes the step of disposing of the sorbent
composition in a landfill.
20. The process of claim 18, wherein said disposing step includes the step of disposing of the sorbent
composition by thermal treatment.
21. The process of claim 20, wherein the sorbent composition is thermally treated as fuel in a furnace.
22. The process of claim 20, wherein the sorbent composition is thermally treated as fuel in a power
generating facility.
23. The process of claim 1, further comprising the step of recovering the liquid.
24. The process of claim 23, wherein said liquid recovering step includes the step of compressing the
sorbent composition.
25. A process for sorbing a liquid using tropical plant material, said process comprising the steps of:
reducing the tropical plant materials to a plurality of separated fiber portions;
washing the plurality of separated fiber portions;
pressing the plurality of separated fiber portions to remove natural liquids;
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เกี่ยวกับ น้ามันปาล์ ม สกัด (Palm oil Extract)
drying the plurality of separated fiber portions to form a sorbent composition;
applying to a body containing the liquid the sorbent composition; and
sorbing the liquid from the body with the sorbent composition.
26. The process of claim 25, further comprising the step of packaging the sorbent composition.
27. The process of claim 25, further comprising the step of compressing the sorbent composition into a
solid mass subsequent to said the drying step.
28. The process of claim 25, further comprising the step of collecting the sorbent composition
subsequent to said sorbing step.
29. The process of claim 25, further comprising the step of recovering the liquid subsequent to said
sorbing step, wherein said recovering step includes the step of compressing the sorbent composition.
30. The process of claim 25, further comprising the step of disposing of the sorbent composition by
thermal treatment subsequent to said sorbing step.Data supplied from the esp@cenet database Worldwide
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