Extraction of organic materials from Green River, Wyoming oil shale
by Raymond Clayton Suiter
A THESIS Submitted to the Graduate Faculty in Partial Fulfillment of the Requirements for the Degree
of Master of Science in Chemical Engineering
Montana State University
© Copyright by Raymond Clayton Suiter (1959)
Abstract:
A study was made of the possibility of recovering worthwhile organic material from Westvaco's Green.
River, Wyoming oil shale.
Alkaline extractions of oil shale In the presence of potassium permanganate and of previously air
oxidized oil shale were both studied.
A sealed Parr reaction apparatus was used to make the extractions. The aim was to extract the organic
material from the shale with alkaline solutions. In the alkaline-permanganate extractions, the organic
material in the shale was. oxidized with potassium permanganate during the extractions. In the air
oxidation studies, the shale was oxidized with air previous to the alkaline extractions. Air oxidation
would be used in a commercial operation.
An investigation was made to determine how much of the organic, material in the shale could be
recovered by the alkaline-permanganate extraction and subsequent treatment of the resulting extraction
liquors. The recovery of the organic material was done in two steps. The first step recovered the acid
insoluble material merely by acidifying the extract liquors. The second step recovered the acid soluble
material by extracting it from the liquors with acetone. Approximately 6.7 per cent of the shale was
recovered as organic material. This recovery corresponded to 70-80 per pent of the organic material
available in the shale. A series of statistically designed runs was made to determine the best conditions
for obtaining optimum yields of organic material from the shale.
Air oxidation studies were made using a heated glass air oxidation column, The oxidized shale was
extracted with alkaline solutions and the liquors were treated for recovery of the organic materials they,
contained.
In these air oxidation runs, about 10 to 20 percent of the available organic, material was recovered.
Considerable work was done on identifying the extraction products obtained. Most of the identification
work was done with the aid. of a Beckman IR-4 infrared spectrophotometer. The products were found
to be essentially,complex organic acids with possible lactone or anhydride structures attached.
However, some crystals which were recovered in the second- step of the analytical procedure were
found to be of an entirely different nature. No definite identification of the crystals could be made with
the available comparison charts. The extraction products were essentially short-chain or. cyclic
compounds with very little aromatics present. E X T R A C T I O N .OF ORGANIC. MATERIALS F R O M GREEN R I V E R * W Y O M I N G OIL SHALE
'
by
R a y m o n d .C. Suiter
A.T H E S I S
Submi t t e d to the Graduate F a c u l t y
1
il
in
P a r tial ,Fulfillment of the Requirements
f o r the D e gree of
Master of Science in C h emical E n g i n e e r i n g
at
M O NTANA ST A T E , C O L L E G E
Ap proved;
Head, Major DepartmGht
■ //
/
C h a i r m a n , E x a m i n i n g Committee
.te D i v ision
Bozeman, M o n t a n a
July,
1959
W
Qjof-
2
-
TABLE OF CONTENTS
A b stract
................................................................
Page
3
I n t r o d u c t i o n ............................................................
4
.....................................................
E q u i pment U s e d
A.
E x t r a c t i o n Apparatus .......................................
B.
A l r - O x l d a t l o n C olumn .......................................
8
8
10
P r ocedure a n d Materials
.
12
.................................................
A.
P r o c edure
1.
Alkaline-Pe r m a n g a n a t e E x t ractions ..................
12
a.
P r e l i m i n a r y R u n s .................................... 12 _
b.
Total Y i e l d S t u d y .................................... 15
c.
Statis t i c a l D e s i g n R u n s ............................. 16
2.
Alr-Ox l d a t l o n R u n s ....................................... I?
B.
M a t e r i a l s ......................................................... 18
Q u alitative Analysis of Products
.....................................
19
D i s c u s s i o n of Results
.............................................
21
A.
Q u antitative Y ields
.....................
. . . . .
21
1.
Total Y i e l d S t u d y ........................
21
2.
A i r - O x i d a t i o n R u n s ....................................... 23
5.
S t atistical D e s i g n R u n s ................................ 23
B.
Qualitative Results
.......................................
25
Bibliography
.........................................................
31
Acknowledgment
.........................................................
32
A p p e n d i x ............................................................
33
138911
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ABS T R A C T
A study was made, of the p o s s i b i l i t y of r e c o v e r i n g w o r t h w h i l e organic
m a t e r i a l from. W e s t v a c o l s G r e e n R i y e r 7 W y o m i n g o il shale *
;;
Alkaline extractions of oil shale i n the pre s e n c e of p o t a s s i u m
peymangana.te and.of p r e v i o u s l y a i r o x i d i z e d . o i l shale we r e bo t h studied.
A se a l e d P a r r r e a c t i o n apparatus was u s e d to make the e x t r a c t i o n s . The
a i m was to extract the organic m a t e r i a l f r o m t h e s h a l e w i t h a l k a l i n e
solutions. -In the alkal i n e ^ p e r m a n g a n a t e e x t r a c t i o n s ^ t h e organic m a t e r i a l
i n the shale was. oxidiz e d . w i t h p o t a s s i u m p e r m a n g a n a t e d u r i n g the-e x t r a c t
tipns. .In the a i r o x i d a t i o n studie s * . t h e s h a l e w a s . o x i d i z e d wi t h air
pr evious to .'the a l k a l i n e extractions. •Air. ox i d a t i o n w o u l d be u s e d in. a
c-ojnmercial operation.
A n invest i g a t i o n was m a d e to.d e termine ho-y m u c h of the o r g a n i c .. '
..material in -the s h a l e couid be r e c o v e r e d b y the a l k a l i n e - p e r m a n g a n a t e
extraptfone. and. s ubsequent treatment of t h e re s u l t i n g e x t r a c t i o n l i q u o r s ,
The recovery, of the organic material, was done i n t w e s t e p s . The first step
r e c o v e r e d the a c i d i n s e l u M e m a t e r i a l merely, by. a c i d i f y i n g the extract
.i i c p i o r s The s e c o n d step r e c o v e r e d the acid soluble, m a t e r i a l -by e x t r a c t i n g
it "from the liquors w i t h acetone.
A p p r o x i m a t e l y 6.7 p e r cent of the s h a l e
w a s . r e c o v e r e d as.organic material.
This r e c o y e r y c o r r e s p o n d e d to 7O-&O
p e r pent of t h e organic m a t e r i a l a v a i l a b l e in -the shale.
A. series of
s t a t i s t i p a l l y designed, r u n e .was m a d e to d e t e rmine t h e best conditions f o r
o b t a ining o p t i m u m y i e l d s .of organic m a t e r i a l f r o m t h e shale.
M r o x i d a t i o n studies y e r e m a d e u s i n g .a h e a t e d glass air o x i d a t i o n
-column, .T h e o x i d i z e d -s h a l e .w a s .e x t r a c t e d w i t h a l kaline s o l u t i o n s a n d the
l i q u o r s .were t r e a t e d . f o r recovery o f the organic m a t erials they.-contained.
.In these air o x i d a t i o n r u n s a b o u t 10 to- 20 per c e n t of the available
organic, m a t e r i a l was recovered.
^
Consi d e r a b l e w o r k was done on i d e n t i f y i n g the extraction, products
obtained, •Most of the i d e n tificati o n w o r k tms done w i t h the aid. of a
. B e c k m a n IR-d infrared-spectrophotometer., -The p r o d u c t s WrCre.f o u n d to be
essentially,complex, organic acids w i t h p o s s i b l e lactone or a n h ydride
structures attached-! However#, s o m e crystals w h i c h were r e c o v e r e d in the
s q c QnU- step of t h e a n a l y t i c a l procedure, w e r e found, to be of a n entirely
di fferent nature. - Np- de f i n i t e iden t i f i c a t i o n of the-crystals could be
m a d e w i t h the a v a i l a b l e comparison, charts.
The e x t r a c t i o n pro d u c t s w e r e
e s s e n t i a l l y s h o r t - c h a i n or. cyclic c o m p o u n d s .w i t h very little aromatics
present.
.I
I
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j
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,;
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I
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_..4 INTRODUCTION.
• In r e cent .years the.W e s t y a c o d i v i s i o n of F o o d M a c h i n e r y a n d - C h e m i c a l
C o rpor a t i o n has b e e n p r o d u c i n g a very, high-grade.soda, a sh f r o m trona—
s o d i u m s esquicarbonate
a mineral, composed.^of hydrous s o d i u m carbonate,
a nd s o d i u m bicarbonate.
Although- t h i s . s o d a . aph w h i c h is p r o d u c e d in
Green'Rl.yer,,-Wyoming is .almost 100 p e r c e n t - s o d i u m carbonate, it contains
v a r y i n g ,amounts of organic i m p u r i t i e s . •The t r o n a lies in, l a r g e m i n e r a l
deposits s e veral ..hundred f e e t - u n d e r the ground.
The trpna deposits are
in a b e d w h i e h ,is encased above and. b e l o w by. two b e d s ,or layers ,of oil?
bearing.,shale.
It.is believed- that the.organic impurities in the soda, ash
are d e rived f r q m these two- beds of shale.
•
I
W a t e r d r a i n i n g t h r o u g h the
.
I
u p per layer of s h a l e has probably,.- leached- a n d washed, out a certain, amount
of organic ,matter-which was
then de p o s i t e d in the -.bed. of trona.
Inyiew
of t h i s W e s t v a c o recently, decided,, that it.might be worthwhile, to.find
out if t h e r e a r e a n y organic,materi a l s
in the shale ■or. in-the . s o d a . a s h
impurities -w h i c h are w o r t h recovering.,
-This i n v e s t i g a t i o n inc l u d e s a
s t udy of recove r i n g . t h e , o r g a n i c m a t e r i a l ,f r o m only the shale-.itself.
-One. p o r t i o n of the w o r k -done, on i d e n t i f y i n g the various organic
m a terials f o u n d in. the. Green River, trona, a n d as impurities in-the variousstages o f t h e W e s t y a p o Soda Ash p r o d u c t i o n was reviewed. (2)
This w o r k ,
•.done by. the Cancer - R e s e a r c h L a b o r a t o r y at t h e U n i y e r s ity. of Utah., in>-dieated t h a t ,t h e organic m a t e r i a l s in the, trona and.the organic,materials
,’
............
1
'
w h i c h a r e i m p u r i t i e s in the- soda ash -production contain:
.
5 ~
a. * ■Monobasic .acids
b. 'Dibasic acids
c. . R o s i n a.cidsd. , Steroids
, I n -addition to. the above •compounds
f o u n d , t o . c o n t a i n small amounts
the- organic', m a t t e r studied-was .also
of u n s a t u r a t e d fatty acids.,.-and indicated
a possibility.of-containing.some s p h i n g o m y e l i n s .
T he a m o u n t of-organic
i m purities p r e s e n t v a r i e d somewhat a t - d i f f e r e n t .stages of the-,soda, a s h
p r o d u c t i o n T h e ,work..done by. the -Cancer R e s e a r c h L a b o r a t o r y was a i m e d at
i d enti f y i n g .any materials in the t r o n a organic m a t e r i a l or t h e soda.ash
impurities w h i c h might be of value to.Tfestvaco.,
Quantitative, d e terminal,
..tions h a v e b e e n deyelpped.'Only,. on t h e steroid f r a c t i o n of the.organic
material.
The-C a n c e r Research-laboratory, f Ounl
I these steroids to be
present, in the ;trona,,. shale,, s o d a ash, -etc ., ■Qhly to. the-.-extent o f a f ew
parts, p e r .milliop.
'
As f o r the other o r g a n i c . c o m p o u n d s , , t h e rosin acids m i g h t - a l s o b e
c o nsi d e r e d for t h e i r e c o n o m i c .v a l u e .. -These acids h a v e b e e n f o u n d t o .b e
very.- s i milar in n a t u r e to. r o s i n acids ,-found, in the -alkaline liquors d e r i v e d
in. pulp and-p a p e r manufacture.
The-monobasic--.and dibasic acids,, m i g h t - a l s o
be. of some -economic, v a l u e .
As a r e s u l t ■o f t h e identi f i c a t i o n w o r k done.-by the C a n c e r R e s e a r c h
Laboratory.and. s i milar w o r k d o n e - o n - o t h e r oil-shales,
t h e Green. R i v e r
s h ale was, suspected, to contain organics q u i t e d i f f e r e n t . f r o m t h e organicm a t e r i a l in m o s t o t h e r o i l-bearing shales.
A n y , d i f f e r e n c e s pro b a b l y
.result f r o m t h e type, of s t r a t a w h i c h s u r r o u n d s the.shale, beds
6
' Since co nsiderable w o r k h a d .already, be e n done on the- identi f i c a t i o n
■ of t h e prganic- m a t e r i a l present, in the natural-shale-, it. was..decided, that
this inves-tigation should include a. study, a i m e d ,at d i s c o v e r i n g wh a t quah-.
.tity a n d what type- of organics could be r e c o v e r e d by ,performing.- different
extractions ,of t h e --oil^shale-.
pounds
If was also decided, that more.- valuable- c o m ­
than, t h o s e already, p r e s e n t m i g h t .'be o b t a i n e d by, cha n g i n g the-nature
o f the-compounds in. the,shale- d u rin g -t h e .extractions.
-It was felt that
this c h ange-might be brought aftout by. o x i d i z i n g the.shale. e i t h e r , before or
during t h e extractions.
.. A, s uryey -of previous w ^ h k done, o n the-, extrac t i o n o f o i l ^ s h a l e .showed
that the Bureau--Qf Mines h a d extrac t e d -Colorado, oil,-shale, with-solutions
.of p o t a s s i u m p e r m a n g a n a t e ,and causffb so d a
(3)..
I n - this work, the i n vesti-*
gators-found, that the alkaline-p.ermanganate-.-extractions c o u l d convert.about.
8 0.p e r cent-of the kerogen* to orga n i c acids ,
A p p r o x i m a t e l y h a l f -of -these
acids were f o u n d to- .be- of h i g h m o l e c u l a r w e i g h t a nd i n s o l u b l e in the a c idic
fied,-extraction s o l u t i o n , w h i l e a n equal -amount -were -found, to -be-lower
m o l e c u l a r weight, acids--and-soluble in the-acidified.-extraction solution.
The -Bureau of Mines f o u n d t h a t .thq- lower m o l e c u l a r w e i g h t acids were m a i n l y
. Sr mixture, of o x a l i c * succinic*, glufapic,,,-adipic
.and a f e w other, unidentified, acids.
Mines
#1pimelic,, -.and. suberic
I n . ear l i e r 'work, done- by. the B u r e a u of
(1
I) f -acids very s i m i l a r to .th e . h i g h e r m o l e c u l a r w e i g h t insoluble
* l n this.article, kerogen. was -defined .as the,organics recoverable-.byshale- retorting.
acfdb
7
acids were studied.,
These acids
(Regenerated "humic"- acids) ,were found,
to be very- ,complex ,.acid mixtures .
No. positive identification -could- tie
m a d e c o n c e r n i n g t h e '" h u m i c " acids.
■Other w o r k h a s •also, b e e n d o n e .on a l kaline permangana t e - e x t r a c t i o n s
of o i l-shale-by Stefanovic -and.-Dragomir
(5.) .
In this w o r k t h e inyesti-
.
■■ '
gatprs a s e d ..a l k a l i u e r p e r i m n g a n & t e .solutions in acetone for- t h e extractions .
■T h e s e - i n v e s t i g a t o r s . s u g g e s t e d , t h a t the,-extraction p r oducts consisted
m a l p l y , of l o n g a l i p k a t i c . c h a i n s whi c h - w e r e p a r t l y unsaturated.
T h e ,prde-
•ducts- w e r e acidic-and. had. little, or no. aromatic.structures, present.
-S i n c e . t h e Green -River s h a l e was s u s p e c t e d to con t a i n different
o r g a n i c m a t e r i a l than the shale used, in.the B u r e a u of Mines studies a nd
other studies ^ it was. -decided that p o s s i b l y t h e a I k a l i n e v p e rmangan ate
extractions of the Green, R i v e r - s h a l e . w o u l t - l i k e w i s e y i e l d - d i f f e r e n t
. p r o d u c t s . -T h e r e f o r e t h i s
report is a n i n v e s t i g a t i o n of alkaline, ext r a c -
.tions.. of o x i d i z e d Green R i v e r oil-shale.
In this investigation, h o w e v e r ,
-so da, ash was-.-used, as the.-alkaline-ingredient instead -of caustic soda.
S o d a ash was u s e d because-it i s cheap and,-available to W e s t v a c o . .'Some
w o r k w a s also ,done-on ,aip^ox-idatlen. of t h e .oil^shale f o l l o w e d by a l k a l i n e
extractions .,
Potassium, p e r m a n g a n a t e - w o u l d b e - a n impractical, ,oxidizing
.,agent i n a, co mmercial extraction.
A-study, was m a d e on. o b t a i n i n g m a x i m u m
y i elds .and de term i n i n g the best extraction, conditions f o r obtaining- these
m a x i m u m yields' of -erga.nic.m a t e r i a l .
Also,,, included in this, report is. an
i d enti f i c a t i o n s t u d y of t h e . o r g a n i c p r o d u c t obtained.
''T'. 8
— -
EQUIPMENT USED
A,,
E x t r a c t i o n Apparatus
In ,ort^er to extract the Green River,, W y o m i n g oil^shale. 1VJlth alkaline
■solutions^ a P a r r s e a l e d r e a c t i o n a p p a r a t u s .was us e d ^ ^Th is',r e a c t ion ’ ,
apparatus is, p h o ^ n i n / F i g u r a 'I.
A-.block f l o w dia g r a m pf, the a c t u a l .e x ­
tr action procedure-,(Figure-3). shows where, t h e re a c t i o n ' a p p a r a t u s fits
into
the. p r o c e d u r e .
F i g u r e I A ,illustrates the s e a l e d r e a c t i o n bo m b w h i c h w a s used.
,extraction st a r t i n g .materials
mised-- di r e p t l y in. t h e bom,^•
The
The bomb
was, than closed, by p l a c i n g the, stai nless s t e a l ,fitted, head,an. t o p ,o f -the
b o mb.
T h i s . h e a d was h e l d "in -place a n d , s e a l e d ' b y t h e t h r e a ^ d d bomb cap
c o n t a i n i n g / socket^tiead .sealing, screws .
_
The sealed, bomp- w as ,th-en. re a d y to
.be h e a t e d - a n d agitated.
Figure- IB ,shows w h e r e t h e sealed, b o m b w a s , p l a c e d i n t h % rea c t i o n
apparatus,
'The bomb was p l a c e d i n s i d e - t h e i n s ulated h e a t i n g jacket.
h e a t input..#' this
jgpkpt was-., s u p p l i e d b y two. w i r e h e a t i n g .elements ,
ThePne
-element-was- f o r m a x i m u m .temperature--and, was controlled- by. a. s w i t c h -p n ■the '
.
m e t a l .switch b.ex on the b a s e p l a t e .
The,other- h e a t i n g , e l e m e n t was f o r
s m a ller h e a t i n g - i n p u t a n d was c o n t r o l l e d b y t h e Vuriac pn th e ' b a s e plate.
In this .investigation.,.-the m a x i m u m h e a t e p was u s e d to.-achieve, the .-desired
e x t r a c t i o n temperature.,
■This h e a t e r was th e n turned-'.of f .and- t h e t e m p e r a ^
ture -was, m a i n t a i n e d by u s i n g t h e s m a l l e r h e a t i n g - e l e m e n t tp -balance th e
h e a t losses f r o m t h e bomb.
The-tem p e r a t u r e - w a s m e a s u r e d by- inserting.,an
i r p n ^ p p n e t a n t a w t h e rmocouple in t h e :t h e r m o w e l l in the- b o m b .
The-th e r m o w e l l
-— 9 ™"
.may also,,be- & e e n l a Figure- I,
The- t h e r m o c o u p l e leads were-connected, to-a,
.MinneapoliS-^Honeywell-Brown,'".Eleotronik"' t e m p eraiure i n d i c a t o r -The tem­
perature. indicatpr. us-ed„ was -,a eingl-e^ppint:precl&ipn. indicator.
The s e a l e d bomb "Was. agitated, throu g h o u t the heatlng\,period ,by the .use
of a m o t oar-run d r i v e .m e c h a n i s m . -In thig way,
the ..extractions- could.be
carried out f o r -a.- considerable length of t i m e t o make..sure- the .extraction
w as c o m p l e t e .,
T h e specifications- a n d - a d e s c r i p t i o n .of. the vital p a r t s
in the -Parr
reaction, apparatus are as follower,
Bomb c y l i n d e r r
The...bomb- cylinder -has a n o m i n a l S i
I z e p f . 5 G 0 .mlllii-
liters and,, a n effective changing- capac i t y . o f about 27 9 . milliliters,. , The
c y linder was m a d e f r o m a. solid forging, of s t a i n l e s s , s t e e l a n d is capable
of w i t h s t a n d i n g v e r y h i g h p r e s s u r e s ...
Epmb- head..*
The. bomb head, was also -made f r o m s o l i d f p r g i n g p f
s t a b i l i z e d siainles-s st,eel-and-.was- machined, to .fit the,, c y linder p-xaptly.
It-contains.a'.small.groove for. h o l d i n g the-head, g a s k e t .
Head-- gasket :■
This gasket- fits be-fween the head- a n d the, cylinder and-
s p r e a d s .w h e n t h e bomb is sealed,. It was- m a d e of seamless -annealed.,copper
and. h a s - a d i a m o n d - s h a p e d , onoss^secflon.
Bomb.-closare-y
This p i e c e - o f the - P a r r a p p a r a t u s ,was .made, of heat
-treated c h r o m i u m - p i c k e d - s t e e k - a n d - F a s threaded, tQ P c r e w on. t o ,the ■b p m b .
It contains eight s o c k e t - h e a d , s c r e w s - w h i c h be a r against- s t e e l washers
•on -the-bpmb h e a d a n d thus compress,the h e p d gasket.
10 ~
T h e r m o w e l l :. ;The,thg-rmowell.is- ja c o p p e r cup -sealed. ,In. t he bottom-,of
the bomb-, c y l i n d e r ,
-T h e r m o c o u p l e :
Thermocouples ,.u^ed-'were.made of I r o n i c onsbantan. and
w e r e - c o n n e c t e d to the M i n n e a p p lis;--Honeywell..t e m p erature i n d i c a t o r .,
heater-;'. T h e heater- tube- is- in s e r t e d w i t h i n the- h e a t i n g japket.-and
^receiyes
t h e bom)p .cylinder.
'This- tube.is- Wppnd--With she a t h e d - w i r e .-,elements
c o n tro l l e d b y tiie base, p l a t e Tariac- a n d , t h e m a i n h e a t e r switch.
The t u b e
,is suppo r t e d by. a heavy--a l p m i n u m endr-pI a t e v a n d h e a v y sheet a s b e s t o s T h e
tube,is,.-encased-by a n o t h e r s t e e l shell -and. the. a n n u l a r s p a c e is. p a c k e d
.w i t h thermal insulating.material,., •L e a d wires, to, t h e hpating-,elements, are
accessible-, through t h e - r e a r - a l u m i n u m - p l a t e ,
■IDrjye -m e c h a n i s m ': /The. b p m b -drlyp consists of a n . a ^ m .attached, to. t h e
h e a t p r trunnion w h i c h r o c k s the-bomb a s s e m b l y through a n -arc -of 4 ^ degrees
This r o c k i n g ’mdVes
t h e bomb-contents .from.-epd- to -end .-at 3 6 cycles p er
■minute, 'A-. c r a n k -connected to -a l / 6 -hp, m o t o r driyes- the cgnnep t i n g / r o d
_ to t h e . r o c k e r arm..
A s w i t c h on, t h e m e t a l -switchbox, controls,, t h e m o t o r
independently, of -t h e h e a t e r ..
In a d d i t i o n to the a b o y e yital.-parts- of t h e -extraptlon. a p p a r a t u s ,
Various other a ccessories w e r e a y a i l a b I e to ,aid in. loading ,.and ,unloading
t h e bomb.,
■B .
A i r r Oxldatipn column,.
This lnyest i g a t i o n includes', e e m e . studies-.made on. air^oxidizlng'-of
the -Green R i y p r shale- i n s tead ..of using- p o t a s s i u m permanganate, in the-
-•11 Tl
e x trac t i o n m i x t u r e . •The air-oxidized..shale was then e x t r a c t e d with
-alkaline solution^.
F o r these p r e l i m i n a r y s t u d i e s a,.simple.glass a i r -
o x i d a t i o n colpmn was constructed, a s . s h o w n in'-Figure 2.
The .column, was
h e a t e d - b y one continuous Nichrpme coil .of 22 phmp r e s i s t a n c e from.tog to
bottom.
P r e y i p u s ly. g r o u n d ,and...dripd.shale, was- intro d u c e d t h r o u g h the top,
of t h e glass, column.
■The .shale was. supported, b y , a rigid.-stainless, s teel
screen, in. t h e b.pttpm of the ■c o l u m n . -The ^cplumn was constructed, so. that
■a b out 200 .grams of the.ground.-shale could, be. o x idized e f f e c t i v e l y .,
The
a i r s t r e a m -Ior e f f e c t i n g the -oxidation was- i n t r o d u c e d through a l/4-;;inc,h
inside-, d i a m e t e r t%bd -connected to. the .bottom, of the, column., , T h e ..air, s t r e a m
p a s s e d through a s e c t i o n of alundum--balls before r e a c h i n g t h e shale-;.
S i n c e some,-of t h e ground, s h a l e . p a r t i c l e s w e r e -yery fine.,, t h e y had. to be
prevented, f r o m i p a y i n g t h e .e p l y m n by. u s i n g .a filter-paper.-trap
. t r ated in F i g u r e 2,
.,as.,illus
The- h e a t input -to the ..column, was c o n t r o l l e d by - a
Variac..c o n n e c t e d to. t h e ,Nichrpme c o i l a nd the t e m p e r a t u r e W a-S m e a s u r e d by
t h e us-c of a t h e r m o c o u p l e Inser t e d into t h e shale.bed*
H o n e y w e l l temper a t u r e - i n d i c a t o r w a s .a g a i n used.
Np attempt w a s , m a d e to
m e a s u r e the a i r - f l o w rates .in th,ese. p r e l i m i n a r y studies.
.operated, conti n u o u s l y for s e y eral.hours.
'This Min n e a p p l i s -
-T h e c o l u m n was
,12— ^
PROCEDURE -AKD MATERIALS
A.
Procedure
I.,
Alkallne-Pegmangariate' Extractions
a.
P r e l i m i n a r y .Runs
The
,
Grfeen R i v e r > Wyoming, Q l l rShale w a s .o b t a i n e d In fair l y
large pieces
(3~ to. — --inch -chunks) .
T h e r e f o r e y.,b e f ore the'
S h a l e could, he'- extracted,, it- h a d t o . b e b r o k e n d o w n to. -a Smaller
pagtiolfe .size.
.The shale,, .which also contained,.a considerable'
a m o u n t of t rona i n a crys t a l l i n e form., was p a s s e d through a.
S m a l l jaw. C r u s h e r a n d r e d u c e d to.pieces .approximately 1/4 -to
l/2 inch a c r o s s .
I t - w a s ,f o u n d that the s h a l e itse'lf Could be
.Crushed -quite e a s i l y j 'however, .the inter-mixed, t rona crystals
w e g e .y e r y h a r d a n d .difficult to, "break, a n d r e m a i n e d in larger
pieces
t h a n the shalet
A f t e r p a s s i n g .through the jaw, c r u s h e r ,
,the shale, was f e d into a M o n t g o m e r y W a r d M o d e l G.h a m m e r mill.,
T h e s h a l e at this p o i n t was r e d u c e d to a f i n e p o w d e r ,,
9Q
p e r cent p f the,milled, s h a l h was
^iOQ,mesh,
At least
It was felt
that .this p a r t i c l e size 1 w o u l d gi v e a .fairly l a r g e s u r f a c e area
f o r t h e ;-extractions witho u t b e i n g so f i n e as.to f o r m ..a cake,.
In the ,first .-alkaline-permanganate, extractions, of .the s h a l e
a n a t t e m p t was m a d e .to sfee if a n y .,appreciable amount.-of-organic
m a t e r i a l . c o u l d be recovered.
,
It. was found that the resulting
^extraction, liquors y f e l d e d y a g y i n g ,amount of o r g a n i c .materials,
d e p e nding o n/how t h e liquors w e r e treated,..
Ethers f -alcohols .,
.w.
ketones.^ and. c h l o - r o f o m w e r e all u s e d to,, r e move organic
m a t e r i a l f r o m the I IqfTior& a n d f r o m thd salts left a f t e r t h e
liquors were .evaporated t o - d r y n e s s .
w e r e e x t r a c t e d just a s
At f i r s t s t h e liquors
they w e r e received, f r o m the bomb.
The
same extractions were th e n m a d e on liquors that h a d b e e n
■a c i d i f i e d and-.o n the dried salts left f r o m t h S e v a p o r a t i o n of
these a c i d i f i e d l i q u o r s .
In a l l cases > It was p o s s i b l e to
O b t a i n extracts * t h e residues
of w h i c h w e r e mostly, amorphous
a n d water-ins oluble.
.On the basis of the very s m a l l a m o u n t s .of organic m a t e r i a l
■obtained in t h e s e p r e l i m i n a r y runs* it w a s , d e c i d e d to increase
extrac t i o n t i m e by a f ac t o r of ten
(i .e .,.f r o m
2
to
20
hours).
This i n c r e a s e . i n . t h e e x t r a c t i o n time m a d e the r e s u l t i n g liquors
very b l a c k and-so m e w h a t v i s c o u s ,
A c i d i f i c a t i o n of these b l a c k
.liquors y i e l d e d a b l a c k t a r KLike p r e c i p i t a t e w h i c h C o u l d be, re-moyed, b y f i l t r a t i o n of the l i q u o r s .
W h e n t h e p r e c i p i t a t e was
r e m o v e d ,.it c o u l d b e o b s e r v e d that the r e m a i n i n g liquor had. lost
m o s t.of the b l a c k color,
h o w e v e r , on analysis it was found
that -the r e m a i n i n g liquor s t i l l . c o n t a i n e d organic .matter, m o s t
of w h i c h could.-be recovered, by a n acetone extraction.
•P r o m the i n f o r m a t i o n g a t h e r e d in -these long e r runs* an
a n a l y t i c a l procedure" was set up to, f i n d . o u t - w h a t t o t a l amount
.of o r g a n i c .m a t e r i a l -was. o b t a i n a b l e from, the s h a l e by this ex­
t r a c t i o n method.
-The an alyses w e r e - d e s i g n e d to -determine the
1^/* *•
alnouat: -Qf organics r e c o v e r e d from, t h e s h a l e tinker-different
e x t r a q t i o n . - c o n d i t i o n s . Seye r a l runs w e r e m a d e i n w h i c h . t h e
.amount -o f .p o t a s s i u m p e r m a n g a n a t e , the' amo,unt ,e f --,oil-shale, a n d
"the tetaperartjire were’ varied.
.The liquors f r o m these yuns were'
then a n a l y z e d f o r organic material,.
T h e a n a l y t i c a l p r o c edure
is illust r a t e d in the b l o c k f l o w diagram- in. F i g u r e 3 ,and was
c a r pied -out, as .fpllon# :
I^
'
T h e e x t r a c t i o n m i x t u r e obt a i n e d f r o m extrac t i n g .the'
■oil-shale was filtered..
The shale r e s i d u e .and
excess
s o d a ash remained'.on. t h e .filter paper.
2„
T h e basic ,filtrate or liquor was then a c i d i f i e d wi t h
.concentrated H C l .to a .pH .of a p p r o x i m a t e l y Z\
A black, tar-,
l i k e . p r e c i p i t a t e -was o b t a i n e d o n ,acidification o f the
filtrate.
,3 .
T h e p r e c i p i t a t e was -separated.from tbe..Iiqubr and,
-quantitative.,measurement o f
t h e amount- of precipitate.
_p e r charge of shale-was .obtained.,
T h e r e m a i n i n g -liquor was .ey.aporated, to,near-dryness
a n d the r e s u lting r e s i d u e was e x t r a c t e d w i t h I p O . * .50.,,
and
25..m i l l i l i t e r
5 ..
T he-acetone extract por t i o n s were, f i l t e r e d and t h e '
por t i o n s .of acetone.
f i l trate evapor a t e d t e dryness* .the residue, t a k e n UP, In
acetone,,, and t h e n e w fi l t r a t e -again e v a p o r a t e d to -dryness.
6.
A quanti t a t i v e - w e i g h t m e a s u r e m e n t of t h e residue
o b t a i n e d from; the- -acetone extractions was- t h e n made.
7.
The total p e r cen t . r e c o v e r y of orga n i c m a t e r i a l
based on
t h e amounts .of extrac t i o n p r e c i p i t a t e - a n d the-.-acetone
extracted..residue.obtained was
then d e t e r m i n e d b y addition,.
This -a n a l y t i c a l procedure-..does n o t take into account .the -weight
of oxygen p i c k e d up in t h e , o x i d a t i o n .of the ,shale organics.
b .,
Total -Yield Study
A fter d e s i gning .the-analytical-procedure, it ^ a s - deQi-ded,that
an ,attempt s hould be m a d e to s e e if a l l of the-,organic.material,
in the shale, c o u l d b e r e c o v e r e d by several extractions of.a
.single- s a m p l e of oiL-shaf.e,,
A b a t c h extra c t i o n was m a d e wi t h
t h e .f o l l o w i n g ,ingredients
I.
-2 .
5.
b.
Potassium permanganate Soda .ash — 6.6 grams
L o w e r s h a l e — 133 grams
W a t e r -- 24-0 grams
20
grams
'
T h e ,p.Qtasslum -permanganate, and,,shale, portions w e r e ,added to .a
21.,5
p e r cent solution, of sodium, c a r b o n a t e in, the. bomb- cylinder
of t h e r e a c t i o n a p p a r a t u s . T h e reaction. m i x t u r e . w a s
.agitated in -the. bomb f o r
20 .h ours
at
200°
then,
centigrade.
T h e Iiqudr obtained f r o m this extra c t i o n was analyzed.by
the p r o c e d u r e p r e v i o u s l y e x p l a i n e d .
The s h a l e residue, was..dried
I’
and..re^extracted. with -a duplicate, of the .-solution u s e d for the
first extraction.
This p a t t e r n was f o l l o w e d u n t i l . t h e p hale
residue-, had., b e e n extracted si x times.
A f t e r -each extraction^.
,
16
t h e r e s u l t i n g liqtior was ,analyzed f o r organic m a t e r i a l a n d the
e x t r a c t i o n r e s i d u e was d r i e d a nd re-extracted.
A s e v e n t h ex­
traction. of the s h a l e . r e s i d u e , y i e l d e d no a p p r e c i a b l e amount of
o r g a n i c , m a t e r i a l - a n d the e x t r a c t i o n s w e r e -concluded.
c.
S t a t i s t i c a l - D e s i g n Runs
Analys-is of s e v eral preliminary, runs i n d i c a t e d that the
a m o u nt-of s h a l e , .the amou n t of p o t a s s i u m pe r m a n g a n a t e , a n d . t h e
■temperature w e r e n o t . t h e o n l y ,variables w h i c h a f f e c t e d the p er
cent recovery of organic m a t e r i a l f r o m t he oil-shale.
Runs of
2 » . IQ, 20, a n d 200 hours were m a d e h o l d i n g , a l l other e xtraction
conditions constant.
after
20
Analysis
of these.runs i n d i c a t e d that
hoars -of e xtrac t i n g the per. cent .recovery, of organic
m a t e r i a l w a s . p r a c t i c a l l y u n a f f e c t e d b y e x t r a c t i o n time.
-There­
fore, a. series of runs was m a d e h o l d i n g time constant a n d v a r y ­
ing. the f o l l o w i n g e x t r a c t i o n c o n d i t i o n s i
1. . O x i d ation l e v e l '(amount-of K M n Q 4 ).
2.
E x t r a c t i o n temperature
J.. S o d a .ash concentration,
4. -Ratio of oil-sha l e to e x t r a c t i o n liquor
These runs.^ e r e m a d e us i n g . a stat i s t i c a l a p p r o a c h a n d the con­
cept of s t e epest ascent
(I,).
W i t h the he l p .-of the M o n t a n a S t a t e
-College Mathe m a t i c s Depar t m e n t a n d - a p e sbarch p a r t n e r , the nqns
w e r e set up to f o l l o w a s t a t i s t i c a l p a t t e r n as s h o w n in Table IX.
T h e e x t r a c t i o n Variables a r e d e n o t e d by- X n a s
T a b l e I.
i n d i c a t e d in
By. .analysing the e x t r a c t i o n liquor's f r o m the s t a t i s t i c a l
runs q u a n t i t a t i v e l y > a n e x p r e s s i o n was d e t e r m i n e d where the p e r
cent recovery, of organic .material was d e f i n e d I n terms of the
f o u r coded, e x t r a c t i o n variables..
This e x p r e s s i o n has the f p r m
Y = Bq + BxZ-x + BgZg + B3Z3 ,+ B4Z4
where
Z 2. = X x
10-0 >
53-
Zg .= X g ?*. 20
10
t
Z3
X 3 T*1200
■ ■ 70
>
Z4 = -X4 h 54
' ■ 35
,-The sign-of t h e coefficients
("Bh ) ,-of.t h e code d - e x t r a c t i Q n
variable's indicates I n w h a t d i r e c t i o n t h e e x t r a c t i o n variables
m u s t b e a l t e r e d f r o m t h e . m e a n v a l u e .used In order to obtain t h e
h i g h e s t p e r cent recoyery.,of organic, m a t e r i a l from the oilshale.
.The. r e s u l t s ,of this s t a t i s t i c a l - d e s i g n
s h o w n later
In the r e p o r t .
6
2.
-~
Air-ox i d a t i o n - R u n s
ITsing the a i r - o x i d a t i o n c o l u m n sho^rn I n B i g u r e
2 ,..runs
were made
W h e r e i n the. Green R i V e r shale was -a i r - o x i d i z e d a n d .later extracted
W i t h - a l k a l i n e solutions.
The oil-shale w a s - f i n e l y g r o u n d
.and. d r i e d f o r s e v e r a l hours in a f o r c e d - a i r cabinet-drier,.
.matoly. 150 grams, of t h e ■d r i e d . s h a l e w e r e u s e d p e r run.
was a d d e d to t h e c o l u m n through the o p e n top.
pre-heate^L to,-approximately
75°
(-100 mesh)
Approxi-.
T h e shale
.T h e - c o l u m n was th e n
c e n t i g r a d e a n d the a ir was intro d u c e d
T h e . a i r entered, t h e b e t t o m of the column, -at a rate- s u c h t h a t .the b o d
1§ —
of shale was
t horoughly flaidhpeh.,
was then raised . u n t i l approx i m a t e l y
The' t e m p e r a t u r e of the column
200°
centigrade.was reached,
a n d the shale was air^oxidiaed. s t e a d i l y f or s e v e r a l - h o u r s ..
After, t h e ■oil— shale- h a d b e e n -oxidized-,, a, d e s i r e d ,amount w as
added, to a n a l k a l i n e s o l u t i o n i n t h e b o m b .
The 'preyiously oxidized
shale- -nas then e x t r a c t e d for seve r a l hours a t the .desired t e m p e r a ^
-ture.
T h e r e s p i t i n g liquors f r o m t h e s e runs- were analyzed, the same
as t h e liquors ,from the-U l k a l i n e ^ p e r m a n g a n a t e extractions.
B.»
M aterials
In the a i r - o x i d a t i o n s a n d extractions of the..Green R i y e r o i l - s h a l e ,
- t h e f o l l o w i n g m a t e r i a l s were- used-:
OjlSshale:
Shale-_ from, the .lower G r e e n R i y e r t ed was ,used in the
e x t r a c t i o n s . s i n c e it was, k n o w n to cont a i n more, orga n i c m a t e r i a l than -the.
s h a l e i n the- upper bed.
The..shale- u s e d in t he alka l i n e - p e r m a n g a n a t e e x ­
tractions yes ground, so .that it wcjuld a l l pass a, iI-Qrmesh s c r e e n ,
The
. shale., used ,in t h e -air-oxidation studies, was ground to ..-IQO mesh.
Potassium permanganate:
B aker a nd A d a m s o n reagent g r a d e KMriQ4 w as
U s e d a s a n oxidizing, ,agent i n the e x t r a c t i o n s .,
S o d a ..a s h f' JTesjiKaeo S o d a Ash was u s e d as t h e .a l k a l i n e i ngredient in
t h e -extractions,.
W a t e r -:,
A j r -:
This soda., ash was.
88
p e r cent s o d i u m carbonate,.,
Tap w a t e r was used.as the -extracting s o l v e n t .
In t h e .air-roxldatlon sfudi-es, th e .,air was obtained, f r o m a
Gardner— B e n y e r O ompres s o r .
1-9
H y drochloric AQld-:
Fiisher •reageni; ,grade c.pncentrated, H Cl was, ts^d
f o r acidif y i n g the e x t r a c t i o n llq,h9^s,.
Acetone:
Redistilled., c o m m e r c i a l acetone- was a p e d for -extracting
the l i q u o r s .
Q U A L I T A T I V E .ANALYSES L E P RODUCTS
The extrac t i o n products, f r o m -the G r e e n River, oil— s h a l e . w e r e handled,
in s e v e r a l ways .
It was s u s p e c t e d .t h a t :some..of t h e p r oducts w o u l d be-
a c i d i c in n ature because -the rigorous, oxidation, of t h e /organic m a t e r i a l
would, v.ery l ikely result ,in, a c i d structures .
oil— s h a l e - o x i d a t i o n
were-acids.
(3 .,.
5)
Also,, pre v i o u s w o r k done on
h a d .s h g w n that mo s t of t h e o x i d a t i o n products
-In view,-of this, t h e resinous . p r o d u c t s
w i t h alcohols to try. a n d -es terif y an y acids,present.
obtained-were.refluxed
In, m o s t cases , a
s mall amount-of liquids w i t h p l e a s a n t odors were.obtained.
However., m o s t
of t h e re s i n ous,substances w e r e only s l i g h t l y a f f e c t e d by, t h i s .t r e a t m e n t ,
Therefore,, a selective .solvent breakdown, of t he -extraction products...was
p r o p o s e d to try, t o ,separate the,dif f e r e n t .orgdnic components..
S e v e r a l ,runs .were ,made. to..collect .a l a r g e a m o u n t of e x t r a c t i o n liquor,,
This, large, b a t c h o f .liquor was acidified- H i t h . c o n c e n t r a t e d H C l to a.pH,of
.approximately 2.
A, l a r g e mass
of- t h e tar - l i k e p r e c i p i t ate,respited.
precipitate-was'-washed and, then dried-,for s e v e r a l h o u r s .
.was then placed, in a
600^ m i l l i l i t e r
Various selec t e d solvents .
f o l l o w s :.
The
T he precipitate
i o x h l e t ,ex t r a c t o r a n d w a s h e d wi t h the
The., o r d e r of the-solvent ,extractions
w a s as
- %
I
2',
3..
4..
Benzene
Chloroform
A c etone
M ethyl Alcohol.
A l s a, a s e p a r a t e -portipn of the,pre c i p i t a t e -was washed, s e v e r a l .times wi t h
c a rbon disulfide..
T h e - a m o u n t ,,o f precipitate- wh i c h d i s s o l v e d varied, direct^.
I y w i t h the order- in w h i c h t h e s o l v e n t s w e r e .used.
It w a s h o p e d that, this
p r o c e d u r e w o u l d -separate the lower- m o l e c u l a r weig h t portions, of the pre^.
.c i p i t a t e f r o m the- h i g h e r ones.
The , c a r b o n . d i s u l f i d e - w a s ,used, separately
in -an a d d e d effort to extract any, low ,-molecular weight p o r t i o n s .
E a c h .of the -above-extract samples was evaporated to dryn e s s - a n d the
residues, r e m a i n i n g w e r e ,analyzed by t h e u s e o f a B e c k m a n IR^-4 infrared
.spectrophotometer (see F i g u r e 4 . through F i g u r e 7).
The i nfrared-anblysis
was u s e d to.find o u t .w h a t s tructura l groups w e r e p r e s e n t in solvent eX-,
t r acted p o r t i o n s .,of „the , p r e c i p i t a t e „
Some..tests .were m d d e toward con­
f i r m i n g the- infrared .analyses.
The- liquors r e m a i n i n g .after t h e t a r - d i k e ,pr e c ip itat os- were,, rem o v e d
w e r e also,-analyzed- to a c e rtain ex t e n t .
The organic.materials in these
liquors .were -collected.as .previously -explained.
,materials were- in.,a resinous
fprm.,
In -most cases-,, -theyorganic
H o w e v e r , s e v e r a l of t h e extractions
yield-ed long needle-like, organic..crystals, a l o n g w i t h t he r-eisinous pro d u c t
It- was first suspe c t e d , t h a t the-crystals we r e inorganic.
to see if the- .crystals w e r e organic..
Tests were, ma d e
F i r s t of a l l , m e l t i n g p o i n t deter.-
.mirations .mode on the.-crystals .showed .them to.melt a t ,approximately,
130^
c e n t i g r a d e .- It,is very u n l i k e l y .t h a t .a ny inorganic- c r y s t a l s , w o u l d be
p r e s e n t w h i c h w o u l d . m e l t - a t this temperature.
Also,*, w h e n p l a c e d , i n ,a.
■
—< 21 -—
hot flame#, t h e crystals charred and a p p e a r e d to be .carbonaceous.
crystals were very s o l u b l e in seyp-ral.organic- solvents.
it was concluded...that the crystals w e r e organic..
The
A f t e r these, tests
B o t h t h e crystals a n d
the r e s inous p r o d u c t were then s u b j e c t e d to i nfrared analysis,
BISCUSSIQH OF- RESULTS
,A.
Q u a n t i t a t i y e Yields
I.
Total Y i e l d -SfudyAs m e n t i o n e d before., a s t u d y was m a d e to see -what,total p e r cent
of fhe-..organic ..material i n a s i n g l e .shale .sample-, c o u l d be r e c o vered
by seyeral extractions-.
results,
This. s t u d y yielded, some very -encouraging
-The.first extrac t i o n of t h e 133 - g r a m s a m p l e y i e l d e d . o r g a n i c
m a t e r i a l corres p o n d i n g t o . 1.34, p e r c e n t ,of the. s h a l e - w e i g h t .
In the
f o l l o w i n g five .extractions of t h e . o r i g i n a l s a m p l e -a c o n s i derable
amount of a d d i t i o n a l organic m a t e r i a l s w e r e r e c o v e r e d
(see Tabie-ill) .
In all six extractions -of. the, shale- sample, approximately'' 6,7 .fer
cent of the,or i g i n a l shale w ei g h t was recovered-as. organic m a t e r i a l
(Runs 31,,
30.,
51#,.52» 56>.
58,
59),
R m
5 2 -was m a d e - w i t h o u t adding
,any K M h Q 4. to determine what p a r t s o l u b i l i t y w a s . p l a y i n g in fhis
study,
-In this. run. an. A d d i t i o n a l
organic- m a t e r i a l .
0,379 ,pep-- cent
w a s recoyered.as
This ,indicated thaf ,solubility was ,a.factor -but
that.most-of the additional, r e c o v e r y .i n each s u c c e s s i v e . r u n was- beingmade p o s s i b l e b y the a dditiona l .oxidation taking place.
Since t h e
-Green R i v e r shale is. k n o w n to, c o n t a i n about. S--^lO p e r cent total
o r ganic material..#, the 6,7 p e r cent r e c o v e r y c o r r e s p o n d e d to about
.•*— 22
70^ 80.,per-, cent: o-f
the, total, organic Jnaterial .available in the shale,
H o w e y e r# these yields d a n o t . t a k e into- a c c o u n t the. w e i g h t of oxygen
p i c k e d up ,in-the process.
The results o b t ained in this t o t a l y i e l d study s h e wed.that
alkaline extractions of t h e.ox i d i z e d s h a l e .could be,used..to p r o d u c e
o r g a n i c .m a t e r i a l f r o m the ..shale.
At this p o i n t y . n o c o n s i d e r a t i o n was
g i y e n -t o t h e specif i c - o r g a n i c m a t e r i a l desired,.
Qf considerable interest -during-,-this study was
w i t h t h e initial-extractj only;
5-7
the fact, that
p e r cent of t h e recovered..-organic
material-was-.obtained by, precipitation, -upon ,acidification of the
extraction liquor.
On t h e see end. extraction^
55.-5 per. cent of the
recovered..organic,material-was' obt a i n e d -by the a c i d i f i c a t i o n
and..on. t h e .third-extraction^
65
p e r cent was -obtained.
step^
After a
f o u r t h - e x t r a c t i o n m a d e i n the -absence of KKtaQ^#, the a m o u n t o f acid
soluble m t e r i a l recovered, w a s - a g a i n gre a t e r than t h e -acid insoluble
material.
This-, remained,.true.f p r each of the. runs- there a f t e r ,and.
the ratio,.of soluble .to -i n s o l u b l e .'material re m a i n e d -quite, c o n s t a n t .
It is -p o s s i b l e that in t h e -first t h r e e extractions some- of t he
oxidized, organic m a t e rials w e r e left in the.-shale r e s i d u e b e c a u s e
of the.so l u b i l i t y limitations of the a lkaline l i q u o r .and- a s they
.
w e r e oxidiz e d . t o . a h i g h e r leyel i n subseq u e n t r u n s * . t h e y were r e ­
covered a s .a c i d i n s o l u b l e jn.af.erIals .
the,excess
In. the fifth e x t r a c t i o n .after
o x i dized organi c . m a t e r i a l had-,been r e m o v e d and..in t he
sixth a n d s e v e n t h e x t r a c t i o n s . w h e p e . s o l u b i l i t y was, n o t a f a ctor be<-.
'2;3 .daT3.se'. of low. yields,
this was- no t the- case,, and a g a i n more,,of the
organic m a t e r i a l a p p e a r e d as a c i d s o l u b l e material,
2.
A i n - O x i d a t i o n Runs
,
I
Rpns .were- m a d e i n w h i c h t h e n il— p h a l e was ,.air-oxidized, and,, then
l a t e r -extracted -with -alkaline.,s plutigns ,
Analysis of these runs
(Runs $5 a n d 57) s h o w e d that it was al s o po s s i b l e to. ob tain c o n s i d e r ­
able, amounts of the-, o r g a n i c . m a t e r i a l f r o m the. o i l - s h a l e by. this
methPd.
55,,
■In. R i m
a h i g h a l k a l i n e .concentration was u s e d in, the-
■extraction a n d in, R y n 57.». a. l o w a l k a l i n e co n c e n t r a t i o n was ysed. .
(see Table I I I ) ,
I n Roth-bases-, a c o n s i d e r a b l e -amount.pf .the. a v a i l ­
able -organic m a t e r i a l was extracted,
In R u n
57.,
the ,shale was air-,
oxidized.-at a, h i g h e r average temperature, than, in R u n 55; h o w e v e r ,,
,in. R y n
55,. the-
Runs. 55 and-.
57
.respectively.
s h a l e was. oxidized. l/2 hour, longer.
The- yields in
were .1.55 and. 1,15 p e r c e n t of t h e shale, sample,
This corresponds
to. a bout .15-2.0-per cent ,and 1 0 - 1 5 p e r
cent.of the available ,organic m a t e r i a l in the shale.
More-air— oxidation, s t u d i e s . aue- n o w b eing.made b y -another in­
vestig a t o r in a , m o r e e f f i c i e n t . o x i d a t i o n unit*
It,is h o p e d that
very h i g h y i e l d a w i l l e v e n t u a l l y b e -ob t a i n e d by this method,.
5*
Statis t i c a l R e s i g n 'Runs
In an attempt to-.-optimize t h e e x t r a c t i o n .-conditions, f o r the
M i g h e a t p e r c e n t .recovery, of o r g a n i c .m a t e r i a l per. s i ngle e x t r a c t i o n ,
a series- of rims was m a d e following.a. s t a t i s t i c al-design.
The- rims
24
■were' set' up w i t h t h e help .of a f e l l o w r e s e a r c h p a r t n e r a n d the
M o n t a n a State College- Mathematics D e p a r t m e n t . ■The. runs w e r e de s i g n e d
(see Tapies I .and II). to..determine in what g e n e r a l - d i r e c t i o n t he e x ­
t r a c t i o n variables s h o p l d p e c h a n g e d f r o m a m e a n .value to -obtain the
h i g h e s t y i e l d ■of organic m a t e r i a l i n a. s i ngle extraction.
An e x ­
p r e s s i o n i n which, the p e r .cen t r e c o v e r y is d e f i n e d in terms of the
-extraction variables was determined.
This e x p r e s s i q n w as f o u n d to be
Y'=.1.669 - o.45^Zi,+ o .266z2 — 0v268z3 ~-q.io4z4 .
T h e p e r c e n t . r e c o v e r y pf o r g a n i c , m a t e r i a l is den o t e d as Y - a n d the
eoded .extraction v a r i a b l e s ..as follows r
Zf = X1 V -100 * Z2 = X2 - 20 , Z3 = X3 .- 200
'55
-10 "
'
■' 70
= X 4 --„54.
55
From, the c a l c u l a t e d values
of the coefficients th e f o l lowing
g e n e r a l conclusions were drawn;
T o .a p p r o a c h the' h i g h e s t y;ield of o r g a n i c , m a t e r i a l in a s i n g l e
e xtraction w i t h 2 4 0 g r a m s .of s o lvent, the e x t r a p t i p n conditions,
must b e altered-as follows i'
I,.
D e c r e a s e the amount of shale, per chargef r o m 100 g r a m s .
■ 2.
.
Increase the a m o u n t -pf K M n Q 4 ,p e r charge
from, 20 g r a m s ,
5.
4.
-Decrease o x i d a f I o n ^ e x t r a c t i p n temperature
f r o m 20O°C.
D e c r e a s e the ,amount of s o d a ash p e r charg'd
f r o m 54 g r a m s .
25' ^
, I n opder t o -establish o p timum ex.trac-tirig ,conditions .more, definitely,
,other sets- of s t a t i s t i c a l l y d e s i g n e d r u n s w o u l d .have t o , b e made.,
jBie-
a b o y e infor m a t i o n was e s t a b l i s h e d w i t h the h o p e , o f h a y i n g ,an idea.of
-What type, of e x t r a c t i o n -conditions s h o u ld-be used, w i t h later air-,
oxidation s t u dies,
A t the' p r e s e n t time, t he d e t a i l e d - s t u d y of the
air-ox i d a t i o n - o f t h e o i l - s h a l e w h i c h is b e i n g .c a r r i e d put by anot h e r
invest i g a t o r is a i m e d at o p t i m i z i n g bo t h the a i r ^ p x i d a t ion. conditions
and, t h e e x t r a c t i o n conditions by t h e use. of statistical.'designs .
•B..
,Qualitative Results
The products
o b t a i n e d in p r e l i m i n a r y extractions w e r e amorphous
taP^iijce materials . ' These p p o ducts- were, suspected.,to b e c o m p l e x acid
mixtures, a n d s e v e r a l attempts w e r e .made to esterify. them.
It was
eyident that some eS t O^if Ic at ion t o o k place-; .however,, most- Of the
tar-tlike .material .remained Unchanged.
Since h i g h conversion^ w h r e
.not obtained*,it w a s . d e c i d e d t h a t - p o s s i b l y the tar— like, materials
s h o u l d . b e -left u n c h a n g e d for i d e n t i f i c a t i o n . a n a l y s i s .
Infrared
analysis was chosen f o r trying to o b t a i n .a p r oduct.identification.
,Infra r e d analysis, was ma d e on the tar-like, ppeeipit.ate obtained
f r o m the a c i d i f i c a t i o n of the e x t r a c t i o n liquors
(se'e F i g u r e 4 — A) .
T h e numbers o f t h e a b s o r p t i o n contributions l i s t e d . b e l o w refer.to
t h e a b s o r p t i o n p e a k s - w h i c h are l i k e w i s e n u m b e r e d - o n the.infrared
analysis
charts.
.I n t e rpretat i o n of a l l - o f the infrared-analysis
- 26
--charts was ..accomplished, w i t h the. aid,, of Br. g. B a k e r o f the- Montana.
State C o l l e g e . C h e m i s t r y B e p a r t m e n t 4 ,.and, the^ results-, obtained-,are as
follows
.I*
B r o a d .band.spectra, -.contribution -of the-, OH ,in a carboxylic
(C G O H )., s truetur-e.
•2.
A l i p h a t i c . c a r b o n - h y d r o g e n s t r e t c h or bonding.*
5.
Contri b u t i o n of either a..lactone or an anhydride,- structure-.
^<-■7. All b r o a d b a n d spectra,-ContributipnB of d i f f e r e n t types
of carbonyl structures,. (i*e,f possibilities.ape- h. — acid;
5 ., k etone or cyclic; 6 . — aldehyde; 7 . k e t o n e . o r
.aldehyde).
1
I
8 ..
B r o a d band, c h a r a c t e r i s t i c - o f - c o m p l e x a c i d - s t r u c t u r e s .,
^.
The same- ap
10.
. 11.,
8
P o s s i b l y e ither anhydride-, or- l a c t o n e a b s o r p t i o n or
a c i d •contribution,.
P o s s i b l e . m e t h y l e n e pr
(h C H 2-<) . linkage.
From.the. a b p y e . analysis,, it.ma y be.,concluded that the-.p r e p i p i t a t e
is more- than likely a mixture, of complex, acids- w i t h the presence".of
s e y e r a l types ,of. carbo n y l groups .,
A l s o 4, the, p r e s e n c e of a lactone-, or
a n anhydride- is indicated by. the.peaks at
5.5
and.
5 .6,microns,
-,Since
there- is-, also, a. p o s s i b i l i t y -of cyclic compounds- being-,present* the
p r e c i p i t a t e was, a n a l y z e d for s u l f u r .a nd n i t r o g e n to s e e - i f these
elements- could, b e tied up ,in heterocyclic- ,structures,*
s h o w e d the p r e c i p i t a t e . t a contain
-0„91
The. analysis
p e r .cent, nitrogen-.and
2.15
p e r cent sulfur.
A - s e c o n d i n f r a r e d a n a l y s i s was m a d e on a carb o n -disulfide
.solution obtained- f r o m w a s h i n g the p r e c i p i t a t e - w i t h p u r e C-S2 »
— , 27
I n t e rpretation of this inf fared, c h a r t is as follows- (see Figure 4-— B ) ;
1.
B f p a d feand.,spectfa confr-ibatipns pf t h e O H ,in a carbpxyllc
(,COOH) structure,
2.
Aliphatic .carbQn-hy-drpgen SvtrefCh or bonding-.
3.
Contri b u t i o n of either, a -Iactpne or a n .anhydride s t r u c t u r e . '
4.
■One type .of carbonyl st r u c t u r e o.ontrfbutipn (possibly
- a l d e h y d e but p r o b a b l y acid.-carbonyl)..'
5.
B r o a d b a n d •c o n t r i b u t i o n of C S 2 solvent.
6.
P o s s i b l y either lactone,., -anhydride, or .acid contribution.
I t.may bp- noticed, that i n b o t h . F i g u r e 4--A a n d . F i g u r e 1M B
considerable .-,amount-Pf e a r b p nd p y d r p g e n bpnding.
there is .-a
B p w e y e r , this c a r b o n -
h y d r o g e n b o n d i n g is in cyclic c o m p o u n d s . r a t h e r than straigh t - c h a i n
.as suggested, in other w o r k d o n e on o i l - s h a l e - o x i d a t i o n
(5-),
This,
may.-be.assumed because the sharp b a n d ,of m e t h y l e n e a b s o r p t i o n at 14.2
m i c r o n s .shows, o n l y s l i ghtly or no t at all,,
-This is true-with-,all -of
the extraction, products w h i c h were, a n a l y z e d i n this,- investigation.
T h e third infrared, analysis was m a d e on t h e ,benzene.-extracted
p o r t i o n of- the tar^-like.precipitate
(see,Figure 5,-4.,) .
In,each.of
t h e solvent e x t r a c t e d p o r t i o n s of t h e precipitate,, t h e solvent was
e vaporated and. t h e infrared-analysis- W a-S m a d e -on th'e r e m a i n i n g film.
I n t e r p r e t a t i o n of F i g u r e 5^-4 is,as -follows:
I.
B r o a d .band .spectra, contributions, of the QH in a Carboxylic
(.COOH), s t r u c t u r e .
2".
A l i p hatic carbon-hydrogen, b o n d i n g .
3 - t 4 B o ^ h e i t h e r a, contri b u t i o n of a l a c t o n e or an. ,,anhydride
structure-.
-29,5.,
P r o b a b l y c o ntribution of a p i d carbonyl structure-.
6- 7 ., B K p u d
8-.
b a n d s p g c t r a c a used b y com p l e x a c i d s t r u c t u r e s .
-Pps-sibiy a. lactone- or ^rx ,anhydride contribution.
F i g u r e 5-B is- the infrare d ana l y s i s of the ,chip-reform, extractedp o r t i o n of' tha.prepipitate. and-shpws--a s u b s t a n c e yery. similar to that
shown in F i g u r e 5 -A.
T h e interpretation, of F i g u r e 5sd3 is.:
1.
B r o a d ..band ,spectra .contributions of t he OH, i n ,a c a r b o x y l i c
(COOH) s t r u c t u r e .
2.
A l i p b a t ip.ca r b o n - h y d r o g e n banding.
5•
P r o b a b l y C o n t r i b u t e # of a c i d carbonyl .groups.,
•4-6. B r o a d b # d
s p e c t r a caused, b y complex, acid-,structures'.
7 v. P r p b a b l y a s mall -amount ,of m e t h y l e n e -(^CH2 -) bptiding
The .main d i f f e r e n c e b e t w e e n F i g u r e
5rA a nd F i g u r p 5-B..,is t h e
.absence,.of the lactpne. or anhydride- a b s o r p t i o n in F i g u r p 5-B,
Inf rare (!-'analysis charts F i g u r e ,6- A .and Figure-.feB a g a i n show
two-pubstances of p r a c t i c a l l y , i d e n t i c a l natu r e except f o r the p r e s e n c e
o f .the l a c t o n e or anhydride, st r u c t u r a l a b s o r p t i o n b a n d i n F i g u r e
6,-A.
F i g u r e .6- A .show?- thd- a c e t o n e e x t r a c t e d - p o r t i o n -of the- precipitate^,
philP. F i g p r e
pprtipn,.
6- B ,i s .a n
a n a l y s i s .of the- .methyl a l c o h p l -extracted
B o t h p o r tions a p e .essentially very c o m p l e x . a c i d ,mixtures *
■F i g u r p 7-A.a n d - F i g u r e
7,-B
app- charts, f r o m t h e a n alysis of
the.products-^obtained- 'frpm t h e . a c e t o n e extractions -of the pilf shaleextract l l p u o r a fter t h e tap— l i k e .precipitate .was remoyed.
7- A .is
Figure
the.analysis, -of the- l o n g .n e e d l e - l i k e -crystals.-pbtpined. in
se-yeral-of. the ,extractions-.,
This- C h a r t c ould-Only be. p a r t i a l l y
- 29 H.
inter p r e t e d w i t h ti>e p r e s e n t I n f o r m a t i o n 6 .I n t e r p r e t a t i o n of Figure
T - A is as f o l l o w s t
I.,
V e r y sharp but u n i d e n t i f i e d . a b s o r p t i o n band,,
2.
Shows 1 the lack of a n y c a r b o m - h y d r o g e n s t r e t c h or b o n d i n g .
3.
Possibility, of a s ma l l ,amount o f carboxylic
structure..
'
4>
U n k n o w n b r o a d b a n d s p e c t r a contribution.
(.COOE)
5^6« P o s s i b l y different c a r b o n y l s t r u c t u r e s .
7•
C o n tribution charact e r i s t i c of .equiplex a cid.structures .
8.
Possibly, an a c i d s t r u c t u r e but unlikely, because, of
its position.
9-
Could., b e methylene, absorption, but this is u n l i k e l y
because, of the lack ,of c a r b o n - h y d r o g e n b o n d i n g in' 2 .
•It m a y be .concluded from the. weak i d e n t i f i c a t i o n data, obtained in
Tr-A,. that •a great" deal more i d e n t i f i c a t i o n w o r k m u s t be done, on the
crystals w i t h m o r e c o m p l e t e facilities.
At first, it was s u s p e c t e d '
that the,.crystals w e r e amido acid, structures
a
(i .e .„ compounds, with
S-EH-CO--Or -S-U=C(OH)- l i n k a g e .and, c o n t a i n i n g the a c i d -COOH ,group) ;
.however, t h e a b s o r p t i o n regions fo r such s t r u c t u r e s .are- too low in
F i g u r e T--1
A,,' Also., analysis, of t h e crystals by, the N i n h y d r i n Test
(6).showed'no evidence of ^ N H 2 or .-NH- groups b e i n g present.,
Anal­
ysis, of the- crystals for- elem ental .nitrogen an d sulfur, show e d them
to be O i 201.p e r cent n i t r o g e n a n d 0.228 p e r cetit sulfur.
Melting
point determinations were made- a nd f o u n d to be q u i t e sharp in t h e
range 1 2 9 0V i33°
centigrade.
A s s u m i n g that an o r g a n i c .'compound m e l t i n g
i n this_ r a n g e has a'm o l e c u l a r w e i g h t of a p p r o x i m a t e l y l80., the
t-s 30
n i t r o g e n and. s ulfur determinations., w e r e calculated, en a mole, p er
cent b a s i s . -This m a d e t h e crystals a -compound w h i c h was appr o x i ­
mately, 1.3 mole- p e r cent- ni t r o g e n and. 1 .3 m o l e p e r cent s u l f u r . ■This
indidates that probably, these two elements w e r e not p r e s e n t , a s pa r t
of the crystalline structure.
Figure
is the infrared- analysis of the resinous g u m -obtained
f r o m the ucetone extractions
analysis- shows
portions
of a c i d i f i e d extract
.l i q u o r s T h i s
the g u m to be q u i t e s i m i l a r to some, of the extract
of .the h e a y i e r p r e c i p i t a t e ..
This again seems, to i n dicate
that the .on l y . d i f f e r e n c e b e t w e e n some, o f t h e .e x t r a c t i o n products
some degree' of polymerization.,
1.
shows ^
B r p a d band s p e c t r a c o n t r i b u t i o n of the OH, in a car-.
.boxylie (COOH),s t r u c t u r e .
'
2.
3.
.I n t e r p r e t a t i o n of F i g u r e
is
Aliphatic carbon-^hydrogen s t r e t c h or. bonding. ■L a c t o n e or a n h y d r i d e ,contribution.
4-.
5“ 6.
Probably, acid.carbony l st r u c t u r e contributions i
B r o a d b a n d - s p e c t r a c h a r acteristic of complex
acid.structures.
7 . /Either,
lactone-,. a n h y d r i d e . o r a c i d contribution.
Once again. F i g u r e Y-1B is .another p r o d u c t w h i c h is. e s s e n t i a l l y a
complex, apid mixture.
E s t e r i f i c a t i o n could b e u s e d to. d e t e r m i n e w h e t h e r the e xtraction
products- contain anhydride--or l a c t o n e structural g r o u p s ,.
anhydride groups- were present,
a n h y d r i d e absorption.
If any
esterification, w o u l d e l i m i n a t e the
H o w e v e r , ,if l a c t o n e s t r u c t u r a l groups were
— 31
p r e s e n t , their absorp t i o n r e g i o n w o u l d . r e m a i n u n c h a n g e d on
esterification.
■B I B L I O G R A P H Y
1.
Cochran* VU G.._, a n d Cox, GL M . 'Experimental -Designs., John. W i l e y &
Sons, Inc.,,. (1957)» P- 575•
2.
I n t e r m p u n t a l n Chemical Company R e p o r t ,, Organic Studies at the
U n i v e r s i t y of U t a h , 1958.
■
'
5.
R o b i n s o n * W. E. ,, Cummins, J. J.,* an d Stanfield, K. E., C o n s t itution
of Organic Acids P r e p a r e d f r o m C o lorado Oil. Shale,
Ind.. & Eng. Chem.,
W
1134-58 (1956).
~
4.
Roblns-qn.* VL E . , - H e a d y > H. H . and.. H u bbard, A. B.,,. A l k a l i n e H e r m a n ^
gapate Oxidation Qf Oil Shale K e r o g e n * I n d . & H n g . Chem., 45,
78891 ( 1 9 5 T T
"
■
-
5.
Stefanoyic * G., and D r a g o m i r ,. V . , N a t u r e of Oil Shale- Kero,gen*
J o urnal of Chem..& Eng. Data* 4
162-67 (1959).
6.
S t e i n , ¥,. H.., a n d Moore-*, S.., Journal -of B i o l o g i c a l - C h e m i s t r y ,
367 (1948),
'
176.
^.-3_2
ACKNOWLEDGMENT
The author wishes to thank the F o o d Ma c h i n e r y a n d C h e m i c a l C o r poration
f o r sponsoring this research project.
The a u t h o r also wishes
to thank
P r o f e s s o r H. A. Saner a n d R e s e a r c h F e l l o w Jerry D. M a s o n f o r their aid,
s u g g e s t i o n s , and criticisms
on this project.
t
- 35 -
APPENDIX
Table I
L evel of E x t r a c t i o n Variables f or S t a tistical Runs
Table II
Series of S t atistical Runs Made
Table III
Analysis of E x t r a c t i o n Products
Page
34
35
from Oil-Shale
Extractions
36
F i gure I
Parr E x t r a c t i o n Apparatus
39
F i gure 2
A i r - O x i d a t i o n Column
40
F i gure 3
B l o c k F l o w D i a g r a m of A l k a l i n e - P e r m a n g a n a t e
Extractions
4l
Figure 4
Infrared Analysis of Products
42
F i gure 5
Infrared Analysis of Products
43
6
Infrared Analysis of Products
44
F i gure rJ
Infrared Analysis of Products
45
F i gure
- 34 TABLE I.
Level of E x t r a c t i o n Variables
for S t a tistical Runs
X ■- Variable
Code and L e v e l
-I
0
+1
X1 —
Grams Shale
67
100
133
X2 —
Grams Perman g a n a t e
10
20
30
X3 —
Temperature
0C
130
200
270
X4 —
Grams Soda Ash
I
34
67
- 35 TABLE II.
Series
Code
— 1— 1—1
R u n No.
6
l
1- 1-1
62
-I 1-1
63
I 1-1.
64
-1-1 I
1-1 I-
39
65
of Statistical Runs Made
Xi
X2
X3
X4
67
10
130
I
2.06
10
130
67
1.13
30
130
67
2.57
30
130
I
1.99
10
270
67
1.62
10
270
I
0 .8l
30
270
I
2.24
133
67
133
67
133
67
% Recovery
-I I I-
66
111
67
133
30
270
67
0.94
0 0 0
68
100
100
200
34
1.59
0 0 0 0
69
100
100
200
34
I .78
TABLE III.
ANALYSIS OF EXTRACTION PRODUCTS FROM OIL-SHALE EXTRACTIONS
PRODUCT ANALYSIS
Run
No.
Remarks
50
200 hr.
Ext.
31
Run for
total %
Recovery
D e t 1n.
50
Residue from
31. (2nd
E x t r .)
Cm.
Low—
Shale
Gm.
H 2O
66
133
240
232
119
0. l4l
0.542
1.00
20
66
133
240
371
121
0.0)8
0.630
1.55
20
66
333"
150
0.405
0.325
1.22
Extr.
Time
(hr)
Extr.
Temp.
'C
Gm.
KMnO4
200
200
20
20
200
20
200
Cm.
SodaAsh
240
133
(orig. w t . )
Total
Ext. V o l .
(ml)
Aliquot
Vol.
(ml)
Gm.
ppt.
Gm.
Acetone R e s .
Total Io
Recovery
I
200
20
66
240
150
Residue from
50. (3rd
E x t r .)
20
52
Residue
from 51•
(Check run)
(No K M n O 4 )
20
200
0
66
133
240
)00
150
0.124
0.127
0.379
56
Residue
f r o m 52.
(4th E x t r .)
20
200
20
66
133
240
290
150
0.242
0.713
1.38
58
R e s idue
f r o m 56.
(5th Extr.)
20
200
20
66
133
240
375
150
0.068
0.206
0.513
51
133
346
0.543
0.292
1.45
O N
I
TABLE III.
ANALYSIS OF EXTRACTION PRODUCTS FROM OIL-SHALE EXTRACTIONS (continued)
PRO D U C T ANALYSIS
•O
3 5
Total
Ext. V o l .
(ml)
59
20
Residue
f r o m 58.
(6th E x t r .)
200
20
66
133
240
240
120
0.036
0.083
0.179
53A
53B
Low Amount
Soda Ash
20
20
200
200
20
20
7
7
133
133
240
240
340
340
150
0.572
0.490
0.644
0.640
2.06
150
54
High Amount
KNfriO4
20
200
40
66
133
240
345
150
0.276
0.703
1.70
55*
Air-Oxid.
Run
20
200
120
217
294
150
0.503
0.443
1.55
HO
(of air
o x i d .)
209
410
150
0.204
0.248
1.13
Run
No.
Remarks
Extr.
Time
(hr)
Extr.
Temp.
°C
Cm.
KMnO
Gm.
SodaAsh
Cm.
LowShale
58
Aliquot
Vol.
(ml)
Gm.
ppt.
Grn.
Acetone R e s .
Total %
Recovery
1.95
(of air
d x i d .)
57*
Air-Oxid.
20
Run &
L o w Soda Ash
200
60
No Soda Ash
20
200
20
0
133
240
-350
150
0.612
0.368
1.72
6l
Statistical
D e s . Run
20
DO
10
1
67
240
375
150
0 .l8 l
0.371
2.06
5.7
*Alr o x i dation conditions u s e d in runs 55 a nd 57 were as follows:
R u n No.
55
A ir oxidation f or l/2 h o u r at I l O 0C
for
3 hours at 115°C
R u n No.
57
A ir oxidation for
f or
3 hours at 2 0 0 °C
6 hours at 200°C
TABLE III.
ANALYSIS OF EXTRACTION PRODUCTS FROM OIL-SHALE EXTRACTIONS (continued)
P R O D U C T ANALYSIS
•CdXi
CO
62
Statistical
D e s . Run
20
130
10
67
133
63
Statistical
D e s . Run
20
130
30
67
64
Statistical
D e s . Run
20
130
30
I
133
240
515
150
0.323
0.448
1.99
65
Statistical
D e s . Run
20
270
10
I
133
240
445
150
0.244
0.117
0.805
66
Statistical
D e s . Run
20
270
30
I
240
330
150
0.347
0.328
2.24
67
Statistical
D e s . Run
20
270
30
67
133
240
445
150
0.110
0.303
0.920
68
S t a t lstical
D e s . Run
20
200
20
34
100
240
400
150
0.172
0.425
1.59
69
Statistical
D e s . Run
20
200
20
34
100
240
42 5
150
0.248
0.381
1.78
39
Statistical
D e s . Run
20
270
10
67
67
240
370
150
0.100
0.340
1.62
Remarks
Extr.
Time
(hr)
Extr.
Temp.
0C
Gm.
KMnO4
Gm.
Acetone R e s .
Gm.
LowShale
Run
No.
67
67
/
Gm.
H2O
Total
Ext. V o l .
(ml)
Aliquot
Vol.
(ml)
Gm.
ppt.
240
365
150
0.426
0.197
1.13
240
4 05
150
0.034
0.600
2.57
Total %
Rec o v e r y
-
39
~
Bomb Head
Cylinder
Thermowell
---- !
Head Gasket
Bomb Closure
A.
BOMB CYLINDER
Heater Tube
Thermowell
Motor
Variac
B.
EXTRACTION APPARATUS
(not to scale)
FIGURE I.
PARR EXTRACTION APPARATUS.
136311
- 40 -
Ilter-Paper Trap
Air Outlet Holes
Thermocouple
Leads
Thermowell
Shale B ed Top
!chrome Coil
Leads
Stainless S creen
Alundum Balls
m
m
n
T
Variac
Air S t r e a m
(not to scale)
Figure 2.
A i r - O x i d a t i o n Column.
41 -
Potassium
Permanganate
Remo v a l
of Acetone
f r o m Organic
Materials
Green R i v e r
L o w e r Shale
W e s t v a c o Soda Ash
Filtration
of Inorganic
Salts
Water
Extraction
With Acetone
Evaporation
of F i ltrate
to Dryness
Sealed E x t r a c t i o n
Bomb
Tar-like
P r ecipita t e
Filtr a t i o n
of E x tract
F igure 3.
F i l t r a t i o n of
Prec i p i t a t e
HCl A c i d i f i c a t i o n
of F i l t r a t e
B l o c k F l o w D i a g r a m of A l k a l i n e - P e r m a n g a n a t e E x t r a c t i o n s .
A
-F
r
or
I
600
7Q0
1100
1200
1300
>400
1500
IfiQO
1700
>800
1900
2000
i
F i g u r e 4-A. I nfrared Analysis of Tar-like Precipitate
F i g u r e 4-B. I nfrared Analysis of CSg F r a ction of Precipitate
B
A
14 15 16
13
12
I
700
F i g u r e 5-A. Inf r a r e d Analysis of B e nzene F r a c t i o n of Pr ecipitate
F i g u r e 5-B. Inf r a r e d Analysis of C h l o r o f o r m F r a c t i o n of Precipitate
Vl
A
F i g u r e 6-A. In f r a r e d Analysis of Acetone F r a c t i o n of Precipitate
F i g u r e 6-B. In f r a r e d Analysis of Methanol F r a c t i o n of Precipitate
B
A
3000
F i g u r e Y -A. Inf r a r e d Analysis of Acetone E x t r a c t e d Crystals
F i g u r e Y-B. Inf r a r e d Analysis of Acetone E x t r acted Resinous Material
gEEgE
14 15 16
r
13
T
12
MONTANA STATE UNIVERSITY LIBRARIES
3 1762 10015591 8
378
I u39e
136911
cop. 2
Suiter, R. C.
Extraction of organic materia
from Green River, Wyoming...
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