Challenges in Oils with High
Chlorophyll Content
Santiago de Chile
August 2013
Jorge Bello
Public
Business Development
08.03.2013
Manager
Canola – A Challenging Oil
08.03.2013
Phosphatides
in crude oil
%
Unsaponifiable
matter
%
Tocopherols
%
FFA
%
Waxes
Chlorophyll
ppm
0.05-0.10
0.19-0.44
0.04-0.07
2.5-5.0
absent
<10
Canola oil
1.8-3.5
0.8-1.0
0.04300.2680
0.4-1.2
trace
10.0-60.0
Soybean oil
1.5-2.5
1.6
0.15-0.21
0.3-0.7
absent
0.5-8.0
Oil or Fat
Palm
Goals of a HA Adsorbent.
High activity on chlorophyll
 Debottlenecking filter equipment.
Improving throughput
 Reduction of: Oil losses; spent cake
disposal and clay dosage.
A beneficial Adsorbent
 Leaving most antioxidants in the oil.
 Reduction of Oil losses, spent cake
disposal and clay dosage.
Canola No 3
Western
Canada
Chlorophyll
(ppm)
Typical HA
Adsorbent
Dosage (%)
Canola
No 2
100
60
High Chlorophyll
Short cycles
3.0
1.5
Canola
No1
15
1.0
Relative Filter
Cycle (1)
1/3
2/3
1
Relative oil lost
in cake (based on
+300%
+50%
ref
dosage)
2
Chlorophyll is a Pro-Oxidant
08.03.2013
A great amount of antioxidants (carotenoids,
tocopherols, etc.) have been removed from RB oil and
the most from RBD oil.
The oil is now more vulnerable to
the effects of light on the attractive
transparent bottles.
3
Chlorophyll and Free Radicals
08.03.2013
When the chlorophyll molecule absorbs light energy (E) in processed oils
two reactions can occur :
1.- The E is dissipated as heat (a great part when the oils are exposed to
direct radiation)
3.- The E adsorbed is released as free radical initiating oxidation reaction.
•e-
4
Oxidation of the a Positions
08.03.2013
a –linoleic acid
•e-
Ataque de a la molécula
Radical libre
Radical libre
Peróxido
Formación de
hidroperóxidos
•
•
•
•
•
•
Odor
Bad Taste
Rancidity
Polymerization
Low stability
Yellowing
5
Natural Decomposition and Fixing
08.03.2013
Disabling enzyme
high chlorophyll in
seeds
BLEACHING
Description
Adsorb.
%
DEODORIZATION
Stability
Heavy Metals (ICP)
Chlorophyll COLOR
ppm
Y
"A"
R
Y
70
10.04
----70
70
70
COLOR
OR CANOLA OIL
---
R
3.0
Adsorbente X
Adsorbente Y
SUP 1206 FF
1.0
1.0
1.0
1.9
2.0
3.0
BLEACHING:220°F, 30 min., 20 mmHg
0.25
0.34
0.12
1.1
0.9
0.8
9.0
10.0
7.1
OSI
AOCM
Cu
P
Ca
Fe
120°C
----
98.7°C
----
ppm
< 0.05
ppm
7.98
ppm
9.77
ppm
0.13
4.10
4.50
5.00
19.35
21.29
23.71
< 0.05
< 0.05
< 0.05
4.10
3.73
< 0.4
5.13
4.03
0.57
Mg
Total
ppm ppm
2.81 20.69
< 0.06 1.49 10.72
< 0.06 1.21 8.97
< 0.06 0.28 0.85
DEODORIZATION: 480°F 120 min., 2 mmHg
6
The Role of Catalytic Acidity
08.03.2013
30000
25000
25000
Acidity
reacts to
attack the
load
centers
22000
22000
ppb
20000
15000
10000
Chlorophyll
5000
25
25
0
Crude
Free acidity also attacks the bonds of the
oxidant compounds.
Acid
Degumming
neutralwashed
RB
RBD
6.5
7.0
6.0
PV
5.0
4.2
4.0
4.3
4.0
O
II
CH2- O-C –CH2-(CH2)n COOH
Acid - Clay
O
II
CH2- O-C –CH2-(CH2)n COOH
O
II
CH2- O-C –CH2-(CH2)m –CH-CH2- COOH
I
O-OH
O
II
CH2- O-C –CH2-(CH2)n COOH
O
II
CH2- O-C –CH2-(CH2)n COOH
O
II
CH2- O-C –CH2-(CH2)m
3.0
2.0
2.0
1.0
1.8
1.7
1.9
AV
0.0
0.0
0.0
Crudo
Desgomado
agua
Desgomado
acido
RB
RBD
7
Chlorophyll is Only Removed During
the Bleaching Step
08.03.2013
COLOR
CELL:
5 1/4"
R
A
ANALYSIS
CHLOROP
HYLL “A”
HEAVY METALS
(ICP)
ppm
Cu
ppm
P
ppm
Ca
ppm
Fe
ppm
Mg
ppm
ppm
CRUDE SOYBEAN OIL
10.0
70.0
0.59
nil
<0.05
379.6
55.34
0.78
32.55
OIL FROM 1st. CENTRIFUGE
8.9
70.0
0.55
480
<0.05
11.73
0.08
0.18
0.42
OIL FORM 2nd. CENTRIFUGE
9.0
70.0
0.55
57
<0.05
3.26
<0.06
0.18
0.19
RB SOYABEAN OIL (Tonsil)
RBD SOYABEAN OIL
8.7
1.0
70.0
9.0
0.02
…..
0
0
<0.05
<0.05
<0.4
<0.4
<0.06 <0.06 <0.1
<0.06 <0.06 <0.1
Oil or Fat
700
600
590
550
550
Chlorophyll
ppm
Palm
<0.100
400
Canola oil
10-60
300
Soybean oil
1-10
Corn oil
<0.5
Palm Kernel Oil
<0.2
Coconut oil
<0.2
500
ppb
SOAP
200
Chlorophyll
100
20
20
0
Crudo
Desgomado
Acido
Neutro
Lavado
RB
RBD
8
Chlorophyll Removed During
Bleaching
08.03.2013
SAMPLES
AND
ANALYSIS
OR CANOLA OIL (1")
Ads
BLEACHING
COLOR: 5 1/4" CLOROFILA
"A"
R
A
ppm
COLOR: 5 1/4"
R
A
Cd 18-90
ANISIDINA
DEODORIZATION
Cd 12b-92
Ca 5a-40
STABILITY, Hrs.
AGL
OSI
AOM
%
120°C 97.8°C
-------
P
ppm
Ca
ppm
Mg
ppm
1.38
<0.06
0.63
----
4.5
72.3
21.24
---
---
---
TIPO SUP 1206 FF
1.2
7.3
70.0
0.170
1.8
9.0
5.95
<0.05
3.85
18.14
<0.40
<0.06
0.45
TIPO SUP 1206 FF
1.4
5.4
70.0
0.077
1.5
7.3
5.50
<0.05
4.10
19.35
< 0.40
<0.06
0.42
TIPO SUP 1206 FF
1.6
4.4
70.0
0.056
1.3
10.0
3.09
<0.05
4.30
20.32
< 0.40
<0.06
0.35
CONDITIONS : BLEACHING: 230°F,30 min.,20 mmHg.
DEODORIZATION: 480°F,120 min.,3 mmHg.
7.00
Recommendations
 In RB oils Chlorophyll <100 ppb.
 Preference <50 ppb
Adsorbent Dosage
1.2
6.00
1.4
1.6
5.00
4.00
3.00
Benefits
 Better Oxidative Stability.
 Oil with more stable color.
2.00
1.00
0.00
AnV
Stability
9
Premium Products for Difficult Oils
08.03.2013
BLEACHING
Adsorb.
DESCRIPTION
DEODORIZATION
LOVIBOND
%
COLOR
LOVIBOND
Chlorop
hyll
A
STABILITY, Hrs
Heavy Metals Method (ICP)
OSI
AOCM
Cu
P
Ca
Fe
Mg
ppm
ppm
ppm
ppm
ppm
< 0.05 1.39
0.62
0.13
0.42
COLOR
R
A
ppm
R
A
120 °C
97.8 °C
---
7.9
70
2.06
---
---
----
----
ACTISIL FF
1.0
3.3
70
0.14
1.7
15
2.9
13.55 < 0.05 < 0.4 < 0.06 < 0.06 < 0.1
SUPREME FF
1.0
2.2
70
0.01
1.0
7.4
3.6
15.00 < 0.05 < 0.4 < 0.06 < 0.06 < 0.1
---
10.0
70
0.81
---
---
----
ACTISIL FF
0.8
6.3
70
0.11
1.2
8.7
4.6
21.77 < 0.05 13.5
SUPREME FF
0.8
4.0
70
0.02
0.9
7.5
5.4
25.64 < 0.05 10.6 < 0.06 < 0.06 < 0.1
---
9.2
70
0.62
---
---
----
ACTISIL FF
0.4
3.4
70
0.04
0.6
4.3
4.3
20.32 < 0.05 < 0.4 < 0.06 < 0.06 < 0.1
SUPREME FF
0.4
3.8
70
0.01
0.5
4.4
4.6
21.77 < 0.05 < 0.4 < 0.06 < 0.06 < 0.1
OR SOYA
OR SOYA
OR SOYA
BLEACHING:220°F, 30 min., 20 mmHg
----
----
< 0.05 19.4
< 0.05 1.56
0.37 < 0.06
0.3
0.15 < 0.06 0.28
0.52
0.27
0.44
DEODORIZATION: 480°F,120 min., 2 mmHg
For difficult oils Premium products show a better cost/benefit
10
Difference Between Activation Grades
(Soybean Oil)
08.03.2013
100
1.8
Actisil
Actisil
90
1.6
Supreme
80
1.4
70
Clorofila RB
1.2
Color RBD
Supreme
1
0.8
0.6
60
50
40
30
0.4
20
0.2
10
0
0
Easy Oil
Regular Oil
Difficult Oil
Easy Oil
Regular Oil
Difficult Oil
The more difficult to bleach the oil, the greater the difference in
cost/benefit between high activated grades and low activated grades
11
TOTAL Activation
Patented Process
08.03.2013
O
O
O
Si
O
Al
O
Si
O
O
Al
O
Na+
O
O
Ca++Mg
O
O
Si
Si
O O
O
Al
O
O O
Al
O O
++ K+
Fe+++
Al
O
O
Si
O
O O
O
Al
O
Al
O O
O
H+
O O
Si
Al
O
H2SO4
O
H+
Na+ Ca++Mg++ K+ Fe+++
Na+ Ca++Mg++ K+ Fe+++
Na+ Ca++Mg++ K+ Fe+++
O
O
O
Si
O
Al
O
Si
O
O
Al
O
90
O
O
Si
Temperature
O
O
Pressure
Al
O O
m2/g
O
Time
H+
Si
O O
Al
O
O O
Al
O
Al
O
H+
O O
O
Si
O
O
Si
O O
Al
O
Brönsted,
Free Acidity
Al
O O
340 m2/g
Acid Sites,
Exchangeable
Acidity, Lewis
Acidity,
Catalytic
12
State of the Art
08.03.2013
$
H2SO4,Temp, Time,
Pressure, Work,
Quality
Before
After
Moisture 35 - 40%
Moisture 10 - 20%
pH Alkaline
pH Acidic
SA = 90 m2/g
SA= 340 m2/g
High Ion Exchange
Low Ion exchange
Heavy (45 lb/ft3)
Light (34 lb/ft3)
Slow Filtration
Fast Filtration
13
TOTALLY Activated Surfaces
08.03.2013
Macro porosity in a particle of a TOTALLY
Activated Adsorbent type
14
Laboratory Results
08.03.2013
25
20
15
10
5
0
22
15.6
Results:
18.8
17
BE dosage (%)
10R+Y (lovibond)
12
Chlorophyll (ppb)
10
5
1.2
Tonsil
Supreme
 Improvement on the dosage rate approx.
25%
Permeability
4.5
 Slightly lower color after deodorization
OSI (120°C)
1.6
 20% higher throughput
Commercial
Adsorbent
 10% higher stability. (more tocopherol left at
the oil)
Results:
 This could meant improvement in
throughput specially for cases where
bleacher is the bottle neck.
 Potentially this clay could be a good
option for a packed bed system
Chlorophyll
(ppm)
 Reaction speed went fast
0.600
0.500
0.400
0.300
0.200
0.100
0.000
Commercial adsorbent
Tonsil Supreme
5
10
15
20
25
30
Time (minutes)
15
Conclusions
08.03.2013
 The goal of bleaching is to obtain a good quality finished oil.
Bleaching effect should be measured after deodorization
 The most harmful impurities are invisible to the human eye, so
measuring bleaching practices by color alone is not accurate
Chlorophyll has a melting point of 248 ° F and is not distillable, but
other oxidizing compounds decompose and are removed. Chlorophyll is
only removed with adsorbents, and the higher the chlorophyll content,
the greater the degree of activation that is required in the adsorbent.
 Carotene has a melting point of 356 ° F and is distillable however it is
an antioxidant that ideally should be retained until distillation
 The color and RBD properties are important in assessing the role of
the adsorbent
 Highly activated adsorbents are more efficient than adsorbents
sprayed with acid
16
08.03.2013
Thanks / Gracias / Obrigado
Anibal Urizar
Technical Support LATAM
Anibal.Urizar@clariant.com
Jorge Bello
Business Development Manager
Jorge.bello@clariant.com