Oil Processing Challenges in the 21th Century:
Enzymes Key to Quality and Profitability
Marc Kellens
Desmet Ballestra Group,
Zaventem, Belgium
De Smet Presentation
1
World Vegetable Oil Production
Malaysia
Indonesia
50
Million tons
45
USA
Mercosur
Canada
Europe
Major vegetable oils evolution
> 85%
PO+PKO
40
SBO
35
PO
%
Palm
30.1
Soybean
29.4
Rapeseed
14.4
Sunflower
8.7
Peanut
4.3
Cotton
4.0
20
Palm kernel
3.7
15
Coconut
2.9
Olive
2.5
30
25
10
5
0
2003/04
2004/05
2005/06
2006/07
2007/08
Production period
De Smet Presentation
2
Palm & Soybean oil production
evolution
PO = high sat oil
39.0
In 30 years a 10-fold increase
35.7
SBO = high unsat oil
In 40 years a 7-fold increase
De Smet Presentation
3
Trends in Oil Processing
Increased demand for high quality oils
Organoleptic/stability
-Bland taste, no odor
-Light color (brilliant)
-High thermal stability
-High oxidative stability
-Long shelf life
Functional Properties
OIL
QUALITY
Refining
- Good melting profile
- Desired Plasticity
- Crystallisation kinetics
Modification
Nutritional Quality
- Balanced FA composition (SFA/MUFA/PUFA, 3-6)
- Low or no trans FA (< 1%)
- High natural antioxidants (tocopherols) and vitamins
De Smet Presentation
4
Trends in Oil refining
Bleaching earth
Crude Oil
Water
FAD
Filtration
Acid / NaOH
Deodorisation
Deodorisation
Gums
(Lecithin)
Degumming
Degumming
Soapstock
Acid gums
Neutralising
Bleaching
Neutralising
Bleaching
Acid
Acid degumming
degumming
RBD Oil
Classical oil processing
>high unsats: chemical (FFA > soaps)
>high sats: physical (FFA > FAD)
De Smet Presentation
Steam
Bottling or
Further
Processing
5
Trends in Oil refining
Strong demand for more efficient processes
* More cost efficient processes:
- Lower investment & processing costs,
- Valorisation and/or reduction of by-products
* Flexible plants:
- Capable of processing multiple oils
* Fully automated plants:
- Higher consistency of operation, lower manpower cost
* Larger capacities (economics of scale):
200-300 TPD
1000 -> 2000 TPD
De Smet Presentation
6
Trends in Oil refining
Refineries need to reply to more and more stringent
environmental rules and at same time need to improve
their efficiency on both operational cost and delivery of
highest quality
Trend: - less chemicals, more physical treatment
- more sustainable, less energy
- less environmental impact: zero effluent
- maximum retention of “nutritional” quality
More bio, eco, green… enzymes a solution?
De Smet Presentation
7
Enzymatic oil processing
Trends in edible oil processing
° More (energy) efficient & environmentally friendly
processes
° Increased attention for the nutritional quality
° Milder processing giving more ‘natural’ products
ENZYMATIC PROCESSES
De Smet Presentation
8
Enzymatic processing
Aspects of enzymatic process
PRO’S
- Mild
, natural process
-Environmentally friendly
- Very specific, less random
CON’S
- Sensitive
to heat and pH
- Sensitive to feedstock quality (impurities)
- Cost (mostly higher than conventional chemicals)
De Smet Presentation
9
Enzyme processes in
Oilseed/Oil processing
Cleaning
Cleaning // Drying
Drying
Cracking
Cracking
Seed
Seed
Speciality
Speciality Fats
Fats
Dehulling
Dehulling
Mechanical
Mechanical Extraction
Extraction
Flaking
Flaking
Preparation
Solvent
Solvent Extraction
Extraction
Extraction
Hydrogenation
Hydrogenation
Frying
Frying oil
oil
Interesterification
Enzymatic IE
Interesterification
Margarine
Margarine
Fractionation
Fractionation
Modification
Soap
Soap
Lubricants
Lubricants
Biodiesel
Biodiesel
Meal
Meal
Oleochemical
Processes
De Smet Presentation
Crude
Crude
Oil
Oil
Enzymes
Degumming
Degumming
Enzymatic
degumming
Neutralising
Neutralising
Refined
Refined
Oil
Oil
Bleaching
Bleaching
Winterising
Winterising
Deodorising
Deodorising
Refining
10
Enzymatic degumming
Main driver: oil quality or oil profitability?
° more selective than chemicals, thus attacking ONLY
phospholipids
° treated gums contain less entrained oil, so higher yield
° with cost of enzymes << additional oil yield : a winner
Why does it take so long to
convince industry?
De Smet Presentation
11
Enzymatic degumming
PHOSPHOLIPIDS
=
O
CH -O-C-R
1
2
=
R2-C-O-CH
X : H (PA), choline (PC),
ethanolamine (PE),
serine (PS), inositol (PI),
O
=
O
R1, R2 : Fatty acids
CH2-O-P-O-X
Hydratable PL
Non-hydratable PL
O-
De Smet Presentation
12
Enzymatic degumming
PHOSPHOLIPASES
Phospholipase A1
Phospholipase A2
O
CH 2-O-C-R1
Phospholipase B
R2-C-O-CH
O
O
CH 2-O-P-O-X
O
5 subclasses of Phospholipases
A1, A2, B, C and D
Phospholipases A1, A2, C
are commercially available
(Novozymes, Danisco, Verenium)
Phospholipase D
Phospholipase C
X = H, choline, ethanolamine, serine, inositol, etc.
De Smet Presentation
13
Enzymatic degumming
ENZYMATIC CONVERSION PLA1/PLA2
O
=
CH -O-C-R
1
2
2
O
CH -O-P-O-X
O
+
H-O-C-R 1
=
O
R -C-O-CH
H 2O
=
O
+
O
=
=
2
2
=
R -C-O-CH
CH OH
Phospholipase A1 or A2
CH -O-P-O-X
2
2
O-
O-
LYSOLYSO-PHOSPHOLIPIDS
PHOSPHOLIPIDS
FFA
- Conversion of (non-hydratable) PL in hydratable Lyso-PL and FFA
- 0.036% FFA formed for each 0.1% PL converted
De Smet Presentation
14
Enzymatic degumming
Past situation EDG
° ENZYMAX® process by Lurgi
- First industrial EDG process started early 90’s
- Use of heat stable phospholipase A2
- Efficient if on high Q and fresh crude oil
- High enzyme cost made enzyme recycling necessary
- From porcine pancreas
problems with acceptability
- limited sources and availability of enzyme
Introduction of costefficient physical degumming alternatives
(TOP, SOFT, IMPAC) blocked breakthrough of EDG
De Smet Presentation
15
Enzymatic degumming
Re-introduction EDG
° Improved EDG by Novozymes (end 90’s)
- Phospholipase A1 (Lecitase Ultra – Novozymes)
- Stable and less expensive enzymes (third generation)
- Temperature optimum : 55°C, pH optimum : 6
- Residence: 3-6 hrs = f(catalyst consumption)
< 2 hr !
- No enzyme recycling necessary , comsumption 50 ppm
- Microbial origin
No problems with acceptability
Several industrial plants running today costcompetitive
Main negative point: what to do with high FFA ?
De Smet Presentation
16
Enzymatic degumming PLA1
(Lecitase Ultra)
Retention
Vessel
Retention vessels
3-6 hours
Oil Tank
30°C
Oil Pump
Degummed
oil
30 min
Crude
oil
To Silica
Treatment
70°C
1 hour
Heater
High
Shear
Mixer
55°C
High
Shear
Mixer
Citric Acid
Enzymatic Degumming
55°C
Low
Shear
NaOH to
Mixer
neutralise
citric acid
Water
De Smet Presentation
Enzyme
Centrifugal
Separator
Hydrolised
gums
To DT
(extraction)
17
Case study
Conventional SBO water- followed
by acid-degumming
Crude soybean oil
100%
2,50% PL
1000 ppm P
Gums
2,80%
yield
2,00% PL
0,80% NO
WDG
97,2%
0,50% PL
200 ppm P
Acid gums
0,90%
yield
0,45% PL
0,45% NO
ADG
96,30%
0,05% PL
20 ppm P
PL: phospholipids
P: phosphorous
NO: neutral oil
LL: lysolecithin
WDG :waterdegumming
ADG: acid degumming
total loss:
3,70%
De Smet Presentation
18
Case study
Crude SBO PLA1 degumming
70% conversion PL to LL+FFA
Partial
EDG
Crude soybean oil
100%
2,50% PL
Full
EDG
Crude soybean oil
100%
2,50% PL
Gums
1,93%
yield
1,68% PL
0,25% NO
PLA EDG
98,1%
0,25% PL
0,57% FFA
Gums
2,10%
yield
1,83% PL
0,27% NO
PLA EDG
97,9%
0,05% PL
0,62% FFA
Acid gums
0,40%
yield
0,20% PL
0,20% NO
ADG
97,67%
0,05% PL
Acid gums
0,00%
yield
0,00% PL
0,00% NO
ADG
97,90%
0,05% PL
total loss:
2,33%
total loss:
De Smet Presentation
2,10%
19
Enzymatic degumming PLA1
° Case study crude SB0 2.5% PL (1000 ppm P)
- Full EDG vs (WDG & ADG)
- P < 20 ppm
- Gain in crude oil yield: about 1.3-1.6%
- Gain in FFA: about 0.5-0.6%
- Net gain in RBD oil yield after full refining: 0.8-1%
- Net gain in FAD yield after full refining: 0.5-0.6%
FAD
loss !
- No soaps, gums but also no lecithin !
De Smet Presentation
20
Enzymatic degumming
New enzymes (1)
° EDG by Danisco
- Acyltransferase (~PLA2 type) (Lysomax Oil – Danisco)
- Temperature 50-60°C and pH 5-7
- Very short reaction (30 min!)
- No enzyme recycling , comsumption 100 ppm
- Microbial origin
No problems with acceptability
- (Part of) FFA esterified with free sterols, giving less/no FFA
No industrial plants yet running, results to be confirmed
De Smet Presentation
21
Enzymatic degumming using
Acyltransferase (AT) (Danisco)
PL
LL
- Conversion of PL in LL and FFA (part) re-esterified with sterols
- 0.036% FFA formed for each 0.1% PL converted to LL
- 0.065% FFA re-esterified with each 0.1% free sterols,
De Smet Presentation
22
Case study
Crude SBO AT degumming
70% conversion PL to LL+FFA
No
Full
FFA
increase
EDG
Crude soybean oil
100%
2,50% PL
0,30% free sterols
Part FFA esterified with sterols
With FFA
increase
Crude soybean oil
100%
2,50% PL
0,30% free sterols
Gums
2,60%
yield
2,27% PL
0,34% NO
AT EDG
Gums
97,4%
2,10%
yield
0,05% PL
1,83% PL
0,00% FFA
0,27% NO
0,50% est. sterols
AT EDG
97,9%
0,05% PL
0,43% FFA
0,50% est. sterols
Acid gums
0,00%
yield
0,00% PL
0,00% NO
ADG
Acid gums
97,40%
0,00%
yield
0,05% PL
0,00% PL
0,50% est. Sterols
0,00% NO
ADG
97,90%
0,05% PL
0,50% est. Sterols
total loss:
2,60%
total loss:
De Smet Presentation
2,10%
23
Enzymatic degumming AT
° Case study crude SB0 2.5% PL, 0.3% Sterols
- Full EDG vs (WDG & ADG)
- P < 20 ppm
- Gain in crude oil yield: about 1.1-1.6%
- Gain in FFA: about 0-0.4%
- Net gain in RBD oil yield after full refining: 1.1-1.2%
- Net gain in FAD yield after full refining: 0.0-0.4%
Any effect esterified vs free sterols on oil stability?
De Smet Presentation
24
Enzymatic degumming using AT
(Lysomax Oil)
Lysomax Oil degumming Process very similar to Lecitase Ultra (less residence)
De Smet Presentation
25
Enzymatic degumming
Recent introduction of new enzymes (2)
° EDG by Verenium
- Phospholipase C (Purifine – Verenium)
- Temperature 60°C and pH 7
- Rather short reaction (1-2 hrs)
- No enzyme recycling , comsumption 200 ppm
- Microbial origin
No problems with acceptability
- Attacks only PE/PC, not PA/PI
First industrial plants under construction, no real industrial
data available yet but highly promissing
De Smet Presentation
26
Enzymatic degumming using PLC
(Verenium)
0.84% DAG formed for each 0.1% PL (40 ppm P) converted
De Smet Presentation
27
Case study
Crude SBO PLC degumming
70% conversion PL (PE/PC) to DAG+ Phosphate residue
Full
EDG
Crude soybean oil
100%
2,50% PL
Gums
1,06%
yield
0,92% PL
0,14% NO
PLC EDG
98,9%
0,25% PL
1,33% DAG
Acid gums
0,40%
yield
0,20% PL
0,20% NO
ADG
98,54%
0,05% PL
total loss:
70%PE/PC
100%
no
conversion + free
PE/PC
FFA
1,46%
De Smet Presentation
28
Enzymatic degumming PLC
° Case study crude SB0 2.5% PL (70% PE/PC)
- EDG vs waterdegumming / ADG
- P < 100 ppm, post-ADG needed (or PLA-EDG!)
- Gain in crude oil yield: about 1.8 / 2.2%
- No FFA, no extra loss in deodorising
- Net gain in RBD oil yield after full refining:1.8 / 2.2%
Best economics when combining PLC-WDG with PLA-EDG
De Smet Presentation
29
Enzymatic degumming: key = yield
Main driving factor: yield
+ Less oil loss with gums, giving higher oil yields
+ Very suitable for high PL-oils (SBO, RSO) not for PO
+ Less effluent, less low value-added side products
+/- Not all processes yet industrially proven,
but high expectations
+/- Enzyme cost main factor in OPEX, low CAPEX
- No lecithin
- what enzyme to use? Now & in future?
De Smet Presentation
30
Enzymatic deoiling of gums (EDO)
Alternative enzymatic processes for oil recovery:
Recovery of oil from lecithin
- Most oils are shipped and traded in a crude form
- Wateredegumming applied mainly to prevent settling of
gums in storage tanks
- Gums contribute to shelf life of crude oils
- Part of gums converted to lecithin
Q: can entrained oil be recovered from the gums?
De Smet Presentation
31
Lecithin deoiling
Process principle
Enzymatic Treatment of Lecithin Fraction (from WDG)
LECITHIN
LYSO-LECITHIN
35-50% oil
50-65% A.I.
+
RECOVERED
OIL
Eg. Lecitase Ultra
250-500 ppm on dry lecithin
Less than
half as
compared to
EDG
Extracted
Meal in DT
Back to main
Oil stream
Wet gums
De Smet Presentation
32
Lecithin deoiling
Wet Gums
Lecitase
Ultra
Oil
+
PLA2
Wet Gums + Enzyme
2-4 hrs
De Smet Presentation
De-oiled
Gums
Deoiled gums + Oil
33
Lecithin deoiling
More enzyme gives :
- Faster Oil Recovery
- More recovered oil
-Darker oil with higher
FFA content
100 ppm
250 ppm
500 ppm
Lab trials conducted by
De Smet Presentation
34
Lecithin deoiling
Enzymaric deoiling of soy lecithin
1.Cooling Soy Lecithin to 55°C
2. Addition of Lecitase Ultra (250 – 500 ppm)
3. Enzymatic reaction (2-4 hr at 55°C)
4. Heating treated soy lecithin to min. 70°C
5. Separation recovered oil from lyso-lecithin
De Smet Presentation
35
Lecithin deoiling potential with PLA
70% conversion PL to LL+FFA
RECOVERED OIL FROM SOY LECITHIN USING PLA2
- Recovery : 80-90% of oil usually entrained in gums
- Calculation example for 1 ton crude soybean oil
LECITHIN
28 kg dry gums
from which 8 kg oil
WDG
PLA2
RECOVERED OIL
10 kg recovered oil
FFA : 35-40%
+
LYSO-LECITHIN
18 kg dry gums
part= lysolecithin
982 kg WDG SBO
with 200 ppm P
?
Meal
1000 kg crude SBO
with 1000 ppm P
De Smet Presentation
36
Lecithin deoiling potential with PLC
70% conversion PL (PE/PC) to DAG+ Phosphate residue
RECOVERED OIL FROM SOY LECITHIN IF USING PLC
- Recovery : 80-90% of oil usually entrained in gums+ DAG
- Calculation example for 1 ton crude soybean oil
LECITHIN
28 kg dry gums
from which 8 kg oil
WDG
PLC
RECOVERED OIL
18 kg recovered oil
DAG : 55-60%
+
LYSO-LECITHIN
10 kg dry gums
990 kg WDG SBO
with 200 ppm P
?
Meal
1000 kg crude SBO
with 1000 ppm P
De Smet Presentation
37
Enzymatic oil degumming (EDG) or
Enzymatic lecithin deoiling (EDO)
EDG:
- When applied on crude oil, recovered oil directly blended
into main oil stream ( PLA: FFA , PLC: DAG
)
- Gums not useable to produce functional lecithins
- Larger volumes to be treated (full crude oil stream)
EDO:
- Phospholipids more concentrated and hence more accessible (?)
- But much higher viscosity (dilution with oil = solution)
- Gums not useable to produce functional lecithins
- Recovered oil kept separate from main oil stream (eg. Biodiesel)
- Much smaller streams to be treated (30-40 times less volume)
De Smet Presentation
38
Trends in Enzymatic
Oil Modification
21-23 october
Application of vegetable oil: determined by physical state
Interesterification
Hydrogenation
chemical
37.4 Mill. tons
42.6 Mill. tons
Cotton oil
Olive oil
(Animal fats)
Palm
and
Soybean
oil
are
Soybean oil
Palm oil
Rapeseed oil dominating the O&F market Palm Kernel oil
(semi)
Sunflower oil
Liquid
oil
but they are so different…
Peanut oil
Coconut oil
Solid oil
Fractionation
De Smet Presentation
physical
39
Trends in Enzymatic
Oil Modification
PHSBO IV 70
% S F C ( s e ria l m e t h o d )
100
47% TFA
41%
35%
30%
23%
16%
12%
80
60
40
Hydrogenation improves the
physical properties but
reduces nutritional value
Main drawback: formation
of TFA
Negative impact on health
(Cholestreol)
Today clear tendency to
avoid, and even ban TFA
out of Foods
20
0
0
10
20
30
40
50
Temperature (°C)
De Smet Presentation
40
Trends in Enzymatic
Oil Modification
TFA intake from
foods (US)
Animal products
(meat, dairy)
Candy Breakfast
21%
1%
cereals
1%
Cakes, cookies,
crackers, bread
40%
Does the consumer know
where these TFA are?
Spreadable
margarine
17%
Salad dressing
3%
Household
shortening
4%
Chips
(potatao,corn)
5%
Fried potatoes
8%
De Smet Presentation
41
Trends in Enzymatic
Oil Modification
PH Soybean oil fractionation
Frying oil
Salad oil
IV
Yield %
TFA %
MP °C
Feed 1
Olein
Stearin
Feed 2
Olein
Stearin
109
112.5
92
87
94
74
85
15
/
65
35
/
Can11fractionation
be a20(partial)
9
20
18
19
/
25
/
solution
to27 reduce TFA?
23
32
SFC
10°C
7
0
33
28
0
65
20°C
2
/
16
9
/
40
30°C
/
/
2
0
/
7
/
>36
/
>10
/
CT 0°C hr
/
De Smet Presentation
42
Trends in Enzymatic
Oil Modification
What alternative do we
have then to avoid TFA
when modifying oils?
Chemical
Interesterification = first
answer to low/zero TFA
chemical modification
De Smet Presentation
43
Trends in Enzymatic
Oil Modification
Ban on TFA and hence partial hydrogenation, has
increased demand for interesterification
But chemical interesterification also under
pressure:
“Early scientific reports -- one of which was released in mid-January 2007 by
joint-researchers from Malaysia and the UK -- suggest that interesterified fat
is far more harmful than trans fats.
Interesterified fat was found to depress the level of HDL (good cholesterol)
more than trans fat.
In addition, interesterified fat raised blood glucose levels and depressed the
level of insulin. This strongly suggests that interesterified fat could lead to
diabetes”
Solution: enzymatic interesterification & MORE USE OF PALM OIL
De Smet Presentation
44
Enzymatic Oil Interesterification:
Proven principle
Enzymatic
interesterification:
today a proven
technology
No
contaminants
CRUDE OIL
PRE-TREATMENT
neutra-bleach-deodo
(Soaps-FAME)
(Dialkylketones)
ENZYMATIC INTERESTERIFICATION
DEODORISATION
(BRUSH)
FFA
Diglycerides
None
4x125 kg
reactors
EIE OIL
Feed
Tank
RBD
blend
By-products
EIE >> Oil quality >> CIE
Product
Tank
EIE reactors
EIE
blend
Deodoriser
De Smet Presentation
45
Enzymatic Oil Interesterification:
Proven process
40
C.I.E.
PST: SBO
35
E.I.E
50:50
30
% S FC
25
IS EIE giving same
results as CIE?
40:60
20
15
30:70
10
10:90 Final CH
20:80 Final CH
30:70 Final CH
40:60 Final CH
50:50 Final CH
10:90 Final Enz
20:80 Final Enz
30:70 Final Enz
40:60 Final Enz
50:50 Final Enz
20:80
5
10:90
0
0
5
10
15
20
25
30
35
40
45
Temperature [C]
CIE full random = EIE 1,3 selective (for commodity blends)
De Smet Presentation
46
Enzymatic Oil Interesterification:
Proven technology
EIE plant
4 x 500 kg
(50-80 tpd)
EIE simpler or more
complicated than CIE?
P
l
a
n
t
-
D
e
s
i
g
n
• Feedstock quality
• Feedstock composition
• Feedstock changes
De Smet Presentation
47
Enzymatic oil processing
What may bring the future?
Enzymatic hydrogenation:
Any potential in future ?
Enzymes in oleochemistry:
Enzymatically produced biodiesel
Enzymes in bleaching:
Selective destruction of
carotene/chlorophyl?
Enzyme assisted expelling:
release of oil under mild conditions
(cfr. Algae)
And what about GM of oil composition inside the crop to ease oil
refining & increase nutritional value
Anything possible... Where will we be in 10 years?
De Smet Presentation
48
Enzymes play an important role in
our foodproducts
Why not in processing of one of its
major ingredients:
OILS and FATS
Marc Kellens
Desmet Ballestra Group,
Zaventem, Belgium
De Smet Presentation
49