Enzymatic Oil Refining :

The Solution to Quality and Profitability

W. De Greyt and M. Kellens

Desmet Ballestra Group

Zaventem, Belgium
 Edible Oil Refining
‘Purpose of refining of oils for edible uses is to remove
undesirable substances and components while maintaining
the nutritional quality and stability of the refined oil’1

Crude Oil REFINING Refined Oil

Required refining capacity : > 500.000 TPD

Undesirable components Quality requirements

- FFA - Good stability
- Phospholipids - Good shelf life
- Traces of metals - Bland odor & taste
- Pigments - Good nutritional quality
- Contaminants - Safe (no contaminants)
- Colouring components - Healthy (vitamins)

2
 Edible Oil Refining - Evolution
1915 2015

Gradual improvement of the process technology

* Processing under low vacuum (for oil quality reasons);
* Evolution from batch to semi- to continuous operation (plant performance);
* Optimized deodorization (low pressure, optimum heat recovery)
* Milder processing, less chemicals (chem > phys) USE OF ENZYMES

3
ENZYMATIC OIL REFINING OILSEEDS

Mechanical Pressing
Oil Extraction Deoiled Meal
Solvent extraction
1 Crude Oil
2
3 Gums LECITHIN
Enzymes in
Oil Refining Waterdegumming
4

WDG Oil

Acid Gums Acid degumming

Soapstock Alkali Neutralisation
5

Spent
Bleaching Bleaching
bleaching earth

Physical deacidification
Deodorization Deodorizer Distillate
Deodorization

Refined Oil

CHEMICAL PHYSICAL

4
 Enzymatic Oil Refining: some proven, some under
development and some waiting to be proven industrially
Enzymatic Process Objective Status
Miscella Degumming Max. PL removal + yield increase. Under development
1 On crude oil miscella (crushing plant)
(Partial)Water Degumming Partial PL removal + yield increase. Industrially applied
2 On crude, non-WDG oils (crushing plant)
Gums Deoiling Max. Oil recovery from wet gums Ready for industrial
3 On wet gums (crushing plant) application
Full (‘deep’) Degumming Full PL removal + yield increase Industrially applied
4 On waterdegummed oils (refining plant)
Bleaching Degradation of color pigments Under development
5 On waterdegummed oils (refining plant)

Enzymatic Oil Degumming : industrially proven and well accepted

Efficient degumming and higher oil yield

5
 Enzymatic oil degumming

The degumming process for the 21st century finally come true ?
CURRENT SITUATION
Phospholipase A1
• Availability of more stable &
O (cost-) efficient enzymes
Phospholipase A2 CH2 -O-C-R 1 • Different enzymes/enzyme suppliers
R2-C-O-CH
Phospholipase B
- Lecitase Ultra (PL-A1, Novozymes)
O - Rohalase PL-XTRA (PL-A2, AB Enzymes)
O
CH2-O-P-O-X - Lysomax Oil (LAT, PL-A2, Du Pont)
O - Purifine PLC (PL-C, DSM)
Phospholipase C Phospholipase D
- Purifine 2G/3G (PL-C + PL-A2, DSM)
X = H, choline, ethanolamine, serine, inositol, etc.
• Different approach
- Increased oil yield as main driver
- (Also) applied on crude oils

6
Industrial Enzymatic Degumming - 2014

Source :

* Worldwide : > 30 crushing/refining plants applying enzymatic degumming

* Mostly soybean oil processors in Latin America and USA

7
Enzymatic water degumming

 Applied in crushing plants

* On crude oil
* With PL-C or PL-C/PL-A cocktails
* Not for Lecithin producers

 Higher oil yield is main driver

* Max. generation of diglycerides (from PL)
* Some formation of FFA (also from PL)
* Less oil entrainment in less gums

 Net revenue will depend on :

* PL-content in crude oil (highest in soybean oil from expandates)
* Price difference between WDG oil and meal (lecithin!)
* Enzyme cost (enzyme price x dosing rate)

8
Enzymatic water degumming: PLC most preferred
O

=
O
CH-O-C-R1

=
CH2-O-C-R1 O

=
R -C-O-CH
+ H2O PLC R -C-O-CH
2 +
HO-P-O-X

=
2
O O-
=

O
O CHOH
=

2
CH -O-P-O-X
2

O-
Phospholipids DIGLYCERIDES PHOSPHATE-ESTER

Yield increase : DAG + Less entrained Neutral Oil in less gums

Commercial Enzyme Active enzymes Selectivity Conversion products

Purifine® - PLC PLC Only PC+ PE Only DAG
Purifine® - 2G PLC + PLA2 Mainly PC + PE Mainly DAG + some FFA
Purifine® - 3G PLC +PLA2 + PI-PLC PC + PE + PI Mainly DAG + some FFA

10
Enzymatic water degumming of soybean oil

Crude soybean oil : Phospholipid composition

Crude oil
. theoretical DAG formation
Total PL (%) 2.06 = PC*0,7717 + PE*0,8154
PC 0.70 Can be degraded by PLC + PI*0,7027
PE 0.54
PI 0.36 Can be degraded by PI- PLC
= 1.23%
PA 0.3

Enzymatic waterdegumming with Purifine 3G (=PLC +PLA2 +PI-PLC)

Crude Enzymatic degummed
FFA (%) 0.83 1.18  Slight FFA increase (from PLA2 action)

P 845 52  No deep degumming (yet)

Ca 111 27
Mg 117 17  0.62% extra DAG (PLC action)
= approx. 50 % of theoretical max.
DAG (%) 0.87 1.49

11
 16 1,5 USD/ton
Revenue i.f.o. enzyme cost

∆ revenue : EDG-WDG (USD/ton)

14
and ∆ (oil-meal)
12 3 USD/ton
Extra Revenue from Enzymatic 10
8 6 USD/ton
Water degumming 6
4
2
0
1200
-2 0 200 400 600 800 1000
1100 SOY -4 ∆(oil-meal) (USD/ton)
1000 -6
900 1.8% oil yield increase
800
∆ = 665 USD/ton
Oil
700
600 Determining Factors
500 ∆ = 250 USD/ton
400
Meal  Price difference oil – meal
300
0 5 10 15 20 25 30
 Enzyme cost
Jan 2013 Sep 2015  Achievable oil yield increase
Average ∆ (01/2013 – 09/2015) : 400 USD/ton
Oil and Enzyme dependent
Average ∆ (01/2010 – 09/2015) : 550 USD/ton

12
 Extra Oil Yield Increase from Enzymatic Water degumming

Enzymatic WDG with Purifine®

POTENTIEL YIELD GAIN PLC Enzymatic WDG of crude soybean oil
3,00 with 2.5% phospholipds
2,50
soya TOTAL INDUSTRIAL DATA
Canola/Sun Enzyme Oil yield increase (%)
2,00
% oil yield gain (max)

VERENIUM DIGLYC Purifine® - PLC 1.4-1.7

D
1,50 VERENIUM OIL
NO VERENIUM TOTAL
Purifine® - 2G 1.9
1,00 DAG
Purifine® - 3G 2.4
0,50

Source : Ventrici, E., Molinos.Data presented at the 2014 AOCS

0,00 Conference (Orlando,FL)
0 200 400 600 800 1000 1200 1400
ppm P in crude oil

DAG : Diglycerides NO : Neutral Oil

Feedstock
dependent (ppm P)
Highest Oil Yield increase with Purifine 3G on crude soybean oil from expandates
(max. P content)

13
Full ‘deep’ enzymatic degumming

 Applied in crushing or refining plants

* On crude or waterdegummed oil
* With PL-A1 or PL-A2
* Not yet fully proven with Purifine® enzymes

 Degumming efficiency vs Yield increase

* Efficient degumming (P < 10 ppm) required
* Yield increase from formation of FFA and reduced entrained oil in gums
* FFA will be stripped during refining and valorized as distillate

 Applications
* Mainly on (crude) soybean oil, but also on other oils (rape, sun,...)
* As part of the pretreatment process for biodiesel production
* Missing link for physical refining of soft oils ?

14
Full ‘deep’ enzymatic degumming
O
CH OH

=
2
CH2-O-C-R1 O
PLA1

=
R -C-O-CH
+ H2O R -C-O-CH
2 + H-O-C-R1

=
2 O
=

O PLA2 O

=
O CH -O-P-O-X
=

CH -O-P-O-X 2
2
-
O-
O
Phospholipids Lyso-Phospholipids FFA

 Phospholipase- A1 (Lecitase Ultra, Novozymes) : most industrially applied

 Phospholipase-A2 (Rohalase PL-XTRA, AB Enzymes) – splits off FFA at sn-2 position
 Conversion of ALL phospholipids in hydratable lyso-phospholipids and FFA

Yield increase : FFA + Less entrained Neutral Oil in less gums

Valorized as deodorizer distillate

16
 Degumming efficiency vs Yield Increase
Deep Enzymatic Degumming of Crude Soybean Oil

2,25 120 min

2 Time (min.) P (ppm) FFA (%)
Lyso-PL
1,75
Mmol/100g oil

0 875 0,34
1,5
1,25
10 32 0,44
1 60 9 0,68
0,75
PL 120 7 0,84
0,5
0,25
300 5 0,96
0
0 50 100 150 200 250 300

Reaction time (min.)

• After 10 min. : good degumming (32 ppm P), but almost no yield increase (∆ FFA= 0.1%)
• After 120 min. : good degumming (7 ppm P), and good yield increase (∆ FFA = 0.5%)

Reaction time required for yield increase

17
 Crude Oil
Applications
DEEP ENZYMATIC Lyso-Gums
DEGUMMING

Extra biodiesel EDG Oil

yield

Silica treatment or
washing

Distillate FFA stripping

Bleaching

Acid Esterification
Physical deacidification
Transesterification Distillate
Deodorization

BIODIESEL
Refined Food Oil

meeting Light color, bland taste

EN/ASTM specs Good stability
No contaminants,....

18
Deep Enzymatic Degumming of Rapeseed Oil
Enzyme assisted Acid assisted
Acid degumming Enzymatic degumming

Crude Oil Rohalase PL-XTRA (PLA2) Lecitase Ultra (PLA1)

Oil conditioning
Citric acid (ppm) 300 650 300 650
NaOH (ppm) 65 150 90 200
Enzyme reaction
Enzyme dosing (ppm) 50 50 50 50
Reaction time (hr) 1 2 1 2
Oil quality
FFA 1.42 1.56 1.68 1.59 1.77
P 477 83 4.6 67 3.7
Ca + Mg 231 77 1.1 63 1.4

 Deep enzymatic degumming (P < 5 ppm) is possible with PLA1 & PLA2
 Correct acid conditioning and enzyme dosing is required

19
Deep Enzymatic Degumming for Biodiesel Production

Crude RS oil
Crude Rapeseed oil FFA : 2.40%
P: 552 ppm
Ca : 213 ppm
Enzymatic degumming Mg : 50 ppm
(50 ppm Lecitase Ultra – 90 min.-55°C)

Silica treatment
(500 ppm citric acid – 0.3% Silica)
Refined RS oil
FFA : 0.15%
FFA stripping P: 0.9 ppm
(235°C - 3mbar – 1.5% steam – 90 min) Ca/Mg : < 0.5 ppm

BIODIESEL
MAG : 0.43%
BIODIESEL
Good quality DAG : 0.12%
PRODUCTION TAG : 0.09%
Free SG : 11 ppm
Brilliant appearance

21
Enzymatic degumming : current situation
Most widely applied enzymatic oil process
• Different enzyme (cocktails) are today commercially available
• Enzymatic waterdegumming or deep degumming
• Proven oil yield increase

Conversion of PL in FFA or diglycerides

Less neutral oil entrainment in the lyso-gums phase

Why not applied more ?

• Economical reasons (crude oil vs lecithin vs meal price)
• Process reasons (consistent full enzymatic degumming remains a challenge)
• Confusion (when to apply, on which oil, what to do with sidestream, dependency..)

Is enzymatic gums deoiling an alternative ?

22
Enzymatic gums deoiling : potential benefits
Enzyme reaction
Wet Gums Lyso-Lecithin + Recovered Oil

1. Applied on a side stream (wet gums) with no impact on the degumming process
* Wet gums : 4-5% of crude oil flow (40-50 TPD vs 1000 TPD enzymatic degumming for SBO)

2. High flexibility
* Can be applied depending on economics (lecithin vs oil vs meal)

3. Recovered oil (additional yield) is collected as separate stream

* Can be recycled back to crude/WDG oil or valorized separately (e.g. biodiesel)

4. Potential Lower enzyme consumption (compared to oil degumming)

23
 Recovered oil quality (from soy gums)
FFA – recovered oil (%) P – recovered oil (ppm)
35 110
FFA recovered oil (%)

100

P recovered oil (ppm)

30
90
25 80
20 70
60
15
Correlation 50
No Correlation
10 40
20 30 40 50 60 70 80 90 100 20 30 40 50 60 70 80 90 100
Oil recovery (% on NO in gums ) Oil recovery (% on NO in gums )

Soy gums with 41% moisture and 32% NO on DM, 250-400 ppm Lecitase Ultra, 4-6 hr at 55°C

Oil recovery : up to 90% (on NO in gums) = 0.8-1.0% on crude soy oil

Recovered oil quality : FFA : 30-35%

P-content : 70-100 ppm

25
 Conclusions
 Enzymatic oil processing appeals to the growing demand for
milder and more sustainable refining;

 Today, enzymatic oil degumming is the only industrially proven

enzymatic process in oil refining

 Enzymatic water degumming is successfully applied on crude soybean

oil, but not yet with same success on other crude oils (too low P-content)

 Full enzymatic degumming is mostly applied in the pretreatment of

soybean/rapeseed oil for biodiesel production.

 Enzymatic lecithin deoiling is an interesting alternative, ready to be

tested industrially (PLC/PLA cocktail)

26
 Thank you for your attention!!

W. De Greyt and M. Kellens

Desmet Ballestra Group

Zaventem, Belgium

Science Behind Technology 28