Global Innovation

Enzyme Degumming for

Physical Refining

SCI
Enzymatic Processing and Modifications-
Current and Future Trends
Het Pand, Univerisity of Ghent, Belgium
21 June 2011
1
 Overview
Global Innovation

• Physical Refining
• Phospholipid Chemistry
• Enzyme Reaction Fundamentals
• Process Comparisons
• Commercial Phospholipase
• Intellectual Property
• Enzymatic Degumming
• Bleaching
• Deodorization / De-acidification

2
© 2011 Bunge
 Lipids and water affinity
Global Innovation
Phospholipid Triglyceride
O O
CH2-O-C-R1 CH2-O-C-R1
O O
R2-C-O-C-H R2-C-O-C-H
O O
CH2-O-P-O-X CH2-O-C-R3
O-

water oil
affinity affinity
R# = fatty acid chains
X = H, choline, ethanolamine, serine, inositol, etc.
3
© 2011 Bunge
 Phospholipids in vegetable oils
Global Innovation

Hydratable PC, PI, and PS

Slightly-Hydratable PA and PE

Non-Hydratable Mg/Ca/Fe salts of PA, PE

oil
water affinity
affinity

© 2011 Bunge
 Hydration
Global Innovation

Phospholipid Relative Rate of Hydration

PC 100
PI 44
PI (Ca salt) 24
PE 16
PA 8.5
PE (Ca salt) 0.9
PA (Ca salt) 0.6

(1) Sen Gupta, A.K., Fette Seifen Anstrichmittel V.88 pages 79-86 (1986) in Segers, J.C., et al., “Degumming – Theory and Practice” published by American Oil
Chemists’s Society in “Edible fats and Oils processing: basic principals and modern practices: World conference proceedings”, edited by David Erickson,
(1990) pages 88-93.
5
© 2011 Bunge
 Non-Hydratable Phospholipid
Global Innovation

6
© 2011 Bunge
 Phospholipid Hydration
Global Innovation

Phospholipid Relative Rate of Hydration

PC 100
PI 44
PI (Ca salt) 24
PE 16
PA 8.5
PE (Ca salt) 0.9
PA (Ca salt) 0.6

(1) Sen Gupta, A.K., Fette Seifen Anstrichmittel V.88 pages 79-86 (1986) in Segers, J.C., et al., “Degumming – Theory and Practice” published by American Oil
Chemists’s Society in “Edible fats and Oils processing: basic principals and modern practices: World conference proceedings”, edited by David Erickson,
(1990) pages 88-93.
7
© 2011 Bunge
 Enzymatic Refining - fundamentals
Global Innovation

• In the conventional degumming and

chemical refining process, gums work
as emulsifiers and are responsible for
the major part of the oil losses.

• In enzymatic degumming, the

enzyme action eliminates the
emulsification properties of the gums.
The oil savings are proportional to the
phosphorus (gums) in a ratio of 1 (oil)
to 2 (gums).
Photographs provided by Verenium – Used with permission

8
© 2011 Bunge
 PHOSPHOLIPASES: mode of action
Global Innovation

© 2011 Bunge
 PLA Enzyme Degumming
Global Innovation

• Phospholipase A1
• Lyso Lecithin
• Phospholipase A2
• Lyso Lecithin

• Phospholipase C
• Phospho-species

10
© 2011 Bunge Photographed by C. Dayton
 Comparing Refining Technologies
Global Innovation Refined Oil Heavy Phase DDO Yield

Caustic + + 96.5

PLA1 + + 97.4

Crude
PLA + PLC + + 98.3
Vegetable
Oil

TAG gum DAG Phosphatidic Group Fatty acid

11
© 2011 Bunge
 Commercial Enzymes for Oil Refining
Global Innovation

AB Enzymes’ PLA2, Rohalase® MPL

Dansico’s PLA2, FoodPro™ LysoMax

Novozymes’ PLA1, Lecitase® Ultra

Verenium’s PLC, Purifine™

DSM’s PLA2, GumZyme™

Generation 1 Generation 2
1990’s 2008

PLA PLA / PLC

Physical Physical Physical Refining
97.4 % 98.3 %

12
© 2011 Bunge
 Intellectual Property
Global Innovation

• US 5,264,367 – Aalrust et al.

• Phospholipase A2 for degumming
• US 7,226,771 – Gramatikova et al.
• Phospholipase C
• US 7,713,727– Dayton et al.
• Antifouling
• US 2008/0182322 – Dayton et al.
• Combination of phospholipases
• US 2009/0069587 – Dayton et al.
• Combination of phospholipases with reduced
reaction rates
13
© 2011 Bunge
 Optimum Enzyme pH
Global Innovation Caustic Water Enzymes

Mixer
Citric Acid

Crude Mixer Acid

Oil Retention cooler
High Shear
Mixer
Economizer

Refined oil
Surge Enzyme
Retention

Preheater
Centrifuge
Citric Acid
US 7,713,727

Heavy Phase
gums

14
© 2011 Bunge
 High Shear Mixing
Global Innovation

15
© 2011 Bunge
 Enzymatic Degummed Specification
Global Innovation

• Phosphorous ≤ 10 ppm
• Calcium ≤ 2 ppm
• Magnesium ≤ 2 ppm
• Iron ≤ 0.001 ppm
• Free Fatty Acid 0.4 – 1.3 %

16
© 2011 Bunge
 Lead-Lag Bleaching
Global Innovation
Silica
Bleaching Earth
Spent Clay
Filter Press

Refined oil
Surge Slurry
Vacuum
Slurry
Dryer

Clay
Filter Press

Vacuum
Bleacher Bleached Oil
Storage

17
© 2011 Bunge
 Enzymatic Degummed and Bleached
Specification
Global Innovation

• Phosphorous ≤ 0.5 ppm

• Calcium ≤ below detection limit
• Magnesium ≤ below detection limit
• Iron ≤ below detection limit
• “Chlorophyll” ≤ 30 ppb
• Free Fatty Acid 0.4 – 1.3 %
• Peroxide Value 0 meq/kg

18
© 2011 Bunge
 Fatty
Acids

Hot Well

High
Unsaponifiable

RB
Deodorized
Oil

19
 Physically Refined Specification
Global Innovation

• Flavor – Bland
• Free Fatty Acid 0.05 % max
• Peroxide Value 0 meq/kg
• OSI ≥ 6 hours at 110° C (typically ≥ 8.5)
• Tocopherols ≤ 800 ppm
• Lovibond Color
• Red ≤ 1.0 (typically 0.3)
• Yellow ≤ 10 (typically 2.0)

20
© 2011 Bunge
 Enzyme Refining – Industrial Scale
Global Innovation
PLA PLA / PLC
Advantages
Caustic Enzymatic Enzymatic
no soapstock Refining Refining Refining
no washwater Starting Phos 500 ppm 500 ppm 500 ppm
lyso-gums and / or level in crude
phospho-species oil
reduced process time Phos level 2 ppm 2 ppm 2 ppm
reduction in chemicals after
robust centrifuge
Centrifuge 3.19 1.13 0.62
Discharge
(dry %)
Yield of oil 96.5 97.4 98.3
(%)

Bunge Physical Refining Plant

21
© 2011 Bunge
 Physically Refined Soybean Oil
Global Innovation

Physically Refining Plant continuously

operated since 2003 producing greater
than 3,500,000 tonnes of commercial
salad oil to customers.

22
© 2011 Bunge
 Thank You!
Global Innovation

Photograph by P. Dayton in October 2010 in Cancun, Mexico. 23

© 2011 Bunge