Enzymatic Degumming (=EDG) today a summary

Novozymes, CS Oils & Fats

26/10/2011

Outline Novozymes brief introduction Enzymatic degumming History and principles Updating the knowledge base Main benefits Tools, documents and CS support EDG in biodiesel production Outlook

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Global presence

Sales Offices Production Research

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Novozymes in brief
World leader in industrial enzymes & microorganisms and market leader in all industries where present More than 700 products used in 130 countries in 40 different industries R&D activities in 5 countries

13-14% of revenue invested in R&D

New products represented around 25% of total sales More than 6,500 granted or pending patents 43 new products launched during the last 5 years
Enzymes for industrial use Market size ~ DKK 19 billion Novozymes' business composition Revenue 2010 ~ DKK 10 billion

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Current & Developing Enzyme applications in oils and fats processing

Enzymatic Interesterification
Change in fat melting properties for margarine and shortenings

Enzymatic degumming
Removal of gums to ensure stability, yield & quality

Ester synthesis
Production of Biodiesel, speciality esters and FAEE

Speciality fats for nutritional use

Synthesis of omega 3 & similar products for healthy nutrition

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What is degumming?
A part of the refining process of vegetable oils A process for removing phospholipids and other impurities Not a single process Can be applied to both crude and water-washed oils Normally associated with significant oil losses if nonenzymatic

Criterion for success is viewed as resulting phosphorus level but improving oil yield has gained more importance

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What is enzymatic degumming & why do it?

Enzymatic Degumming with Lecitase Ultra is a combination of a mild acid treatment to convert Ca & Mg salts to a form that the enzyme can attack with an enzyme hydrolysis to make all the gums hydrophilic Increased yields result from decreased oil binding by gums because they are now hydrophilic resulting from the partial hydrolysis of phospholipids Full phosphorus reduction results from a combined effect of enzyme and acid

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First enzyme-based process

Patent filed by Lurgi in the early 1990s Good final P level Heat stable High enzyme cost required recycling of gum phase Porcine enzyme Phospholipase A2

http://www.lurgi.de/lurgi_headoffice_kopie/english/nbsp/menu/products/food_and_oleochemicals/degumming/index.html

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Phospholipid chemistry I
Fats and Phospholipids
Fatty acid

Glycerol

Glycerol Head group

Phosphate

Phosphatidic acid

Some phospholipids have a charged head group, making this part of the molecule hydrophilic. Phosphatidic acid is present as Ca or Mg salt and bears no charge making it fully oil soluble

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Phospholipid chemistry II
Nature PC (Phosphatidyl PC is hydratable at all pH-values choline)
PE (Phosphatidyl enthanolamine) When PE has a net charge, it is hydratable(<pH3, >pH9)

PI (phosphatidyl inositol)
PA (phosphatidic acid) NHP (nonhydratabel phosphatides)

PI hydratable at all pH values

To make PA hydratable, it must be dissociated and be present as alkali salt No net charge, calcium and magnesium salts of phosphatidic acid & non hydratable, the NHPs have to be at the oil/water interface for hydrolysis

Adapted from: A. Dijkstra, 101st AOCS Annual Meeting & Expo Timothy L Mounts Award Address

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Phospholipid chemistry III phospholipase PLA1

Enzymatic removal of one fatty acid from lecithins enables extractive removal of the lysolecithins

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The principle of enzymatic degumming is to modify the phospholipid

Oil Oil

Hydrolysis Water Water

Splitting off a fatty acid makes the molecule more hydrophilic making the L-PA (lyso-phosphatidic acid) & L-PI (Lyso-phosphatidyl inositol) easy to hydrate and remove with the water phase.
A fine dispersion increases the interfacial area and decreases diffusion

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First microbial alternative to PLA2

Product was called Lecitase Novo Degumming was at least as good as PLA2 (phospholipase A2) Heat stability was inferior Lower cost made single use acceptable But improvements were needed (next slide)
Lecitase Novo for Degumming of Vegetable Oils

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Second microbial alternative to PLA2

Product is called Lecitase Ultra Degumming at least as good as PLA2 Heat stability significantly improved
Lecitase Ultra for Degumming of Vegetable Oils

Used in many oil refining plants worldwide

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Performance of the three phospholipases

Lecitase Ultra Pancreatic PL Lecitase Novo
Relative performance

100 80 60 40
3.5 3 3.7 4.0 4.2 4.5 5.0 pH 5.5 6.2 8.0 30-35 40 45

20
C) Temp. (C)
50 55 60 65

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What does enzyme have to do?

1) Crude oil
Remove phosphorus without totally hydrolysing the gum Enhance the water degumming process Stop the gum from being hydrophobic Degrade the NHP fraction 2) Water degummed oil Remove remaining phosphorus Degrade the NHP fraction Limit FFA generation

EDG is not only an enzyme process but works in conjunction with chelating/buffering agents

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Standard Enzymatic Degumming Process

Retention vessel Oil tank

12 hours

(70-80)C

20 min
Retention vessels

Refined Oil

30 C Heater

Centrifugal separator Highshear mixer

70 C
Highshear mixer

55 C
NaOH to neutralize citric acid water
Mixer

Oil pump

Lyso gums

Citric acid

Enzyme

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Enzymatic Degumming the role of the stages I

The incoming oil contains Ca/Mg salts of PA that have to be turned into hydratable PA. Citric or other acids convert the PA salt to the dissociated form. A temperature >60C is preferable

Acid addition

Shear mixing

Ensures the citric acid is well distributed and brought into contact with the phospholipids to make conversion of the PA and any other non-hydratable PL

Caustic addition

The addition of acid results in a water phase pH below the optimum for the enzyme, so NaOH is added to avoid this and to (possibly) convert the free PA to the hydratable sodium salt

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Enzymatic Degumming the role of the stages II

A total of 3% water is normally used for crude oil degumming. Mixing enzyme & water in-line aids dispersion and avoids the risk of making up dilute enzyme solutions

Water + enzyme addition

Shear mixing

Ensures the enzyme is well distributed and by producing small droplets, ensures a large surface area for lecithin modification

Reactor design

Enzymatic degumming is normally a continuous process so a CSTR or multi tank design avoids any problems with oil by-passing the reactor

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Enzymatic Degumming the role of the stages III

Calcium citrate may precipitate in centrifugation but lowering pH by acid addition can reduce this.

2nd citric addition

Emulsion needs to be converted from water in oil to oil in water and heating facilitates this conversion and allows gums to contract, squeezing out oil. A secondary function is Heating to to inactivate residual enzyme. 70-80C

Separation of heavy gum phase from oil. Some difficult oils e.g. cotton seed and rice bran benefit from a second water Centrifugawashing to remove more phosphorus.
tion

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Main benefit of enzymatic degumming

Oil losses are virtually eliminated because:

The gum phase becomes hydrophilic and does not bind oil

The gum volume is reduced and is virtually oil free

From left to right: sediment of soybean oil from lab tests. Left (2% water) and right (2% water with Lecitase Ultra)

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How phospholipids bind oil

The ability of water to hydrate the phospholipid depends on the balance between the attraction of water to the hydrophilic head and the solubility of the hydrophobic tail in the oil phase

Phospholipids will distribute themselves at the oil/water interface when water is added. When the gum is removed by centrifugation some oil is trapped by this structure leading to a loss of the entrained oil

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Additional benefits for Bio-Diesel

Degumming of raw material Enzymatic degumming applied to crude or water degummed oils
Increases yield Improves separation of glycerol and FAME phases Reduces carry over of acid 1 Enzymatically degummed 2 Acid degummed

Reduces catalyst consumption

Phosphorus WDG Oil Oil Loss

pH

Crude SBO

175 ppm 5 ppm

6.09

50 ppm Enzyme

30ppm EDG SBO

Acid + Neutralization

0.1% ADG SBO

0.47% 5.14 13 ppm 1.62% 3.26

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Economic Evaluations
Overall Loss %

5.73% 5.80% 5.60% 5.40% 5.20% 5.00% 4.80% 4.60% 4.40% 4.20%

5.57% 5.41% 5.18%

4.79%

Overall Loss %

Water Degumming Water Degumming Water Degumming Water Degumming + Chemical + Semi Physical + Acid + Enzyme Refining Refining Degumming Degumming

Full Enzyme Degumming

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Cost calculation example

100,000,000 Kgs. Of Oil Processed Chemical Refining
% Amount (#) Value ($) %

Particulars COST: Crude oil

Phosphoric acid (85%) Citric acid (100%) NaOH (100%) Lecitase Ultra Acid silica usage Std. silica usage Steam (gum drying) TOTAL COST INCOME: Refined oil Soapstock sold Gums in meal Clay in meal Distillate Fatty acid TOTAL INCOME

$/#

Enzymatic Refining
Amount (#) Value ($)

0.76 0.82 1.87 0.42 1.65 1.21 0.02

0.05 0.10 0.08 -

100,000,000
50,000 100,000 80,000 -

(76,000,000) (41,000) (42,000) (132,000) (76,215,000)

0.04 0.01 0.00 0.05 1.50

100,000,000
40,000 12,000 3,000 50,000 1,500,000

(76,000,000) (74,800) (5,040) (60,500) (30,000)

(76,170,340)

0.85 0.04 0.11 0.13 0.77 0.55

94.30 3.23 0.20 -

94,300,000 3,230,000 200,000 -

80,155,000 129,200 154,000 80,438,200

95.20 2.00 0.20 0.50

95,200,000 2,000,000 200,000 500,000

80,920,000
220,000 154,000

275,000
81,569,000

PROFIT / (LOSS)

4,223,200

5,398,660

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Objections to EDG
Tank volumes required FFA generation Lyso-lecithin production Cost of retro-fitting

No or little experience

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Objection handling
Tank Volumes
Short time degumming, i.e. 1-2 h, reduces contact time without compromising yield

FFA Generation
Stochiometric amounts not reached in STDG probably due to difference between phosphorus reduction, oil binding versus PL hydrolysis

Quality of gums
Lower viscosity and limited hydrolysis doesnt rule out use for food

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Objection handling cont.

Retro-fitting
Short time degumming reduces contact time so limited amount of tanks needed Plants running acid degumming need almost zero new equipment

No experience
Big swing to EDG in S. America, Europe, Russia, Middle East over the last 12 months they cant all be wrong!

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>50 plants World-wide Use our enzymatic solutions to improve their oil & fats processing
Enzymatic Degumming plants

Synthesis and modification plants

Enzymatic Interesterification plants Pilot biodiesel plants

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How can NZ support implementing EDG ?

Trials and analytical services in O&F lab in Malaysia
CS-Support on site with experienced technicians Largest experience based on 2 decades working with EDG Dialogue and information exchange with engineering companies Degumming handbook, PDS, AS, MSDS, data on storage stability of Lecitase Ultra etc.

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Future directions

Simultaneous degumming and FFA removal Simultaneous degumming and methylation Analytical developments Yield measurement Quantification of phospholipids ?

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Conclusions Enzymatic degumming is the main method for yield saving in refining today It improves sustainability without increasing costs Intervention is possible in many parts of the refining process So why not ?