Enz Degumming General July 11 V2

Novozymes, CS Oils & Fats

Enzymatic Degumming (=EDG) today – a summary

26/10/20112

Novozymes – brief introduction

Enzymatic degumming – History and principles

Updating the knowledge base

Main benefits

Tools, documents and CS support

EDG in biodiesel production

Outlook

Outline

26/10/20113

Global presence

Sales Offices

Production

Research

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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 useMarket size ~ DKK 19 billion

Novozymes' business compositionRevenue 2010 ~ DKK 10 billion

Novozymes in brief

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Current & Developing Enzyme applications in oils and fats processing

Enzymatic Interesterification

Enzymatic degumming

Ester synthesis Speciality fats for nutritional use

Change in fat melting properties for margarine and shortenings

Removal of gums to ensure stability, yield & quality

Production of Bio-diesel, speciality esters and FAEE

Synthesis of omega 3 & similar products for healthy nutrition

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 non-enzymatic

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

8

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Fatty acid

Glycerol Glycerol

Phosphate

Head group

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

Fats and Phospholipids

Phospholipid chemistry I

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

Phospholipid chemistry II

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Nature

PC (Phosphatidylcholine)

PC is hydratable at all pH-values

PE (Phosphatidylenthanolamine)

When PE has a net charge, it is hydratable(<pH3, >pH9)

PI (phosphatidylinositol)

PI hydratable at all pH values

PA (phosphatidicacid)

To make PA hydratable, it must be dissociated and be present as alkali salt

NHP (non-hydratabelphosphatides)

No net charge, calcium and magnesium salts of phosphatidic acid & non hydratable, the NHPs have to be at the oil/water interface for hydrolysis

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Phospholipid chemistry III – phospholipase PLA1

.

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

The principle of enzymatic degumming is to modify the phospholipid

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Oil

Water

Hydrolysis

Oil

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 distance to interface

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First microbial alternative to PLA2

Product was called Lecitase®

Novo

Degumming was at least as good as PLA2 (phospholipaseA2)

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

Used in many oil refining plants worldwide

Lecitase Ultra for Degumming of Vegetable Oils

Performance of the three phospholipases

Lecitase

3.53.74.04.24.55.05.56.28.0 0

20

40

60

80

100

30-35 40 45 50 55 60 65

pH

Relative performance

Temp. (°C)

Lecitase® NovoUltra Pancreatic PL

3.534.04.24.55.05.56.28.0 0

20

40

60

80

100

30-35 40 45 50 55 60 65

°C)

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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 withchelating/buffering agents

What does enzyme have to do?

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Standard Enzymatic Degumming Process

Citric acid

NaOH to neutralize citric acid water

Oil tank

Oil pump

Heater

Retentionvessel

30 °C70 °C

20 min

Centrifugalseparator

Lysogums

55 °C

Mixer

1–2 hours

Enzyme

High-shear mixer

Refined Oil

(70-80)°C

High-shear mixer

Retentionvessels

Enzymatic Degumming –the role of the stages I

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Acid addition

• 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 >60°C is preferable

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 hydratablesodium salt

Enzymatic Degumming –the role of the stages II

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Water + enzyme addition

• 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

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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2nd citric addition

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

Heating to 70-80°C

• 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 to inactivate residual enzyme.

Centrifuga-tion

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

Enzymatic Degumming –the role of the stages III

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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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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

Reduces catalyst consumption

Phosphorus Oil Loss

WDG Oil 175 ppm -

50 ppm Enzyme 5 ppm 0.47%

Acid + Neutralization

13 ppm 1.62%

pH

Crude SBO 6.09

30ppm EDG SBO 5.14

0.1% ADG SBO 3.26

1 2

1 Enzymatically degummed

2 Acid degummed

Additional benefits for Bio-Diesel

Economic Evaluations

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4.20%

4.40%

4.60%

4.80%

5.00%

5.20%

5.40%

5.60%

5.80%

Water Degumming

+ Chemical

Refining

Water Degumming

+ Semi Physical

Refining

Water Degumming

+ Acid

Degumming

Water Degumming

+ Enzyme

Degumming

Full Enzyme

Degumming

5.73%5.57%

5.41%

5.18%

4.79%

Overall Loss %

Overall Loss %

Cost calculation example

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100,000,000 Kgs. Of Oil Processed

% Amount (#) Value ($) % Amount (#) Value ($)

COST:

Crude oil 0.76 - 100,000,000 (76,000,000) - 100,000,000 (76,000,000)

Phosphoric acid (85%) 0.82 0.05 50,000 (41,000) - - -

Citric acid (100%) 1.87 - - - 0.04 40,000 (74,800)

NaOH (100%) 0.42 0.10 100,000 (42,000) 0.01 12,000 (5,040)

Lecitase Ultra - - - - 0.00 3,000 -

Acid silica usage 1.65 0.08 80,000 (132,000) - - -

Std. silica usage 1.21 - - - 0.05 50,000 (60,500)

Steam (gum drying) 0.02 - - - 1.50 1,500,000 (30,000)

TOTAL COST (76,215,000) (76,170,340)

INCOME:

Refined oil 0.85 94.30 94,300,000 80,155,000 95.20 95,200,000 80,920,000

Soapstock sold 0.04 3.23 3,230,000 129,200 - - -

Gums in meal 0.11 - - - 2.00 2,000,000 220,000

Clay in meal 0.13 - - - - - -

Distillate 0.77 0.20 200,000 154,000 0.20 200,000 154,000

Fatty acid 0.55 - - - 0.50 500,000 275,000

TOTAL INCOME 80,438,200 81,569,000

PROFIT / (LOSS) 4,223,200 5,398,660

Particulars $/#Chemical Refining Enzymatic Refining

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Tank volumes required

FFA generation

Lyso-lecithin production

Cost of retro-fitting

No or little experience

Objections to EDG

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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 doesn’t 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 can’t all be wrong!

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

Enzymatic Degumming plants Enzymatic Interesterification plants

Synthesis and modification plants Pilot biodiesel plants

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 ?

Conclusions

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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… ?