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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
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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… ?