enzymatic oil-degumming a technology in...
TRANSCRIPT
Enzymatic oil-degumming a technology in motion
DSM Zhao Xiangguo
Processing & refinment of oilseed and edible oil, AOCSPudong ShanghaiNovember 17-18
DSM and enzymes
State of affairs in the industry
Principles enzyme degumming
A technology in Motion
Applications today
Applications tomorrow
Contents
nutrition health materials
We create solutions to bring healthier, better
performing and more sustainable products to the
lives of people today and for generations to come.
Active in:
Net sales approx. € 10,000m
Workforce 24,500
DSM Life Sciences and Material Sciences company
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Feeding the world’s growing population with
more and better food by enhancing yield,
quality and nutritional value of the Earth’s
limited resources
Getting most out of the gifts of Nature
DSM Enzymes creates brighter lives by:
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Enzymes in your daily life
Natural – they come from living
organisms like animals, plants,
bacteria
Proteins – made of amino acids
just like other proteins
Ubiquitous – present in every
living organism
Catalysts – nature uses them to
make biological reactions
happen faster
Specific – unlike most chemical
catalysts in industrial use,
enzymes facilitate targeted
molecular conversions
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Status quo: the environment is complex
It’s tough to stay
relevant and
profitable with
your crushing and
refining operations
in a continously
changing world …
Sources: Reuters,
Economist, Soyatech
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Harsh Winter and Rail Delays Impact Ethanol Industry
To a large extent you can control what’s happening in your plant
Harvest
Seed
Preperation
Crude oil Meal
Extraction
Biodiesel Bottled oil
Export market Export or
local market
Crude
degummedAnimal feed
Degumming
Caustic refining
Bleaching
Deodorizing
Desolventizing
Drying
Grinding
Pelletizing
Gums
Transport
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Principles of enzyme assisted degumming
Emulsion causes yield loss
Phospholipids are emulsifiers:• Phospholipases reduce surface tension between water and oil• Oil is emulsified (& trapped) in the gum fraction
Oil losses in degumming & caustic refining are caused by intact phospholipids
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Principles of enzyme assisted degumming
Not all phospholipids are created equal¹
• Quantity and type of phospholipids vary by oil type, geography and quality• Rate of hydration increases with polarity and correlates with emulsifying strength • Formation of metal salts reduces polarity and results in “non-hydratable” phospholipids• Total phosphorus measurements (e.g. ICP²) only indicate the presence of phospholipids
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.
2. ICP – Inductively Coupled Plasma
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Principles of enzyme assisted degumming
Drivers for success
+ Oil
1,2-Diacylglycerol (DAG)
PLA2
PROCESS FLEXIBILITY
Elimination of soapstock
Capture of fatty acid as value stream
Less waste
YIELDConversion of phospholipids to DAG oil
Reduction in gums
Release of entrained oil
QUALITYLow phosphorus after degumming
Ultra low phosphorus from deep degumming
Reduced dilution of meal protein
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Principles of enzyme assisted degumming
Process principles
Principle Rationale
Cooling the crude oil Enzyme activity + emulsion stability
High shear mixing Enzyme connected with substrate + emulsion stability
Plug-flow reactor with agitation Maintain connection and sufficient reaction time
Heating reacted oil Break residual emulsion to facilitate phase separation
Disk stack centrifugation Separation of the degummed oil and reacted gum
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Principles of enzyme assisted degumming
Best practices
Design / Process / Equipment recommendations Other recommendations
• Buffer tank before degumming process
• CIP on heat exchanges and separators
• Two parallel lines of heat exchangers
• Positive displacement pump on oil flow to
primary separator
• Pump on gums existing primary separator
• DAG measurement at or close to plant
• Appropriate design enzyme cold storage
• Acid dosing before primary separator
• Caustic addition prior to enzyme reaction
• Auto samplers installed
• Easy to access manual sampling ports
• Operate expanders at temperature >100⁰C
Purifine® enzyme assisted degumming yields optimal results with a well designed and
implemented process, that is operated under controlled process conditions with
minimal interruptions.
Based on 5 years of proven industry results and >20 Purifine® plants operating
around the world, >10 plants commissioned, start usage in 2014-15
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Applications of today
Enzyme assisted water degumming
Results* Analysis
Phosphorus (ppm) 1151 ICP
Total phospholipids (% wt) 2.05 P31 NMR
Reaction efficiency (%) 86 -
DAG yield gain (% wt) 1.03 HPLC
Degummed oil P (ppm) 41 ICP
Total yield gain (% wt) 2.2-2.6 Oil inventories
Required process parameters
• Temperature; Crude 55-
60⁰C , Reacted 85-90⁰C
Reaction Time; 2+ hours
• Enzyme dose: 50-300
• Water 1-3% of crude oil
Required equipment
• Ultra High Shear mixer such as an
IKA brand
• Segmented reaction tank
• Accurate flow meters (Coriolis type)
• Ratio controllers to ensure dosing
accurately
• The first application of
Purifine® PLC, started
in 2010
• Molinos Rio de La Plata
in Argentina since
2010, reported net oil
gain of $60 mln since
adoption
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Applications of today
Required process parameters
• Temperatures: Acid treatment at 70-90⁰C; caustic dosage at 55-60⁰C;
water wash at 85-90⁰C
• Acid treatment time: 30 minutes.
• Phosphoric acid: 100 – 1000 ppm (dry basis and based on 85% solution)
• Citric acid: 400 – 2000 ppm (dry basis and based on 50% solution)
• Caustic dose: 50 – 2000 ppm (dry basis and based on 50% solution)
Required equipment
• Ultra High Shear mixer such as an IKA brand
• Segmented reaction tank
• Accurate flow meters (Coriolis type)
• Ratio controllers to ensure dosing accurately
Enzyme assisted deep degumming
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A technology and industry in Motion
1997
Dahlke³ re-inforced focus on NHP , only a PLA2 enables full degumming. Recirculation, conventional equipment
1993
Röhm GmbH (Lurgi) EnzyMax² process, PLA2 from porcine pancreas;Features: Oils rich in NHP,Oils < 250 ppm P
2000
Introduction of microbial, fermentation based PLA enzymes that allow better process control, secured product availability. Still focus on low P and NHP’s
2006
Purifine® PLC⁴commercialized; a new enzyme with PLC activity able to hydrolyze PC and PE, game-changer due to focus on high P SBO, driving oil yields up
2008
Dayton and Galhardo⁵report synergy between PLA and PLC as they describe use of a combination of enzymes
Engineering companies adopt technology andn between 2008 and 2012, install >50 plants online that use enzymatic degumming on a daily basis. Various processes & enzymes & oilseeds used
2013
DSM launches 2nd generation degumming solution based on synergy PLA2 & PLC
Sen Gupta¹ publication on relative rate of hydration of different phospholipids found in vegetable oils, separating between hydratable and non hydratable phospholipids
1986 2014
DSM launches 3rd generation degumming solution able to convert all phospholipids
¹Sen Gupta, A.K. Micellar structures and their implication in the chemistry and technology of fats and other lipids. Fette Seifen Anstrichm., 88, 79-86 (1986).
²Aalrust, E., Beyer, W., Ottofrickenstein, H., Penk, G., Plainer, H. and Reiner, R. (Röhm GmbH and Metallgesellschaft AG), Enzymatic treatment of edible oils, US
Patent 5,264,367 (1993).
³Dahlke, K. The enzymatic degumming - EnzyMax. Oléagineux Corps Gras Lipides/OCL, 4,55-57 (1997).⁴Gramatikova, S.(Verenium Corporation), Phospholipases, nucleic acids encoding them and methods for making and using them, US Patent 7,977,080 (2011).
⁵Dayton, C.L.G. and Galhardo, F. (Bunge Foods Corporation), Enzymatic degumming utilizing a mixture of PLA and PLC phospholipases, US Patent Application
Publication 2008/0182322 (2008).
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2nd Generation Purifine® Enzymes
In short:• Designed for more complete reaction of phospholipids
• Reaction PC, PE plus conversion of NHP (PA)
• Same DAG yield as PLC
• Small increase in FFA
Implications:
Increased total oil yield due to more complete PL reaction
Easier removal of P & metals due to NHP reaction
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3rd Generation Purifine®: Complete Degumming
In short:
• Goal: Reaction of all phospholipids in crude oils
• Further boost in DAG & total oil yields
Implications:
Product undergoing regulatory approval
process – 2014 launch
Trials in USA per Q3 & Q4 2014
Launch in target markets 2015
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Advantages of DSM enzymatic degumming
Robust implementation & operation
Engineering:• Attention to critical design details
• Complete equipment list
Process:• Accurate measurement & control
• Protection from other process perturbations
• Understanding of critical non-EDG factors
Operation:• Alignment with production targets
• Ownership by user & training of key personnel
• In-field support from enzyme supplier
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Changing the game - complete Purifine® solution development
Improved enzyme technology
Technical industry knowledge
Process development in DSM lab
Plug-and-play in your processes
Process validation in DSM plant
DSM Application & Analytical Support
DSM Center for Oils & Fats enzymes business established in San Diego:Global Applications Support lab capable of:
• Commercially relevant & industry recognized analytical methods
• Scaled-down degumming & refining assays, with measurement of
reaction substrates and products
• Support for trial and implementation of EDG in plants
• Equipment includes HPLC, GC, ICP, 500 MHz NMR
Refer to the
AOCS sample
check DAG
series …
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No matter what …
… it will remain
tough to stay
relevant and
profitable with
your crushing and
refining operations
in a continuously
changing world …
But DSM’s Purifine®
gives you the edge
to stay ahead of
the competition
and get the highest
value out of your
beans
Sources: Reuters,
Economist, Soyatech
Page 21
Harsh Winter and Rail Delays Impact Ethanol Industry
While making reasonable efforts to ensure that all information in this presentation is
accurate and up to date, DSM makes no representation or warranty of accuracy, reliability,
or completeness of the information. The information provided herein is for the
informational purposes only.
This publication does not constitute or provide scientific advice and is without warranty
of any kind, express or implied. In no event shall DSM be liable for any damage arising
from the reader’s reliance upon, or use of, this presentation. The reader shall be solely
responsible for any interpretation or use of the materials contained herein.
Crude Oil
Purifine
Cooling Tower
High Shear
Mixer
TIC
FIC
Economizer
Cooler
Reacto
r
Degummed Oil
To Drier
55 – 60 oC
Cooling
Wate
r
Lysogums
Reactors
LIC
Steam
Condensate
TIC
Econom
izer
Econom
izer
Water
85oC
2 – 4 % (pH 5.5 – 8,0 %)
Oil Heater2 hrs/ pH 6 – 8,0
Degumming
FIC
Oil Heater
Appendix > visual slide 12 in detail
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