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AOCS FUNDAMENTALS OF OILSEED AND EDIBLE OIL PROCESSING AND REFINING
Review of Degumming and Refining Technologies
Shanghai, China
17-18 November 2014 Greg Waranica
Crown Iron Works Company
2 Crown Iron Works – A CPM Company
Crown Contacts USA
Greg Waranica or Derek Masterson Crown Iron Works Company Phone: +1 651 639 8900 E-mail: [email protected] [email protected] Web: www.crowniron.com
3 Crown Iron Works – A CPM Company
Crown Contacts China
Crown Asia Engineering (Wuhan) Co., Ltd Phone: +86 (27) 6784 7581 E-mail: [email protected] Web: www.crownironasia.com
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Oils & Fats Refining Roadmap
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Oils & Fats Refining Processes
• Key Processes – Degumming
– Neutralizing (Refining)
– Bleaching
– Deodorizing
• Degumming can be a separate process or combined with Neutralizing
• Processes collectively produce what is termed RBD oil
• Additional Processes – Winterizing
• Dewaxing • Winterizing
– Oil Modification • Dry Fractionation • Hydrogenation • Chemical Interesterification
– Byproduct • Oil Filtration and Lecithin
Drying • Soapstock Acidulation • Fatty Acid Distillation
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Purpose of Degumming and Neutralizing
• Remove contaminants from crude oil prior to bleaching, deodorizing or other refining processes: – Insoluble solids (meal) – Phospholipids (gums) – Free fatty acids (FFA) – chemical/caustic refining – Oxidative materials (metal ions) - limited – Color bodies (chlorophyll and carotenes) - limited – Waxes (requires special operating conditions) - limited
• Preserve valuable minor components (tocopherol)
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Degumming and Neutralizing
• Degumming – Typically used with high FFA feedstocks such as palm oil and animal fat
– Removes phosphatides (P), not FFA
– Used when recovering lecithin or improving soapstock quality
• Neutralizing – Typically used with low FFA feedstocks such as soybean oil and
canola/rapeseed oil
– Removes both free fatty acids (FFA) and phosphatides (P)
– Neutralizing also called refining
– Refining has two definitions • Neutralizing process only; aka “once refined”
• Complete RBD process; aka “fully refined”
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Degumming
• Degumming can be either a single or two step process – Water removes the hydratable phosphatides (gums)
– Acid converts the non-hydratable phosphatides to hydratable phosphatides
– Phosphatide removal is further increased by caustic addition, water wash, silica adsorption or high speed centrifugation
– Enzymatic degumming is a unique process using enzymes which increases the oil yield
• Silica adsorption quality slightly better, water treatment plant is not necessary and control of feedstock and process are necessary
• Water washing is more forgiving, a water treatment plant is required and less control of feedstock and process are necessary
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Neutralizing
• Neutralizing is a two step process – Neutralizing removes a majority of the FFA (soaps) and
phosphatides (gums)
– Purification either by silica or water removes most of the residual soaps and gums
• Silica adsorption quality slightly better, water treatment plant is not necessary, solids disposal required and control of feedstock and process are necessary
• Water washing is more forgiving, a water treatment plant is required, solids disposal not required and less control of feedstock and process are necessary
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Degumming Processes
• Degumming – Water (100 - 200 ppm P) – Acid (20 - 50 ppm P) – Single stage Special
(20 - 30 ppm P) – Two stage Special w/water
wash (15 - 20 ppm) – Two stage Special w/silica
adsorption (< 5 ppm) – Super/Uni (5 -15 ppm P) – TOP (5 -10 ppm P) – Enzymatic (5 -150 ppm)
• Super/Uni- and TOP Degumming are patented processes held by Westfalia Separator
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Phospholipid Content
Oil Phospholipid (%) As Phosphorus (ppm) Coconut 1 0.025 – 0.05 10 - 20 Palm 2 0.04 – 0.1 15 - 40 Sunflower 0.8 – 1.8 300 - 700 Maize (Corn) germ 0.7 – 2.0 300 - 800 Rapeseed/Canola 0.5 – 2.3 200 - 900 Cottonseed 1.0 – 2.5 400 - 1000 Soybean 1.0 – 3.0 400 - 1200
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Note 1: Acid added in Neutralizing Note 2: Acid added in Bleaching called acid conditioning
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Phospholipids
• Two types of phospholipids – Hydratable (removed by water alone)
• Phosphatidyl choline (PC) • Phosphatodyl inositol (PI)
– Non-hydratable (reacted with an acid then removed) • Phosphatitic acid (PA) • Phosphatidyl etholamine (PE)
• Non-hydratable phospholipids contain calcium and
magnesium salts
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Purposes for Different Degumming Processes
• Water Degumming – Storage (prevent formation and settling of gums in tanks) – Meet soybean oil trading standard (prevent formation and settling of
gums during transportation) – Produce lecithin (food grade) – Improve acidulation process (soapstock)
• Acid Degumming – Meet canola oil trading standard
• Special Degumming – Two stage with water wash or silica adsorption
• May physical refine oil • Same design as 2 – stage neutralizing
– Single stage • Meet canola oil trading standard
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Purposes for Different Degumming Processes
• TOP Degumming – May physical refine the oil – Minimize phosphatide content of oil
• Enzymatic Degumming – Improve oil yield – PLA1 and PLA 2
• May caustic refine • May physical refine if oil is total degummed (< 5 ppm P)
– PLC • Meet soybean oil trading standard
– Blending PLA1 or PLA2 with PLC may optimize process
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Water Degumming
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Courtesy of Westfalia Separator
AI = 65 to 70
P = 100 to 200 ppm
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Water Degumming Operating Parameters
• Oil temperature: 75 – 90 °C
• Water addition: corresponding to the phosphatide content
• Hydration time: - with static mixers 20 – 30 minutes - with high shear mixing, not required but recommended
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Acid Degumming
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Courtesy of Westfalia Separator
AI = 60 to 70
P = 20 to 50 ppm
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Acid Degumming Operating Parameters
• Oil temperature: 75 – 90 °C • Acid addition: 0.1 – 0.3 % w/w phosphoric or citric
acid • Mixing: high shear • Retention time: minimum 5 minutes • Water addition: 2 – 3 % vol. • Mixing: static mixer
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Special Degumming
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Courtesy of Westfalia Separator
AI = 50 to 60
P = 15 to 20 ppm
P = 20 to 30 ppm
Alternative: silica adsorption
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Special Degumming Operating Parameters
• Oil temperature: 60 – 75 °C • Acid addition: 0.1 – 0.3 % w/w phosphoric or citric
acid • Mixing: high shear mixer • Acid retention time: minimum 5 minutes • Caustic soda addition: partial neutralization of acid, not FFA • Water addition: corresponding to phosphatides
content • Mixing: static mixer • Hydration time: minimum 30 minutes • Heating for separation: 75 – 90 °C • Wash water addition: 3 – 5 % by volume • Water temperture: 90 – 95 °C • Washing time: 0 – 10 minutes
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TOP Degumming
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Courtesy of Westfalia Separator
AI = 60 to 70
P = 5 to 10 ppm
Patented owned by Westfalia Separator
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TOP Degumming Operating Parameters
• Oil temperatures: 90 – 105 °C • Acid addition: 0.1 – 0.3 % w/w phosphoric or
citric acid • Mixing high shear mixer • Acid retention time: 3 minutes • Caustic soda addition: partial neutralization of acid, not
FFA • Gums separation: by standard refining separator • Wash water addition: 3 % vol. • Water retention time: 3 minutes • Water separation: by high speed nozzle separator • Recycling: water, fine gums, oil to the first
separator
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Super/Uni - Degumming
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Patented by Unilever & licensed by Westfalia Separator
Courtesy of Westfalia Separator
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Enzymatic Degumming
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Courtesy of Westfalia Separator
Liquid Disposal only
P < 20 ppm
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Enzymatic Degumming Operating Parameters
• Oil temperature: 55 – 70 °C • Acid addition: 0.04 – 0.1 % w/w citric acid • Acid retention time: 10 - 30 minutes • Oil temperature: cooling to 55 – 65 °C • Caustic soda addition: as needed to adjust pH 4,5 – 7
(enzyme dependent) • Enzyme addition: approx. 30 – 200 g/mt • Water addition: corresponding to phosphatides
content • Hydration time: 2 – 6 hours • Oil temperature: 70 – 80 °C for separation
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Enzymatic Degumming
• PLA reacts with all four primary phospholipids (PA, PC, PE and PI)
• PLC reacts with only two of the primary phospholipids (PC and PE) – PC is hydratable and PE is non-hydratable
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Soybean Oil Canola Oil Sunflower Oil P (ppm) 400 - 1200 200 - 900 300 - 700 Phos-ester (%) 1.0 - 2.9 0.5 - 2.3 0.8 - 1.8 PC (HP) 47% 27% 29 - 52% PI (HP) 24% 17% 11 - 22% PE (NHP) 20% 17% 17 - 26% PA (NHP) 9% 39% 15 - 30%
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Enzyme Reaction Locations
• PLA1: Novozyme Lecitase Ultra • PLA2: Danisco LysoMax DSM GumZyme AB Enzymes Rohalase • PLC: DSM Purfine
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Neutralizing Processes
• Neutralizing (< 0.1% FFA and P decrease) – 2-stage w/water wash
(< 5 ppm P)
– 3-stage w/water wash (< 5 ppm P)
– 2-stage w/silica adsorption (< 5 ppm P)
– Cold Refining (<5 ppm P)
– ORP (Organic Refining Process) (5-10 ppm P)
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Purposes for Neutralizing
• 2 – Stage Neutralizing – Used to remove FFA from low FFA oils – Most used neutralizing process – Combines (acid) degumming and neutralizing – May use water wash or silica adsorption
• 3 – Stage Neutralizing – Used infrequently today – Neutralize FFA and remove gossypol from press extracted
cottonseed oil – May use water wash or silica adsorption
• Miscella Refining – Neutralize hexane extracted cottonseed oil – Neither water washing nor silica adsorption needed
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Purposes for Neutralizing
• Wet Winterization (Dewaxing) – Three stage process combining neutralizing and winterizing – Oil neutralized before winterizing – Used for sunflower oil (long chain alchols) and corn oil (sugars and
starches) – May use water wash or silica adsorption – Second chilling and filtration may be required for low wax
specifications • Cold Refining (Dewaxing)
– Two stage process combining Neutralizing and Winterizing – Oil cooled before neutralizing – Used exclusively for sunflower oil – May use water wash or silica adsorption – Second chilling and filtration may be required for low wax
specifications
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2 – Stage Neutralizing
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Courtesy of Westfalia Separator
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2 – Stage Neutralizing (Long Mix)
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Static mixer typically used
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2 – Stage Neutralizing Process Parameters
• Oil temperature: 80 – 90 °C • Acid addition: 0.1 – 0.2 % w/w phosphoric or citric
acid • Mixing: high shear mixer • Acid retention time: minimum 10 minutes • Oil temperature: 70 – 90 °C • Caustic soda addition: neutralization of acid and FFA • Water addition: corresponding to desired caustic
concentration • Mixing: static mixer • Neutralizing retention time: 3 to 10 minutes (pressure vessel) or minimum 30 minutes (atmospheric tank) • Heating for separation: 75 – 90 °C • Wash water addition: 5 – 10 % by volume • Water temperature: 90 – 95 °C • Washing retention time: 0 – 10 minutes
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3 – Stage Neutralizing
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Courtesy of Westfalia Separator
Short mix process does not use a retention mixer
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3 – Stage Neutralizing Process Parameters
• Oil temperature: 80 – 90 °C (65 °C for cottonseed oil) • Acid addition: 0.1 – 0.2 % w/w phosphoric or citric
acid • Mixing: high shear mixer • Acid retention time: minimum 10 minutes • Oil temperature: 70 – 90 °C • Caustic soda addition: neutralization of acid and FFA and remove
gossypol • Water addition: corresponding to desired caustic concentration • Mixing: static mixer (1st neutralizing) high shear mixer (2nd neutralizing) • Neutralizing retention time: 3 to 10 minutes (pressure vessel) or minimum 30 minutes (atmospheric tank) for 1st neutralizing; 0 to 30 seconds for short mix 0 to 30 seconds for 2nd neutralizing • Heating for separation: 75 – 90 °C • Wash water addition: 10 % by volume single washing 5% by volume each for two washings • Wash water addition: 3 – 5 % by volume • Water temperature: 90 – 95 °C • Washing retention time: 0 – 10 minutes Crown Iron Works – A CPM Company
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Miscella Refining
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Courtesy of Westfalia Separator
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Miscella Refining Process Parameters
• Miscella concentration: > 65% oil in hexane • Miscella temperature: 50 - 55 °C • Caustic soda addition: neutralisation FFA • Water addition: corresponding to desired caustic
concentration • Mixing: static mixer • Neutralizing retention time: approximately 12 minutes
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Wet Winterizing
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Courtesy of Westfalia Separator
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Wet Winterizing Process Parameters
• Oil temperature: 80 – 90 °C • Acid addition: 0.1 – 0.2 % w/w phosphoric or citric
acid • Mixing: high shear mixer • Acid retention time: minimum 10 minutes • Oil temperature: 70 – 90 °C • Caustic soda addition: neutralization of acid and FFA and form 2500 –
3500 ppm soap • Crystallizing temperature: 5 – 10 °C • Crystallizing time: 8 – 10 hrs • Water addition: 3 – 5% into crystallizer • Separation temperature: 20 °C • Oil temperature for 2nd washing: 75 – 90 °C • Wash water addition: 5 – 10 % by volume • Water temperature: 90 – 95 °C • Washing retention time: 0 – 10 minutes Note: Cold stability is 12 hr @ 0 °C Note: Further crystallizing and filtration may be necessary to meet a more stringent Cold Stability
specification
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Cold Refining
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Courtesy of Westfalia Separator
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Cold Refining Process Parameters
• Oil temperature: 20 – 30 °C • Acid addition: 0.1 – 0.3 % w/w phosphoric or citric
acid • Mixing: high shear mixer • Acid retention time: minimum 5 minutes • Crystallizing temperature: 5 – 10 °C • Caustic soda addition: neutralization of acid and FFA • Crystallizing time: 8 – 10 hrs • Separation temperature: 20 – 25 °C (requires larger capacity centrifuge
due to high viscosity of oil) • Oil temperature for washing: 75 – 90 °C • Wash water addition: 5 – 10 % by volume • Water temperature: 90 – 95 °C • Washing time: 0 – 10 minutes Note: Cold stability is 12 – 24 hr @ 0 °C Note: Further crystallizing and filtration may be necessary to meet a more stringent Cold Stability
specification
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The MultiPure Degumming/Neutralizing System
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Water Wash
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Silica Adsorption
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Silica Filtration
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The MultiPure Degumming/Neutralizing System
• Special “Super Long-Mix” Neutralizing Reactor with variable retention time for minimizing processing losses, as well as residual soap and phosphorus after separation
• Atmospheric reactor
• System designed for all degumming processes and long mix neutralizing
• Zero water effluent
• Optional designs for Enzymatic Degumming
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The DoublePass Bleaching System
Color after pre-bleaching
Silica Earth Filter Aid
Solid 25 mm cake with less than 30% oil
• Silica treatment and pre-bleaching reduces earth consumption by up to 50%
• Silica adsorption of soap enables neutralizing without washing
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THANK YOU FOR YOUR ATTENTION