Post on 02-Feb-2018
GEA Mechanical Equipment / GEA Westfalia Separator Group GmbH
Breakdown and Distribution of Substances in Mechanical Rapeseed/Canola Processing Ted Neuman, Steffen Hruschka, Robert Zeldenrust, Renewable Resources
GEA Mechanical Equipment 2
1. Seed and pre-treatment 2. De-oiling 3. Oil processing – Refining and Transesterfication 4. Deoiled cake fraction 5. By-products
Agenda
Dr. St.Hruschka/R.Zeldenrust / Renewable Resources
GEA Mechanical Equipment 3
1 Seed and pre-treatment
• With 12% of the world-wide vegetable oil production, rapeseed represents the third highest volume after palm (18%) and soy (26% )
• Total: approx. 60 mill. to oil (or about 90 mill. to cake) • EU = 30 % of the world ; Germany 30% of EU
Rapeseed production 2012 according to „Indexmundi“
Dr. St.Hruschka/R.Zeldenrust / Renewable Resources
GEA Mechanical Equipment 4
1 Seed and pretreatment
according Diss. Heift 2001 and * B. Matthäus 1998 1 Aiple 2002, 2 Jeroch et al 2008, 3 Diss. Natsch 2006
Seed compl Hull Kotyledon Weight [mg] 3,5 – 5,5 0,5 -0,9 3,0 – 4,6 mg color , size black, 2,0 – 3,2 yellow
Water content [%] 6 – 8 %
Part of seed [%] 100 12–17 (15-22) 2 84 – 88
Fraction comp. [%]
Triglycerides 44,41 14 3 39 – 50
Proteins 22,71 13 3 20 – 27
Carbohydrates 20,91 (n-free extrtact)
22-24 Poly; 1-3 <Oligo 3
3-6 Poly; 5- 6 <Oligo 3
Lignin 4-6 3 29-35 3
Phospho- + Glycolipids 0,5 – 1,5
Sinapin* 0,57-0,9 % 0,07-0,23 0,83-1,15
Glucosinalate <25µmol/g 2 6,1 (14 Ukrain)
Phytinacid 2,4-3,5 *,3 0,2-1 3 3-4 3
Dr. St.Hruschka/R.Zeldenrust / Renewable Resources
GEA Mechanical Equipment 5
• Basic flow sheet
Introduction
Pre-Treatment
De-Oiling
seed
feed
cake Crude oil
Oil processing Cake & Flakes processing
Isolate Concentrate
etc.
By Product processes
Glycerin, FFA, PL,
Tocopherol
Edible oil Biodiesel
etc. Polyphenol
etc.
Oil and derivates
PL, Soap..
PP, fibre… Proteins
Dr. St.Hruschka/R.Zeldenrust / Renewable Resources
GEA Mechanical Equipment 6
Introduction
Pre-Treatment
De-Oiling
seed
feed
solids Crude oil
Oil processing Cake & Flakes processing
Isolate Concentrate
etc.
By Product processes
Glycerin, FFA, PL,
Tocopherol
Edible oil Biodiesel
etc.
Polyphenol etc.
Oil and derivates
PL, Soap...
PP, fibre… Proteins
Dr. St.Hruschka/R.Zeldenrust / Renewable Resources
GEA Mechanical Equipment 7
• No pre-treatment for cold and medium warm press (press cake) - PK (Non food biodiesel)
• Heating for hot pressing (expeller) - REK • Dehulling in order to
reduce fiber content (kernel cake) - KeK
• Besides this: • Heating reduces Sinapin (Jeroch et. Al 2008)
• No difference in the oil content (8 to 20%) between Expeller and PK (Till 2007)
• Sinapin and Sinapinacid are increased after dehulling by 14 to 50% • Phytinacid is increased after dehulling by 12.7-38% (Matthäus 1998) • Pre-preatment: increased NHP
1 Seed and pre-treatment
Dr. St.Hruschka/R.Zeldenrust / Renewable Resources
GEA Mechanical Equipment 8
2 – Deoiling; cake
Press cake
press Extraction
drying
Seed
feed
Lecithin
solid
Crude oil
oil oil
Presss oil clarifying
Water degumming
gums
% Oil Protein Fibre Glycosinolate Sinapin Cold press 13 35 12,5 Hot expeller
11 36 13 reduced reduced
Flakes 3,2 38 14 7.6 -10 ppm Dehulled 2 + (14-57)%
Dr. St.Hruschka/R.Zeldenrust / Renewable Resources
GEA Mechanical Equipment 9
2 – deoiling; cake
Press cake
press Extraction
drying
Seed
feed
Lecithin
solid
Crude oil
Presss oil clarifying
Water degumming
gums
% Oil Protein Fibre Glycosinolate Sinapin Cold press 13 35 12,5 Hot expeller
11 36 13 reduced reduced
flakes 3,2 38 14 7.6 -10 ppm dehulled + (14-57)%
0.8 to 2.0 % FFA Low NHP Cold/hot =150/500 ppm P
0.8 to 2.0 % FFA High NHP 600-1000 ppm P
Result 0-200 ppm HP 80-200 ppm NHP
Dr. St.Hruschka/R.Zeldenrust / Renewable Resources
GEA Mechanical Equipment 10
2 – deoiling; cake
Press cake
press Extraction
drying
Seed
feed
Lecithin
solid
Crude oil
Presss oil clarifying
Water degumming
gums
% Oil Protein Fibre Glycosinolate Sinapin Cold press 13 35 12,5 Hot expeller
11 36 13 reduced reduced
flakes 3,2 38 14 7.6 -10 ppm dehulled + (14-57)%
0,8 to 2,0 % FFA Low NHP Cold/hot =150/500 ppm P
0,8 to 2,0 % FFA High NHP 600-10o0 ppm P
Result 0-200 ppm HP 80-200 ppm NHP
Dr. St.Hruschka/R.Zeldenrust / Renewable Resources
GEA Mechanical Equipment 11
3 oil processing
Pre-Treatment
De-Oiling
Seed
Feed
solids Crude oil
Oil processing Cake & Flakes processing
Isolate Concentrate
etc.
By Product processes
Glycerin, FFA, PL,
Tocopherol
Edible oil Biodiesel
etc.
Polyphenol etc.
Oil and derivates
PL, Soap...
PP, fibre… Proteins
Dr. St.Hruschka/R.Zeldenrust / Renewable Resources
GEA Mechanical Equipment 12
3- Press oil clarifying
Clarified crude oil
0,1 to 0,3 % DS
seed
press
Decanter
Crude oil with solids
4 to 15% DS Proteins, fibre…
Process water
Solids recycling
75 % DS 20-25 % Oil abs.
Decanter 2 phase clarifier: 20 t/d to 1500 t/d Alternatives: Ultrasonic Filter
70-100°C
Dr. St.Hruschka/R.Zeldenrust / Renewable Resources
GEA Mechanical Equipment
3 Degumming
• Removal of phospholipids from fats and oils
• Phospholipids are phosphorous containing organic substances with a character of a fat
• The content of phospholipids is determined by analyzing the phosphorous content in the oils and fats
• Factor to convert phosphorous to phospholipids: • 25.4 for pure phospholipids • 30.0 for simplification and to include glycolipids and sugars
Degumming
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GEA Mechanical Equipment
3 Composition PL in rapeseed
Soybean Oil Canola Oil Sunflower Oil
Phosphorous content [%] 400 - 1200 200 – 900 300 – 700 Phospholipids content [%] 1.0 – 2.9 0.5 – 2.3 0.8 – 1.8 Phospholipids distribution [%]
PC (MW 784) 32-47 27-37 29-52 PI (MW 861) 21-24 17-22 17-30 PE (MW 742) 20-23 17-20 17-26 PA (MW 699) 9 8-39 6 -30
• Hydratable phospholipids • Phosphatidyl choline (PC) • Phosphatodyl inositol (PI)
• Non-hydratable phospholipids • Phosphatitic acid (PA) - (calcium, magnesium and iron salt) • Phosphatidyl etholamine (PE) (dissociate + pos- amino group = internal salt)
A.Dijkstra, Source AOCS lipid library
14 Dr. St.Hruschka/R.Zeldenrust / Renewable Resources
GEA Mechanical Equipment
3 PL
• Hydratable phospholipids (HP) • Can be removed by precipitation with water ⇒ Water degumming
• Glycolipids and sugars are also removed
• Non-hydratable phospholipids (NHP) • The Ca- and Mg-complexes of PA and PE have to be decomposed by a
strong acid before the phospholipids can be precipitated with water ⇒ Acid degumming
Gly
cero
l Fatty Acid
Fatty Acid
Polar rest P O O
O
O-
15 Dr. St.Hruschka/R.Zeldenrust / Renewable Resources
GEA Mechanical Equipment
3 Degumming
• Non-hydratable phospholipids are calcium, magnesium and iron salts (Remark: Not all PA and PE are non-hydratable)
• Non-hydratable phospholipids are formed by an enzymatic reaction of damaged cell structures of the seeds with phospholipases
16
Degumming – without neutralisation Water degumming HP (Lecithin) Special + Top degumming NHP (Gums) Enzymatic degumming NHP (PL-derivate) Alcohol degumming dry for Biodiesel
Dr. St.Hruschka/R.Zeldenrust / Renewable Resources
GEA Mechanical Equipment
3 Integration of degumming in refining processes
Acid-Degumming
Dewaxing
Bleaching
Deacidification/ Deodorisation
Bleaching
Deodorisation
Alkali- Neutralisation
Dewaxing
Water-Degumming Gums Drying
Edible oil
Crude oils
Lecithin
Soapstock Splitting Acid oil
Edible oil
GumsNHP
Fatty acids
Distilled fatty acids
Physical Refining
Chemical Refining
17
Water-Degumming Lecithin HP
< 3% FFA > 3% FFA
Dr. St.Hruschka/R.Zeldenrust / Renewable Resources
GEA Mechanical Equipment
3 Pre-conditions for refining processes
Demands • Chemical Refining
• FFA- content: < 3-10 % ideally < 3% • P-content: < 1200 ppm ideally < 200 ppm
• Physical Refining • FFA-content: > 3 % also for 2-5% • P-content: < 10 ppm (after degumming) • Iron content: < 0.2 ppm
18 Dr. St.Hruschka/R.Zeldenrust / Renewable Resources
GEA Mechanical Equipment
3 Special Degumming
• Flexible plant • Can be used for degumming and neutralization
• Degumming with one or two stages • One stage, without washing
• less effective, • no waste water
• Two stages, with washing • Lower P-content • Wash water as additional effluent stream
19
Steam
Crude oil Gums
Acid
M
Lye
Vacuum
Degummed oil
Washwater
Water
M
Water Steam
M M
Dr. St.Hruschka/R.Zeldenrust / Renewable Resources
GEA Mechanical Equipment
3 Special Degumming Process 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: min. 5 minutes • Caustic soda addition: partial neutralisation of acid, not FFA • Water addition: corresponding to phosphatides content • Mixing: dynamic mixer • Hydration time: min. 60 minutes • Heating for separation: 75 – 90 °C • Wash water addition: 3 – 5 % vol. • Mixing: dynamic or inline static mixer
20
M
M
M M
Dr. St.Hruschka/R.Zeldenrust / Renewable Resources
GEA Mechanical Equipment
3 TOP Degumming
• Highly effective and specialized degumming process • Process based on a combination of two centrifuges
• First separator to remove the bulk of phosphatides, second separator to remove remaining fines
• Second separator is a highly efficient nozzle separator with 14,000 g
• The process is very simple and the plant very compact • Short retention times • Works with crude and pre-degummed oils
• Patented process • Patent rights taken over by Westfalia Separator
21 Dr. St.Hruschka/R.Zeldenrust / Renewable Resources
GEA Mechanical Equipment
TOP-Degumming Process 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, no hydration time • Caustic soda addition: partial neutralisation of acid, not FFA • Gums separation: by standard refining separator • Wash water addition: 1.5 - 3 % vol. • Mixing: In-line static mixer • Water retention time: 3 minutes • Water separation: by high speed nozzle separator • Recycling: water, fine gums, oil to the first separator
M M
22 Dr. St.Hruschka/R.Zeldenrust / Renewable Resources
GEA Mechanical Equipment
3. Degumming/ Refining Results
23
P & Fe -content: Special degumming Top degumming
P for one stage process, no washing: 20 - 30 ppm 10 ppm P for two stage process, with washing: 15 - 20 ppm
Fe- < 0,2 ppm
Content in gums
Acetone insoluble (AI): 50 - 60 % 60 – 70 % Oil content on dry base: 40 - 50 % 30-40 %
Water 50 - 60 % >50
Waste water quality
Oil content approx. 5 %
Moisture content in the degummed oil
Without vacuum drying: < 0,5 % < 0,5 % With vacuum drying: < 0,1 % < 0,1 %
Dr. St.Hruschka/R.Zeldenrust / Renewable Resources
GEA Mechanical Equipment
3 Reaction of Enzymes
Gly
cero
l Fatty Acid
Fatty Acid
Polar rest P
PLC
PLA2
PLA1
Products with the use of specific enzyme: • PLA1: MonoAcylGlycerol - Phospholipid (Lyso-Phospholipid)
+ Free Fatty Acid
• PLA2: MonoAcylGlycerol - Phospholipid + Free Fatty Acid
• PLC: Di-Acyl-Glyceride + Phophoroester
24 Dr. St.Hruschka/R.Zeldenrust / Renewable Resources
GEA Mechanical Equipment
3 Enzymatic Degumming with PLA 1
Gly
cero
l
Fatty Acid
Fatty Acid
Polar rest P O O
O
O-
PLA 1
In enzymatic degumming with PLA 1 only the Mono-Acyl-Glyceride-Phospholipids are separated from the oil, the free fatty acid will stay in the oil. So the losses are reduced. Additionally there will be less emulsification because the amount of the emulsifier Di-Acyl-Glyceride-Phospholipid has been decreased by the enzyme.
Mono-Acyl-Glyceride Phospholipid
Free Fatty Acid
25 Dr. St.Hruschka/R.Zeldenrust / Renewable Resources
GEA Mechanical Equipment
3 Enzymatic Water Degumming with PLC
Gly
cero
l Fatty Acid
Fatty Acid
Polar rest P O O
O
O-
PLC
In enzymatic water degumming only the Phosphoroesters are separated from the oil, the Di-Acyl-Glycerides stay in the oil. So the losses are reduced. The PLC will not reduce the level of PA/PE But the lecithin will not have the typical parameters and functions.
Phosphoroester
Di-Acyl-Glyceride
26 Dr. St.Hruschka/R.Zeldenrust / Renewable Resources
GEA Mechanical Equipment
• Low residual gum content • Long storage stability of the degummed oils due to low iron content • Lower losses, higher yield • No additional wash water discharge • Low consumption of water and chemicals
3 Advantages of the Enzymatic Degumming
Crude oil
Steam Acid Lye
Vacuum
M
Enzyme + Water
Cooling water
M
Gums
Degummed oil
Steam
27 Dr. St.Hruschka/R.Zeldenrust / Renewable Resources
GEA Mechanical Equipment
3 Comparison of caustic vs. enz. degumming
Utilities Special TOP Degumming Enzymatic degumming
Acid 0.1 – 0.3 % 1 or 2 0.05- 0.3 % 1 0.04 – 0.1% 2
Caustic ( 50 %) 0.5-3 kg/t oil 0.5-3 kg/t oil 0.4-1 kg/t oil
Steam 22 kg/t oil 22 kg/t oil 22 kg/t oil Cooling water - - If crude oil > 45 °C Process water 5 - 7 % 2 - 3.5 % 2.5 - 3 %
Enzymes - - 30-60 g / t crude oil
Retention time 5 min acid./ 60 min caustic
3 min acid./ 3 min water
20 min acid 2-3 h enzyme reaction
Space 12 m x 6 m (2 floors)
12 m x 6 m (2 floors)
12 m x 9 m ( 2 floors)
Losses Approx. 20% reduction vs. TOP
P in degummed oil 15-20 with washing max. 10 ppm 10 – 20 ppm (on Enzyme)
Yield 96 96,5 3 97,4 (PLA1) 98,3 (PLC) 3
* 1 Phosphoric Acid * 2 Citric Acid
55.030*P∆
28
* 3 Chris Dayton/Het Pand, Bunge 2010
6.030*P∆
Dr. St.Hruschka/R.Zeldenrust / Renewable Resources
GEA Mechanical Equipment
Comparison for oils with 150 ppm P Costs for utilities plus oil losses for 400 tpd
0200400600800
1,0001,2001,4001,6001,8002,000
Util
itiy
Cos
ts [T
EUR
/ Ye
ar]
Special Deg.TOP Deg.Enzyme Deg. (2-stage)
Crude Oil specification: FFA: 1% Phosphorous: 150ppmP Moisture: 0.1% Impurities: 0.1%
29
Water degummed oil: Typical if Lecithin processing is applied
Dr. St.Hruschka/R.Zeldenrust / Renewable Resources
GEA Mechanical Equipment
Comparison for oils with 500 ppmP Costs for utilities plus oil losses for 400 tpd
0
500
1,000
1,500
2,000
2,500
3,000
3,500
Util
itiy
Cos
ts [T
EUR
/ Ye
ar]
Special Deg.TOP Deg.Enzyme Deg. (2-stage)
Crude Oil specification: FFA: 1% Phosphorous: 500ppmP Moisture: 0.1% Impurities: 0.1%
30 Dr. St.Hruschka/R.Zeldenrust / Renewable Resources
GEA Mechanical Equipment
< 50 ppm P 50 – 200 ppm P > 500 ppm P
Degumming in Bleaching section TOP-Degumming Enzymatic
Degumming
3 Matrix for choosing the right degumming process
Remark: • For enzyme costs between 30-35 EUR / kg and enzyme dosage
of approx. 50 g / t crude oil • Combined process of TOP and Enzymatic degumming is possible • For oils between 200 ppmP and 500 ppmP more accurate
calculations need to be done.
31
according to theoretical cost calculations
Dr. St.Hruschka/R.Zeldenrust / Renewable Resources
GEA Mechanical Equipment
4 Cake and Expeller
32
Pre-Treatment
De-Oiling
seed
feed
solids Crude oil
Oil processing Cake & Flakes processing
Isolate Concentrate
etc.
By Product processes
Glycerin, FFA, PL,
Tocopherol
Edible oil Biodiesel
etc.
Polyphenol etc.
Oil and derivates
PL, Soap...
PP, fibre… Proteins
Dr. St.Hruschka/R.Zeldenrust / Renewable Resources
GEA Mechanical Equipment 33
• Press cake for feed : After the oil extraction approx. 60% of the seed remains as protein containing press cake or flakes. This is used to feed pigs, cattle, and poultry.
• In Germany the portion of these rape cake/flakes in the total animal feed increased from 1.2 to 3 million from 1985 to 2008 and is higher than in other countries.
• Today the intermixture has achieved the upper limit due to the minor com- ponents (e.g. phenols) in the standard cake.
• Current demand: feed, industry • Medium term: food
More demand for proteins without the disturbing minor components
4 Solids: Market Opportunity
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GEA Mechanical Equipment 34
• Concentrate > 60% protein • Deoiled material (solvent extraction, risk: protein denaturation and washing) • UDP (un-degradable protein)
Seed 15%, REK 15% cold , Rape-Flakes 35% (DLG Futtermittel 2011)
• Isolate > 90% protein • NSI and water binding potential vs. Soy (Kodagoda1973, Aluko 2001, Kroll 2009) • NSI: 0.1%-0.9% (low Phytinacid) water: 1.32%-1.57% oil: 0.61%-1.29%
4 Protein Isolate & Concentrate
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GEA Mechanical Equipment 35
• The feed quality is reduced by • Cell wall carbohydrates • Lignin
• Dehulling reduces this, but increases Sinapin and Phytinacid
• Breeding reduces Glycosides
• New patents are filed recently > 2008 for Isolates and products e.g.
from Bioexx, Burcon, and others…
4 Protein products
Dr. St.Hruschka/R.Zeldenrust / Renewable Resources
GEA Mechanical Equipment 36
5 By-Products
Pre-Treatment
De-Oiling
Seed
Feed
Solids Crude oil
Oil processing Cake & Flakes processing
Isolate Concentrate
etc.
By Product processes
Glycerin, FFA, PL,
Tocopherol
Edible oil Biodiesel
etc.
Polyphenol etc.
Oil and derivates
PL, Soap...
PP, fibre… Proteins
Dr. St.Hruschka/R.Zeldenrust / Renewable Resources
GEA Mechanical Equipment 37
• Sinapine and Sinapine acid content % SP sinapine 0.9- 1.6 SA (sinapine acid) 0.6 -1.2 SG Synapoil Glycose) ~ 0.1
(SynRG) Khattab, JAOCS 2010
• Phytinacid < 3.5 % in seed, 4% in Cotyledons… forms phytates with Mg, K, Ca
• Hull and fiber content complete de-hulling before extraction is economically questionable.
5 Minor Components
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GEA Mechanical Equipment 38 Dr. St.Hruschka/R.Zeldenrust / Renewable Resources
Sinapin
0.00
0.50
1.00
1.50
2.00
2.50
3.00
Kernbruch Kalt Vollkorn Kalt Vollkorn Warm Vollkorn Heiß
Poly
phen
ole
in m
g/g
Pressart
Polyphenol in the water after special protein precipitation
Sinpinsäure
Sinapin
Dehulled cake complete seed cake: cold, warm, hot pressed
GEA Mechanical Equipment 39
• Drying and grinding
Globulinphase
Parameter % abs
% TS
TS 20 Öl 10-15 Protein 55-60 Sonst (KH)
30-35
GEA Mechanical Equipment 40 Dr. St.Hruschka/R.Zeldenrust / Renewable Resources
Hemp