breakdown and distribution of substances in … · breakdown and distribution of substances in...

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


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“



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



• 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



Introduction

Pre-Treatment

De-Oiling

seed

feed

solids Crude oil


Isolate Concentrate

etc.


Glycerin, FFA, PL,

Tocopherol


etc.

Polyphenol etc.

Oil and derivates

PL, Soap...




• 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



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)%



2 – deoiling; cake

Press cake

press Extraction

drying

Seed

feed

Lecithin

solid

Crude oil


Water degumming

gums



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



2 – deoiling; cake

Press cake

press Extraction

drying

Seed

feed

Lecithin

solid

Crude oil


Water degumming

gums



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



3 oil processing

Pre-Treatment

De-Oiling

Seed

Feed

solids Crude oil


Isolate Concentrate

etc.


Glycerin, FFA, PL,

Tocopherol


etc.

Polyphenol etc.

Oil and derivates

PL, Soap...




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


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

13 Dr. St.Hruschka/R.Zeldenrust / Renewable Resources


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



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-



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



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



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



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



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



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



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



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 %



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



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



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



• 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



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∆



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



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%



< 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



4 Cake and Expeller

32

Pre-Treatment

De-Oiling

seed

feed

solids Crude oil


Isolate Concentrate

etc.


Glycerin, FFA, PL,

Tocopherol


etc.

Polyphenol etc.

Oil and derivates

PL, Soap...




• 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 components (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



• 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



• 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



5 By-Products

Pre-Treatment

De-Oiling

Seed

Feed

Solids Crude oil


Isolate Concentrate

etc.


Glycerin, FFA, PL,

Tocopherol


etc.

Polyphenol etc.

Oil and derivates

PL, Soap...




• 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


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


• 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

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