Fractionation of rapeseed from oil extraction to minor

GEA Mechanical Equipment / GEA Westfalia Separator Group GmbH

Fractionation of rapeseed from oil extraction to minor products

Dr. Ing. Steffen Hruschka

Renewable Resources

GEA Mechanical Equipment

1. Rapeseed is an important oil seed

2. Press cake is a source for proteins and for minor compounds

3. Processes towards valuable compounds out of expeller cake

4. By-products like fibers, phytic acid, and phenols (sinapine etc.) are

produced

Agenda

Rapessed Congess Saskatoon 2015-07-06; Hruschka 2


1 Seed and pre-treatment

• With 12% of the global vegetable oil production, rapeseed represents

the third greatest volume after palm (18%) and soy (26% )

• Total production: approx. 60 million t/a

• EU production: 30% of global production; Germany 30% of EU

Rapeseed production 2012

according to „Indexmundi“

Rapessed Congess Saskatoon 2015-07-06; Hruschka

(FAO)

3


Rapeseed – Processing standards today

Oil 45%

Protein 20%

Hull 15%

Others 20%

(polyphenols,

phytic acid,

glucosinolates,

cellulose, sugars)

Oil press cake

by-product from processing the

rapeseed oil

About 36 Mio tons of oil press cake are

produced every year, mostly in EU,

Canada, China, India*

percent

*Source: FAO, 65 Mio tons of rapeseed



Seed and pre-treatment

according Diss. Heift 2001 and * B. Matthäus 1998 1 Aiple 2002, 2 Jeroch et al 2008, 3 Diss. Natsch 2006

Seed compl Hull Cotyledon

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- and glycolipids 0,5 – 1,5

Sinapine* 0,57-0,9 % 0,07-0,23 0,83-1,15

Glucosinolates <25µmol/g 2 6,1 (14 Ukrain)

Phytic acid 2,4-3,5 *,3 0,2-1 3 3-4 3







produced

Press cake



• Press cake for feed:

• After oil extraction approx. 60% of the seed remains as press cake or flakes

containing proteins

• The press cake can be used as feed for pigs, cattle, and poultry.

• German rape seed consumption:

• The proportion of this rape cake compared to the total animal feed

increased from 1.2 to 3 million (1985 to 2008) and is greater than in other

countries

• Current demand: feed, industry

• Medium term: food

Increasing demand for proteins without

disturbing minor components

Press cake



• No pre-treatment is needed

for cold and medium warm press (press cake) - PC

• Heating for hot pressing ( rape expeller cake) - REC

• Dehulling in order to

reduce fiber content (kernel cake) - KeC

• Hexane oil extraction - Flakes

Known facts:

• Heating reduces sinapine (Jeroch et. Al 2008)

• No difference in oil content (8 to 20%) between REC and PC (Till 2007)

• Sinapine and sinapic acid content is increased by dehulling (from

14% to 50%)

• Phytic acid is increased by dehulling from 12.7% to 38% (Matthäus 1998)

• Pre-pretreatment: increased NHP in oil

Press cake characteristics


PC: phosphatidylcholine; NHP:

8


• Concentrate > 60% protein

• Deoiled material (solvent extraction, risk: protein denaturation and washing)

• UDP (un-degradable protein)

Seed 15%, REC 15% cold , Rape-Flakes 35% (DLG Futtermittel 2011)

• Isolate > 90% protein

• NSI* and water binding potential: rape protein vs. soy protein (Kodagoda1973,

Aluko 2001, Kroll 2009)

• NSI:0.1%-0.9% (low phytic acid); water:1.32%-1.57%; oil:0.61%-1.29%

• Food EU-Law

Press cake & some products


*NSI: nitrogen solubility index

9


• To date the use of the intermediate rape protein products is limited

due to the minor components (e.g. phenols) in the standard cake

• Glycosinolates

• Tannines (phenolic components)

• Phytic acid

• Fibers

Source (Leming, R. and Lember, A.: Chemical Composition of Expeller-Extracted and cold pressed

rapeseed cake; Agrararteadus, Journal of Agricultural Science , 2005)

Press cake - antinutritional factors







produced

Process



Process overview

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



Process: press oil & extraction

Press

cake

Pressing Extracting

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* + (14-57)%


* B. Matthäus 1998

13



Press

cake

Pressing Extracting

Drying

Seed

Feed

Lecithin

Solid

Crude oil


Water degumming

Gums



Hot

expeller


Flakes 3,2 38 14 7.6 -10 ppm

Dehulled* + (14-57)%

Low NHP

Cold/hot =150/500 ppm P

Result

0-200 ppm HP

80-200 ppm NHP


* B. Matthäus 1998

14



Press

cake

Pressing Extracting

Drying

Seed

Feed

Lecithin

Solid

Crude oil


Water degumming

Gums



Hot

expeller


Flakes 3,2 38 14 7.6 -10 ppm

Dehulled* 42 + (14-57)%

Low NHP

Cold/hot =150/500 ppm P

High NHP

600-10o0 ppm P

Result

0-200 ppm HP

80-200 ppm NHP


* B. Matthäus 1998

15


• New patents are recently filed (2008) for isolates and products

• Dehulling reduces fibers but increases sinapine and phytic acid

• Breeding reduces glycosides

Process material


0

10

20

30

40

50

60

70

80

90

100

raw saat Hull Kotyledon Cake no hull cake

co

nte

n in

kg

of

100 k

g s

eed

substance

Phytinsre.

Sinapin+sSre.

Lignin

KH total

Prot

PL

TAG

16

GEA Mechanical Equipment Rapessed Congess Saskatoon 2015-07-06; Hruschka

Raw material

Raw material is preferable cold pressed cake

17


Process indicated diagram

Dehulling Step 0

Pressing Step 1

Mixing Step 2

Hull separation Step 3

Hull

Protein separation Step 4

Degassing of albumins and PP*

+H2O +Additives

+ Additives

Phytic acid

Oil

Globulin powder Degassing of globulin curd

Albumins and PPs

Dry Hulls

Press cake

Oil

*PP: polyphenol

18


Process


Additives

Soft temperature protein phase extraxtion – patent pending

Phytic Acid

Additives

Additives

Sinapin

Globuline

Fibers (hull) and sinapine are part of the SynRG research project (BMEL, FNR)

19


Steam CA 225-02-32

Step one: wet decanter de-hulling

Water and additives

Hulls

Protein distribution

20-30 % 70-80%

Dispersion

No remaining lignin left in

the light phase


DECANTER SEPARATES

20


Globulin separation from dispersion

Overflow

containing

foaming

albumins

Protein curd

containing

globulins

1) ~25% of the proteins 1) ~50 % of the proteins

Up to 60% Protein in DM


Albumin

Globulin

21


Final product globulins

Pulver

7

Wet protein curd:

Volume ~100-200%

of the rape cake

30-40% of the total dry matter

contains ~40-50% of the total

rape seed proteins


Parameters %

abs.

% DM

Dry matter 20

Oil 10-15

Protein 50-60

Other matters 30-35

22

GEA Mechanical Equipment 23 Rapessed Congess Saskatoon 2015-07-06; Hruschka

Parameter Probe

Curd I

(Test11228,1)

Curd II

(Test 11228,2)

Curd 0

(Test 11198)

DM-% 94,85 95,56 94,65

Protein -%

(as it is) 52,06 49,03 57,45

Protein-%

(on DM) 54,89 51,31 60,70

Waterbinding

ml H2O/ 1g DM 1,7 1,6 1,8

Oil binding**

G oil/1g DM 0,64 0,63 0,49

Emulsifying

ml oil/1g DM 770 780 780

Globuline

GEA Mechanical Equipment 24

Globuline Composition


1850 mg/kg P from phytic acid

lecithin

GEA Mechanical Equipment 25 Rapessed Congess Saskatoon 2015-07-06; Hruschka

Globuline Quality vs. rapeseed and soy

Dry Matter

Ash

Protein

Un degradable protein

Starch

Fat

Fibre

K

P

Na

k






produced

By-products



Albumin phase

Parameter % abs % TS

Dry matter 8

Oil 20

Protein 30-40

Other matters

(CH*)

40-50

Albumin phase:

• 200-300% of the initial rape cake

volume

• <30% of the initial dry matter of

the cake

• Approx. 25% of the initial cake

proteins


*CH: carbohydrates

27


Albumin phase: sinapine

0,00

0,50

1,00

1,50

2,00

2,50

3,00

Kernbruch Kalt Vollkorn Kalt Vollkorn Warm Vollkorn Heiß

Po

lyp

he

no

l [m

g/g]

Pressing

Polyphenols in the albumin phase

Sinpinsäure

Sinapin

Dehulled cake complete seed cake: cold, warm, REK

Research results from SynRG project (BMEL, FNR); * different raw material


Sinapic acid

Sinapine

Sinapine*

28


• Sinapine and sinapic acid content %

SP sinapine 0.9- 1.6

SA (sinapic acid) 0.6 -1.2

SG (synapoil glycose) ~ 0.1

(SynRG)

Khattab, JAOCS 2010

1) Overflow containing sinapine

• Extracted out of albumin phase

• Contains of ~90% water

(patent pending)

2) Sinapine polymerisation

Albumin phase: five minor components



Wet hull phase

extracted Flakes Wet hulls

dehulled seed B

Analyses done by ATB ICT

Oil 1

Protein 54 35

Glucose 3,8 14

Xylose 7,6

Acid soluble lignin 7,4

Lignin 10 32

Phytic acid 4

Cellolose 11

Hemicellulose 17,1

total 95,6 100,7

The total lignin content in the hull fraction

increases to approx. 40%

(hand separated hull: 35%)

30


• Phytic acid

• < 3.5 % in seed, 4% in cotyledons

• Forms phytates with Mg, K, Ca

• Recovered from hull fraction

Patent pending

Wet hull phase: phytic acid



• Rapes seed press cake is separated into

• Globuline phase (50-60% protein + carbohydrates, oil and

lecithine)

• Albumine phase with Sinapine (approx. 33% Protein on DM)

• Wet hulls

• Minor components are separeted from Glubulines, like:

• Glycosinolates

• Tannines (phenolic components)

• Phytic acid

• Fibers

Summary

32


• Part of this development was performed within the SynRG project

• Thanks to the GEA colleagues, who performed further work on this

project

• Financed by BMEL and supported by FNR Gülzow

Thanks



Documents

Fractionation of rapeseed from oil extraction to minor