Breakdown and Distribution of Substances in Mechanical Rapeseed/Canola Processing

Transcription

1 Breakdown and Distribution of Substances in Mechanical Rapeseed/Canola Processing Ted Neuman, Steffen Hruschka, Robert Zeldenrust, Renewable Resources / GEA Westfalia Separator Group GmbH

2 Agenda 1. Seed and pre-treatment 2. De-oiling 3. Oil processing Refining and Transesterfication 4. Deoiled cake fraction 5. By-products 2

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 3

4 1 Seed and pretreatment according Diss. Heift 2001 and * B. Matthäus 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 [%] (15-22) Fraction comp. [%] Triglycerides 44, Proteins 22, Carbohydrates 20,9 1 (n-free extrtact) Lignin Poly; 3-6 Poly; 1-3 <Oligo <Oligo 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,

5 Introduction Basic flow sheet seed Pre- Treatment De-Oiling Crude oil cake Oil processing Cake & Flakes processing feed Oil and derivates PL, Soap.. PP, fibre Proteins By Product processes Edible oil Biodiesel etc. Glycerin, FFA, PL, Tocopherol Polyphenol etc. Isolate Concentrate etc. 5

6 Introduction seed Pre- Treatment De-Oiling Crude oil solids Oil processing Cake & Flakes processing feed Oil and derivates PL, Soap... PP, fibre Proteins By Product processes Edible oil Biodiesel etc. Glycerin, FFA, PL, Tocopherol Polyphenol etc. Isolate Concentrate etc. 6

7 1 Seed and pre-treatment 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 % (Matthäus 1998) Pre-preatment: increased NHP 7

8 2 Deoiling; cake % Oil Protein Fibre Glycosinolate Sinapin Cold press ,5 Hot expeller reduced reduced Flakes 3, ppm Dehulled 2 + (14-57)% Seed Press cake press Extraction feed solid oil oil Presss oil clarifying Water degumming gums drying Lecithin Crude oil 8

9 2 deoiling; cake % Oil Protein Fibre Glycosinolate Sinapin Cold press ,5 Hot expeller reduced reduced flakes 3, ppm dehulled + (14-57)% Seed Press cake press Extraction feed solid 0.8 to 2.0 % FFA Low NHP Cold/hot =150/500 ppm P Presss oil clarifying 0.8 to 2.0 % FFA High NHP ppm P Water degumming gums drying Lecithin Result ppm HP Crude oil ppm NHP 9

10 2 deoiling; cake % Oil Protein Fibre Glycosinolate Sinapin Cold press ,5 Hot expeller reduced reduced flakes 3, ppm dehulled + (14-57)% Seed Press cake press Extraction feed solid 0,8 to 2,0 % FFA Low NHP Cold/hot =150/500 ppm P Presss oil clarifying 0,8 to 2,0 % FFA High NHP o0 ppm P Water degumming gums drying Lecithin Result ppm HP Crude oil ppm NHP 10

11 3 oil processing Seed Pre- Treatment De-Oiling Crude oil solids Oil processing Cake & Flakes processing Feed Oil and derivates PL, Soap... PP, fibre Proteins By Product processes Edible oil Biodiesel etc. Glycerin, FFA, PL, Tocopherol Polyphenol etc. Isolate Concentrate etc. 11

12 3- Press oil clarifying Decanter 2 phase clarifier: 20 t/d to 1500 t/d Decanter C Crude oil with solids 4 to 15% DS Proteins, fibre Alternatives: Ultrasonic Filter seed press Solids recycling 75 % DS % Oil abs. Clarified crude oil Process water 0,1 to 0,3 % DS 12

13 3 Degumming 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 13 Dr. St.Hruschka/R.Zeldenrust / Renewable Resources

14 3 Composition PL in rapeseed Soybean Oil Canola Oil Sunflower Oil Phosphorous content [%] Phospholipids content [%] Phospholipids distribution [%] PC (MW 784) PI (MW 861) PE (MW 742) PA (MW 699) 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

15 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 Fatty Acid Fatty Acid Glycerol O O P O Polar rest O - 15

16 3 Degumming Degumming without neutralisation Water degumming Special + Top degumming Enzymatic degumming Alcohol degumming HP (Lecithin) NHP (Gums) NHP (PL-derivate) dry for Biodiesel 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 Dr. St.Hruschka/R.Zeldenrust / Renewable Resources

17 3 Integration of degumming in refining processes Physical Refining > 3% FFA Crude oils < 3% FFA Chemical Refining Lecithin HP Water-Degumming Water-Degumming Gums Drying Lecithin Gums NHP Acid-Degumming Alkali- Neutralisation Soapstock Splitting Acid oil Dewaxing Dewaxing Bleaching Bleaching Fatty acids Deacidification/ Deodorisation Deodorisation Distilled fatty acids Edible oil Edible oil 17

18 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

19 3 Special Degumming Steam Acid Lye Water Steam Water Vacuum M Degummed oil M M M Crude oil Flexible plant Can be used for degumming and neutralization Degumming with one or two stages 19 Gums One stage, without washing less effective, no waste water Two stages, with washing Lower P-content Wash water as additional effluent stream Washwater

20 3 Special Degumming Process Parameters M M M M Oil temperature: C Acid addition: % 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: C Wash water addition: 3 5 % vol. Mixing: dynamic or inline static mixer 20

21 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

22 TOP-Degumming Process parameters M M Oil temperatures: C Acid addition: % 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: % 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 22

23 3. Degumming/ Refining Results P & Fe -content: Special degumming Top degumming P for one stage process, no washing: ppm 10 ppm P for two stage process, with washing: ppm Fe- < 0,2 ppm Content in gums Waste water quality Acetone insoluble (AI): % % Oil content on dry base: % % Water % >50 Moisture content in the degummed oil Oil content approx. 5 % Without vacuum drying: < 0,5 % < 0,5 % With vacuum drying: < 0,1 % < 0,1 % 23

24 3 Reaction of Enzymes Products with the use of specific enzyme: PLA 1 : MonoAcylGlycerol - Phospholipid (Lyso-Phospholipid) + Free Fatty Acid PLA 2 : MonoAcylGlycerol - Phospholipid + Free Fatty Acid PLC: Di-Acyl-Glyceride + Phophoroester PLA 1 PLC Fatty Acid Fatty Acid Glycerol P Polar rest PLA 2 24

25 3 Enzymatic Degumming with 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. Free Fatty Acid PLA 1 Fatty Acid Fatty Acid Glycerol O O P Mono-Acyl-Glyceride Phospholipid O Polar rest O - 25

26 3 Enzymatic Water Degumming with 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. Di-Acyl-Glyceride PLC Fatty Acid Fatty Acid Glycerol O O P O Phosphoroester Polar rest O - 26

27 3 Advantages of the Enzymatic Degumming 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 Steam Acid Lye Cooling Enzyme + Steam Vacuum water Water M Degummed oil Crude oil M Gums 27

28 3 Comparison of caustic vs. enz. degumming Utilities Special TOP Degumming Enzymatic degumming Acid % 1 or % % 2 Caustic ( 50 %) kg/t oil kg/t oil 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 % % % Enzymes 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 P * P * Approx. 20% reduction vs. TOP P in degummed oil with washing max. 10 ppm ppm (on Enzyme) Yield 96 96,5 3 97,4 (PLA 1 ) 98,3 (PLC) 3 28 * 1 Phosphoric Acid * 2 Citric Acid * 3 Chris Dayton/Het Pand, Bunge 2010

29 Comparison for oils with 150 ppm P Costs for utilities plus oil losses for 400 tpd Utilitiy Costs [TEUR / Year] 2,000 1,800 1,600 1,400 1,200 1, Crude Oil specification: FFA: 1% Phosphorous: 150ppmP Moisture: 0.1% Impurities: 0.1% Special Deg. TOP Deg. Enzyme Deg. (2-stage) Water degummed oil: Typical if Lecithin processing is applied 29

30 Comparison for oils with 500 ppmp Costs for utilities plus oil losses for 400 tpd Utilitiy Costs [TEUR / Year] 3,500 3,000 2,500 2,000 1,500 1, Crude Oil specification: FFA: 1% Phosphorous: 500ppmP Moisture: 0.1% Impurities: 0.1% Special Deg. TOP Deg. Enzyme Deg. (2-stage) 30

31 3 Matrix for choosing the right degumming process according to theoretical cost calculations < 50 ppm P ppm P > 500 ppm P Degumming in Bleaching section TOP-Degumming Enzymatic Degumming Remark: For enzyme costs between 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

32 4 Cake and Expeller seed Pre- Treatment De-Oiling Crude oil solids Oil processing Cake & Flakes processing feed Oil and derivates PL, Soap... PP, fibre Proteins By Product processes Edible oil Biodiesel etc. Glycerin, FFA, PL, Tocopherol Polyphenol etc. Isolate Concentrate etc. 32

33 4 Solids: Market Opportunity 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: Medium term: feed, industry food More demand for proteins without the disturbing minor components 33

34 4 Protein Isolate & Concentrate 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% 34

35 4 Protein products 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 35

36 5 By-Products Seed Pre- Treatment De-Oiling Crude oil Solids Oil processing Cake & Flakes processing Feed Oil and derivates PL, Soap... PP, fibre Proteins By Product processes Edible oil Biodiesel etc. Glycerin, FFA, PL, Tocopherol Polyphenol etc. Isolate Concentrate etc. 36

37 5 Minor Components Sinapine and Sinapine acid content % SP sinapine SA (sinapine acid) 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. 37

38 Sinapin Polyphenol in the water after special protein precipitation Polyphenole in mg/g Sinpinsäure Sinapin Dehulled cake complete seed cake: cold, warm, hot pressed Kernbruch Kalt Vollkorn Kalt Vollkorn Warm Vollkorn Heiß Pressart 38

39 Globulinphase Drying and grinding Parameter % abs TS 20 % TS Öl Protein Sonst (KH)

40 Hemp 40

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