Enzymatic Degumming Processes for Oils from Soya, Rape and Sun. Dr.-Ing. Ernst W. Münch

Transcription

1 Enzymatic Degumming Processes for s from Soya, Rape and Sun Date: September, 00

2 Degumming processes Enzyme reaction and Enzymes Different steps of the enzymatic process Process for Rape and Soya Process for Sun Summary

3 Phospholipids Carbohydrates Proteins Metals Soap Part of Waxes

4 Phosphatidic-Choline P. -Inositol P. -Acid P. -Ethanolamine P. -Serine

5 Lipids and affinity Phospholipid O CH -O-C-R 1 O R -C-O-C-H O CH -O-P-O-X O Triglyceride O CH -O-C-R 1 O R -C-O-C-H O CH -O-C-R 3 R # = fatty chains X = H, choline, ethanolamine, serine, inositol, etc. affinity affinity

6 What are enzymes? Enzymes are proteins Present in all living cells, but not alive Control vital metabolic processes Break down and build up materials in organisms Enzymes are catalysts Speed up chemical processes Are not consumed in the process Operate under gentle conditions

7 Types of Phospholipase subclasses of phospholipase A1, A, B, C and D Only phospholipases A1 and A are currently commercially available Cleave one fatty per molecule of lecithin Phospholipase A Phospholipase A1 O CH -O-C-R1 R-C-O-CH O O CH -O-P-O-X O Phospholipase C Phospholipase B Phospholipase D X = H, choline, ethanolamine, serine, inositol, etc.

8 The phospholipids in the crude are packed as metal ion containing micelles Low amounts of and a high amount of metal ions is making the micelles hard olie Fe Ca Ca Ca Ca The citric step in degumming is loosening up the micelle and enables the phospholipase to get in The citric is chelating the metal ions

9 The enzyme operates on phospholipids on the interface between and The phospholipids are located at the interface of the The enzyme is in the phase Enzyme olie

10 Model of the phospholipids PC PI PE PA The groups on the phosphor differ in size and structure. The larger the group the more hydratable is the phospholipid Lyso-forms of phospholipids are easier to hydrate

11 When phospholipid is hydrolyzed to lyso-form they become hydratable olie hydrolysis olie Splitting off a fatty makes the molecule more hydrophilic That makes the PA easy to hydrate and remove with the phase

12 The basic stages in the process Bring the phospholipids to the / interface Add citric to chelate metals Emulsify the mixture to provide a large surface area Enzymatic reaction Convert phospholipids to the lyso form Separation Centrifugation to remove the and phospholipids By low content

13 Enzymatic refining conditions Caustic () Temperature Hold time 0 ppm for Sun 00 ppm 1. to mole equivalents relative to citric 0-ºC 1-3% depending on quality 0 ppm for Sun 30 ppm 3 to hours

14 Effect of on Degumming Increases ph for Optimum Enzyme Activity Rapeseed Phosphorous (ppm) 300 addition 0 Caustic addition 00 0 Enzyme addition 0 0 Equivalents of added 1. (ph.) 1. (ph.0) 1. (ph.3).0 (ph.) Time (hours) 1. mole equivalents relative to citric is optimum for this

15 Temperature Dependence of Lecitase Ultra Rapeseed 30 Phosphorous (ppm) addition Enzyme addition Caustic addition 0 C 0 C C 0 C C Time (hours) 0- o C is optimum

16 Effect of on Degumming Rapeseed Phosphorous (ppm) 300 addition 0 00 Caustic addition 0 Enzyme addition 0 0 added % 3%.% 1.3% Time (hours) % is optimum with this

17 Effect of Lecitase Ultra Dose Rapeseed 00 addition Phosphorous (ppm) Caustic addition Enzyme addition ppm 0 ppm 0 ppm 0 ppm Time (hours) Start with 0 ppm and optimize. Note the relationship between dose, time and final phosphorus level.

18 Degumming process of Soya and Rape with the Enzyme Crude or 0 C 1 Centrifuge gums 0 C -Stage 0 C 1 Full degummed a

19 Equipment List for Enzymatic Refining for a capacity of 0 t/d Number Process Equipment Size, etc. 1 3 a 1 a 1 Heat exchanger Storage Dosing Pump tank Centrifugation pump Heat exchanger Caustic Caustic Dosing Pump addition Enzyme tank Enzyme Dosing Pump High shear Dosing Pump Heat exchanger Separator l 0 l/h 1 m 3 m 3 /h 1. m 3 0 l/h l/h 0 l ml/min 0 m 3 m 3 /h

20 Crude Degumming process for sunflower with integrated predewaxing with Phospholipase A1 C 1 0 Washing and predewaxed a C -Stage 0 m 3 3 h C 1 a a gums Ammonia 1 1 Waxes a Hot a 1a 3

21 Equipment List for Enzymatic Refining incl. Predewaxing for a capacity of 0 t/d Number Process Equipment Size, etc Na Heat exchanger Storage Dosing Pump tank Heat exchanger Caustic Caustic Dosing Pump addition Enzyme tank Enzyme Dosing Pump High shear Heat exchanger Crystallizer Heat exchanger Separator Heat exchanger Crystallizer Heat exchanger Separator Static Mixer Heat exchanger Seperator Pumps l l/h 1 m 3 1. m 3 l/h 00 0 l/h 0 l ml/min 0 m 3 0 m 3 m 3 0 m 3

22 Crude Degumming process for sunflower with integrated predewaxing with Phospholipase A1 C 1 0 Washing and predewaxed The temperature is adjusted to o C. a C -Stage 0 m 3 3 h C 1 a a gums Ammonia 1 1 Waxes a Hot a 1a 3

23 Crude Degumming process for sunflower with integrated predewaxing with Phospholipase A1 C 1 0 Washing and predewaxed The citric dosage is initially 00 ppm (0.00%) and can be optimised. The citric is added as a 0% solution in. a C -Stage 0 m 3 3 h C 1 a a gums Ammonia 1 1 Waxes a Hot a 1a 3

24 Crude Degumming process for sunflower with integrated predewaxing with Phospholipase A1 C 1 0 Washing and predewaxed A shear, e.g. Alfa Laval MX, Silverson or Bran+Lubbe, ensures good contact between the citric and the metal ions that it has to chelate. Efficient mixing is very important. a C -Stage 0 m 3 3 h C 1 a a gums Ammonia 1a 1 1 a Waxes Hot a 3

25 Crude Degumming process for sunflower with integrated predewaxing with Phospholipase A1 C 1 0 Washing and predewaxed A single-stage retention tank with to 30 minutes of residence time allows the reaction to reach completion. a C -Stage 0 m 3 3 h C 1 a a gums Ammonia 1 1 Waxes a Hot a 1a 3

26 Crude Degumming process for sunflower with integrated predewaxing with Phospholipase A1 C 1 0 Washing and predewaxed to o C to provide the conditions for the enzyme reaction and for the crystallization. a C -Stage 0 m 3 3 h C 1 a a gums Ammonia 1 1 Waxes a Hot a 1a 3

27 Crude Degumming process for sunflower with integrated predewaxing with Phospholipase A1 C 1 0 Washing and predewaxed The ph is adjusted by adding 1.- mole equivalents of (or 0-0 ppm when 00 ppm of is used). % or 1 M is typically used. a C -Stage 0 m 3 3 h C 1 a a gums Ammonia 1 1 a Waxes Hot 1a a 3

28 Crude Degumming process for sunflower with integrated predewaxing with Phospholipase A1 C 1 0 Washing and predewaxed 1-% is added. Once the system is operating, optimisation is carried out. a C -Stage 0 m 3 3 h C 1 a a gums Ammonia 1 1 Waxes a Hot a 1a 3

29 Crude Degumming process for sunflower with integrated predewaxing with Phospholipase A1 C 1 0 Washing and predewaxed is dosed at 30 ppm and optimised after steadystate operation has been achieved. a C -Stage 0 m 3 3 h C 1 a a gums Ammonia 1a 1 1 a Waxes Hot a 3

30 Crude Degumming process for sunflower with integrated predewaxing with Phospholipase A1 C 1 0 Washing and predewaxed It is extremely important to use a very highshear at this point to ensure complete mixing and emulsification of the enzyme into the. a C -Stage 0 m 3 3 h C 1 a a gums Ammonia 1a 1 1 a Waxes Hot a 3

31 Crude Degumming process for sunflower with integrated predewaxing with Phospholipase A1 C 1 0 Washing and predewaxed A retention time of 3 hours should be provided in a -stage reactor (or more). Mild agitation is sufficient. a C -Stage 0 m 3 3 h C 1 a a gums Ammonia 1 1 Waxes a Hot a 1a 3

32 Crude Degumming process for sunflower with integrated predewaxing with Phospholipase A1 C 1 0 Washing and predewaxed down to C to start the crystallization process. a C -Stage 0 m 3 3 h C 1 a a gums Ammonia 1 1 Waxes a Hot a 1a 3

33 Crude Degumming process for sunflower with integrated predewaxing with Phospholipase A1 C 1 0 Washing and predewaxed Crystallizators cooling down the to C a C -Stage 0 m 3 3 h C 1 a a gums Ammonia 1 1 Waxes a Hot a 1a 3

34 Crude Degumming process for sunflower with integrated predewaxing with Phospholipase A1 C 1 0 Washing and predewaxed Heat the to 0 C a C -Stage 0 m 3 3 h C 1 a a gums Ammonia 1 1 Waxes a Hot a 1a 3

35 Crude Degumming process for sunflower with integrated predewaxing with Phospholipase A1 C 1 0 Washing and predewaxed Gums and some waxes, are removed by separation. a C -Stage 0 m 3 3 h C 1 a a gums Ammonia 1 1 a Waxes Hot 1a a 3

36 Crude Degumming process for sunflower with integrated predewaxing with Phospholipase A1 C 1 0 Washing and predewaxed Ammonia (%) is added, 0 ppm. The reaction should take about minutes a C -Stage 0 m 3 3 h C 1 a a gums Ammonia 1 1 a Waxes Hot 1a a 3

37 Crude Degumming process for sunflower with integrated predewaxing with Phospholipase A1 C 1 0 Washing and predewaxed The is cooled down to C to start the crystallization again. a C -Stage 0 m 3 3 h C 1 a a gums Ammonia 1 1 Waxes a Hot a 1a 3

38 Crude Degumming process for sunflower with integrated predewaxing with Phospholipase A1 C 1 0 Washing and predewaxed Crystallizators cooling down the to C a C -Stage 0 m 3 3 h C 1 a a gums Ammonia 1 1 Waxes a Hot a 1a 3

39 Crude Degumming process for sunflower with integrated predewaxing with Phospholipase A1 C 1 0 Washing and predewaxed The is heated to 0 C for the predewaxing centrifuge. a C -Stage 0 m 3 3 h C 1 a a gums Ammonia 1 1 Waxes a Hot a 1a 3

40 Crude Degumming process for sunflower with integrated predewaxing with Phospholipase A1 C 1 0 Washing and predewaxed The centrifuge removes the waxes. The wax content is lower than 0 ppm. a C -Stage 0 m 3 3 h C 1 a a gums Ammonia 1 1 Waxes r a Hot a 1a 3

41 Crude Degumming process for sunflower with integrated predewaxing with Phospholipase A1 C 1 0 Washing and predewaxed Hot process is added about 0 l/ton and mixed in a static. a C -Stage 0 m 3 3 h a C 1 a gums Ammonia 1a 0a a Waxes Hot

42 Degumming process for sunflower with integrated predewaxing with Phospholipase A1 Crude 0 Washing C 1 and predewaxed The dewaxed is heated to 0 C for the washing centrifuge. a C -Stage 0 m 3 3 h C 1 a a gums Ammonia 1 1 Waxes a Hot a 1a 3

43 Crude Degumming process for sunflower with integrated predewaxing with Phospholipase A1 C 1 0 Washing and predewaxed The washing centrifuge removes the washing and the soap. a C -Stage 0 m 3 3 h C 1 a a gums Ammonia 1 1 Waxes a Hot a 1a 3

44 Results: Sun P< mg/kg Iron<0,1mg/kg Rape P<mg/kg Iron<0,mg/kg Soya P< mg/kg Iron<0,mg/kg

45 Benefits of enzymatic degumming High yield Gums contain little Safety process with low content of Phosphorus, less of Bleaching earth Significant cost savings Reduced usage Reduce waste Reduced silica and bleaching earth usage Simple, environmental-friendly process Works with crude or degummed from many sources Robust and stable process Biodegradable enzyme that is deactivated in the process

46 Summary - With the phospholipase A1 it is possible to change the phospholipids into a lyso form and free fatty. - The lyso form is hydratable and the free fatty content increase by 0.0 % per 0 mg/kg Phosphorus in the. - The citric chelates the metals to open the molecules for the enzyme. - The process is running in several industrial plants. In Mannheim, Germany an enzymatic degumming process is running for Rape and Soya since 1. The results are stable and the process is robust. - The yields of the process are high. The Phosphorus content is below mg/kg and the Iron content below 0. mg/kg. - A new process with integrated predewaxing was developed in Mannheim. It is running since 1. - The yields of the degumming and predewaxing process are high. The Phosphorus content is below mg/kg and the Iron content is lower than 0.1 mg/kg. - The process is easy to run and very robust. - In total the degumming with enzymes is well established. It is an environmentally friendly degumming process.

47 Thank you for your attention!