EP0257388A2 - Verfahren zur Umesterung von Fetten - Google Patents

Verfahren zur Umesterung von Fetten Download PDF

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Publication number
EP0257388A2
EP0257388A2 EP87111327A EP87111327A EP0257388A2 EP 0257388 A2 EP0257388 A2 EP 0257388A2 EP 87111327 A EP87111327 A EP 87111327A EP 87111327 A EP87111327 A EP 87111327A EP 0257388 A2 EP0257388 A2 EP 0257388A2
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EP
European Patent Office
Prior art keywords
reaction
lipase
fats
transesterification
diglyceride
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP87111327A
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English (en)
French (fr)
Other versions
EP0257388A3 (de
Inventor
Kazuhiro Nakamura
Hideki Yokomichi
Koichi Okisaka
Tsutomu Nishide
Yoshiharu Kawahara
Seizi Nomura
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Kao Corp
Original Assignee
Kao Corp
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Filing date
Publication date
Application filed by Kao Corp filed Critical Kao Corp
Publication of EP0257388A2 publication Critical patent/EP0257388A2/de
Publication of EP0257388A3 publication Critical patent/EP0257388A3/de
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
    • C11C3/10—Ester interchange
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
    • C11C3/08—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils with fatty acids

Definitions

  • This invention relates to a process for tran­sesterifying fats with the use of a lipase. More particularly, it relates to a process for tran­sesterifying fats with the use of an enzymatic pre­paration containing a lipase which has a thermo­stability at a sufficiently high temperature to melt the fats to be used as the substrate.
  • transesterification of fats is an important technique in the production of edible processed fats such as margarine or shortening.
  • the transesterification of fats has been carried out through chemical processes. Namely, there have been employed alkaline materials such as alkali metal, alkali metal alcholates or alkali metal hydroxides or various metal salts as catalysts therefor.
  • alkaline materials such as alkali metal, alkali metal alcholates or alkali metal hydroxides or various metal salts as catalysts therefor.
  • these conventional methods would result in rearrange­ment of fatty acids in the fats according to the principle of random distribution with regard to the position where a fatty acid binds hydroxy group of glycerol. No specificity is observed at all in the binding position of the fatty acid in the transesterified fats.
  • Fats are transesterified with a lipase selectively in relation to position.
  • the lipase used is an enxyme being capable of hydrolyzation of fats. See Japanese patent publication A (unexamined) No. 104506/1977. According to this process, it is required that moisture be present in the reaction system in order to activate the lipase.
  • the required amount of the moisture is as small as 0.2 to 1.0 %, it is unavoidable that the inherent properties of the lipase induce the hydrolysis of the fats to thereby form by-product, e.g., diglyceride, which lowers the yield of the transesterified product.
  • by-product e.g., diglyceride
  • thermostable enzymatic preparation cf. Japanese Patent Laid-Open No. 98984/1985.
  • an enzymatic reaction at a relatively high temperature, i.e., 50°C or above without using any solvent would be frequently accompanied by the liberation of the moisture from the enzymatic preparation to the reaction system, which accelerates the formation of by-product, i.e., diglyceride to thereby lower the yield of the aimed product.
  • the present invention relates to a process for transesterifying fats with the use of a lipase preparation, characterized in that said lipase preparation has a thermostability at a sufficiently high temperature to melt a substrate; that no solvent is used; and that moisture is removed from the reaction system during the reaction.
  • the invention provides a process for transesterifying fats with an enzymatic preparation containing a lipase having the thermostability at a sufficiently high temperature to melt a reactive substrate, without use of a solvent, water being removed out of the reaction system during the reaction.
  • Fig. 1 is a schematic view of the reactor which is an external circulation reactor provided with a packed column as used in Example 5 wherein:
  • transesterification of fats includes transesterification between fats and fatty acid or its ester; mutual transesterification between different fats; transesterification between fatty acid ester and fatty acid; and mutual transesterification between different fatty acid esters.
  • the transesterification of fats with the use of a lipase preparation capable of hydrolyzing the fat can be carried out in a single step without requiring any complicated reaction process by employ­ing preferably 5 to 100 part (by weight; the same will apply hereinafter) of said lipase preparation per 100 parts of a substrate mixture and continuously removing moisture from the reaction system from the initiation or in the course of the reaction.
  • the transesterification can be carried out in a single step in a shorter period of time, accompanied by neither any complicated reaction process nor a decrease in the yield of transesterification product caused by the hydrolysis of the substrates. Further the decrease in the transesterifying activity of the lipase preparation can be suppressed thereby, which makes it possible to repeatedly use the preparation.
  • the type of a reactor is not strictly limited.
  • a conventional batch type reactor provided with a stirrer or a circulation reactor provided with a packed column may be effectively employed from the viewpoint of the dehydration efficiency.
  • a falling or fluidized bed type continous reactor may be used.
  • thermostable immobilized lipase preparations supported on various carriers are preferable.
  • the lipase preparation is preferably used in an amount of 5 to 100 parts per 100 parts of the fats.
  • the presence of the lipase preparation in an amount exceeding the above upper limit is undesir­able since it might cause an increase in the slurry concentration in the reaction system to thereby lower the workability.
  • Examples of the lipase of the lipase preparation to be used in the present invention include animal lipases such as those originating from microorganisms belonging to the genera Rhizopus , Aspergillus , Chromobacterium , Mucor and Pseudomonas , each having a high positive selectivity; those originating from microorganisms belonging to the genus Candida , each showing no specificity; and pancreatic lipases.
  • these lipases those produced by thermostable strains belonging to the genera Rhizopus , Pseudomonas , Chromobacterium , Mucor and Candida are particularly preferable.
  • the porcine pancreas lipase may be used.
  • the lipase is preferably immobilized on a known carrier.
  • Any carriers for immobilization for example, inorganic materials insoluble in the transesterification system, such as Celite, kieselguhr, kaolinite, silica gel, perlite, glass fiber, molecular sieves, activated carbon and calcium carbonate and organic polymers exerting no adverse effect on the lipase activity, such as cellulose powder, ion exchange resins and chitosan may be employed.
  • the carrier may be in various forms such as powder, granule, fiber or sponge. It is further preferable that the thermo­stability and activity of the enzyme are enhanced by immobilization. Thus it is particularly preferable to use a lipase immobilized on a macroscopically porous anion exchange resin.
  • the fats to be used in the present invention are selected from among common vegetable and animal oils and fats, processed products thereof and mixtures thereof. Examples thereof are soybean oil, cotton seed oil, rapeseed oil, corn oil, safflower oil, sunflower oil, coconut oil, beef tallow, lard and fish oil.
  • oils and fats mainly comprising glycerides having an oleic acid group bound to the 2-position thereof, such as palm oil, olive oil, sunflower oil containing a large amount of an oleic acid group, safflower oil containing a large amount of an oleic acid group, tsubaki oil, sasanqua oil, sal fat, shea butter, illipe butter, kokum butter, mowrah fat, phulwara butter, Bornean tallow, mango kernel oil and fractionation products thereof may be employed.
  • the transesterification may be carried out by reacting ester with fatty acid, ester with ester or ester with alcohol.
  • fatty acids are straight-chain ones having 2 to 24 carbon atoms and occurring in nature, e.g., saturated fatty acids such as palmitic, stearic and behenic acids as well as unsaturated ones such as oleic, linolic and eicosapen­taenoic acids.
  • the transesterification may be carried out at a temperature of 30 to 90°C, which is somewhat higher than that of general enzymatic reactions.
  • the reaction may be carried out under a reduced pressure lower than the vapor pressure. It is perferable that the reduced pressure may be within a range of 3 to 150 mmHg, although it is not restricted thereto.
  • the moisture content in the reaction system at the completion of the reaction is preferable to adjust to 0.03 part per part of the fat used as the substrate, from the viewpoint of suppressing the formation of diglyceride. Since rapid dehydration may lower the reaction rate, dehydration may be carried out at a rate of 1.0 ⁇ 10 ⁇ 3 to 1.0 ⁇ 10 ⁇ 2 g/g of sub­strate/hr from the viewpoint of maintaining a desir­able reaction rate, although it is not restricted thereto. It is also possible to blow an inert gas such as dry nitrogen into the reaction system to thereby remove moisture therefrom, if required.
  • an inert gas such as dry nitrogen
  • fatty acid a small amount of partial ester such as monoglyceride and diglyceride and unreacted alcohol may be readily removed by any conventional purification procedure such as liquid/liquid extraction, neut­ralization with an alkali or vacuum or molecular­distillation.
  • the transesterification product can be obtained in a pure form.
  • the process of the present invention aims at allowing a lipase to fully exhibit its synthesis activity by taking advantage of the fact that the synthesis activity of lipase is directly proportional to the concentration of the enzyme and inversely proportional to the moisture content thereof.
  • the present invention exhibits an additional effect such that a sufficiently high concentration of a lipase preparation would result in a mutually stabiliz­ing effect of enzymes, which lowers the denaturation of the enzymes with the lapse of time.
  • the lipase preparation recovered after the reaction can be effectively reused, which significantly enhances the productivity per unit weight of the lipase when this process is carried out on an industrial scale.
  • the process of the present invention brings about an improvement in economy.
  • the process of the present invention may be applied to, for example, the production of a substitute for expensive cacao butter from inexpensive palm oil with the use of a positionally selective lipase preparation.
  • the reaction ratio thus calculated was 91.8 %, suggest­ing that the reaction proceeded sufficiently.
  • Example 1 The procedure of Example 1 was followed except that the reaction was carried out under atomospheric pressure. The reaction ratio after five hours was as high as 101 %. However the diglyceride content was extremely high, i.e., 25.2 %, while the yield of the aimed transesterified fat was low and the quality of the same was poor.
  • Example 1 The procedure of Example 1 was followed except that the reaction was not carried out under reduced pressure but 0.01 v/v/m of dry nitrogen was blown into the head space. According to the same analyses as those described in Example 1, the reaction ratio was 91.4 % while the diglyceride content was 9.6 %, suggesting that satisfactory results were obtained similar to the case of the reaction under reduced pressure.
  • Example 2 The procedure of Example 2 was followed except that the reaction was carried out under a reduced pressure of 100 mmHg from three hours after the initiation of the reaction.
  • Example 1 The procedure of Example 1 was followed except that 50 parts of a commercially available thermostable immobilized enzyme (mfd. by Novo Industri A.S.), which comprised a lipase originating from Mucor miehei immobilized on a macroscopically porous anion exchange resin and had been previously dried in vacuo to reduce the moisture content from 8.0 % to 5.5 %, and that the reaction was carried out at 70°C.
  • a commercially available thermostable immobilized enzyme mfd. by Novo Industri A.S.
  • reaction ratio was 98.1 % while the diglyceride content was 4.1 %, i.e., lower than that in the starting materials, suggesting that the synthesis had been effected.
  • thermostable immobilized enzyme (mfd. by Novo Industri A.S.), which comprised a lipase originating from Mucor miehei immobilized on a macroscopically porous anion exchange resin and contained 8.0 % of moisture, was dried in vacuo to give a moisture content of 6.2 %.
  • 30 g of the immobilized enzyme was packed in a packed column 1 and a mixture of 100 g of a medium-melting fraction of aplm oil and 100 g of stearic acid was circulated through said packed column at 65°C. The flow rate of the mixture was 0.18 cm/sec in terms of the super­space velocity.
  • a receiver 3 was directly connected for recovering the cirulated solution.
  • the pressure in the receiver 3 was reduced to 160 mmHg.
  • the reaction ratio was 90.2 % while the diglyceride content was 9.0 %.
  • the circuration was further continued until eight hours after the initiation of the reaction.
  • the reaction ratio was elevated to 96.9% while the diglyceride content was lowered to 8.1 %.
  • 2 and 2 ⁇ represent each a jacket
  • 4 represents a fixed blade
  • 5 represents a stirring blade
  • 6 represents a liquid feed pump
  • 7 represents a flowmeter
  • 8 represents a pressure gauge.
  • Example 5 The procedure of Example 5 was followed except that the pressure in the receiver was atmospheric. After five hours, the reaction ratio was 90.6% while the diglyceride content, which had been increasing with the lapse of time, reached a significantly high level, i.e., 18.0 %. Table 2 shows the results.
EP87111327A 1986-08-13 1987-08-05 Verfahren zur Umesterung von Fetten Withdrawn EP0257388A3 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP190007/86 1986-08-13
JP61190007A JPS6344892A (ja) 1986-08-13 1986-08-13 油脂類のエステル交換反応方法

Publications (2)

Publication Number Publication Date
EP0257388A2 true EP0257388A2 (de) 1988-03-02
EP0257388A3 EP0257388A3 (de) 1989-08-30

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Family Applications (1)

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EP87111327A Withdrawn EP0257388A3 (de) 1986-08-13 1987-08-05 Verfahren zur Umesterung von Fetten

Country Status (4)

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EP (1) EP0257388A3 (de)
JP (1) JPS6344892A (de)
MY (1) MY102463A (de)
PH (1) PH23724A (de)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3815961A1 (de) * 1987-05-11 1988-11-24 Kanegafuchi Chemical Ind Verfahren zur enzymatischen umesterung bei einem geringen wassergehalt
GB2236537A (en) * 1989-09-13 1991-04-10 Unilever Plc Transesterification
WO1991006661A1 (en) * 1989-11-03 1991-05-16 Opta Food Ingredients, Inc. Lipase-catalyzed in situ generation of mono- and di-glycerides
US5093256A (en) * 1989-02-22 1992-03-03 Shen Gwo Jenn Essentially purified, thermostable and alkalophilic lipase from bacillus sp. a30-1 atcc 53841
US5166069A (en) * 1989-02-22 1992-11-24 Michigan Biotechnology Institute Bacillus sp. A30-1 ATCC no. 53841
EP0652289A1 (de) * 1993-11-05 1995-05-10 Unilever Plc Statistische Umesterung von Triglyceridfetten
US7666618B2 (en) 2004-07-16 2010-02-23 Danisco A/S Lipolytic enzyme: uses thereof in the food industry
US7718408B2 (en) 2003-12-24 2010-05-18 Danisco A/S Method
US7781001B2 (en) 1998-07-21 2010-08-24 Danisco A/S Foodstuff
US8652809B2 (en) 2007-08-17 2014-02-18 Dupont Nutrition Biosciences Aps Method for producing ultra-heat treatment milk
EP3847895A1 (de) 2020-01-07 2021-07-14 Bunge Loders Croklaan B.V. Verfahren zur herstellung eines zufällig interesterifizierten fettprodukts

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02142484A (ja) * 1988-11-25 1990-05-31 Japanese Res & Dev Assoc Bio Reactor Syst Food Ind 高濃度トリグリセライドの製造法
US5311937A (en) * 1992-07-08 1994-05-17 Raito Kogyo Co., Ltd. Extractor for an injection pipe
JP2796925B2 (ja) * 1993-09-17 1998-09-10 日清製油株式会社 リパーゼによるエステル交換法
US6936289B2 (en) 1995-06-07 2005-08-30 Danisco A/S Method of improving the properties of a flour dough, a flour dough improving composition and improved food products
NZ528260A (en) 2001-05-18 2005-09-30 Danisco Method of improving dough and bread quality with the addition of an enzyme that hydrolyses a glycolipid and a phospholipid and incapable of hydrolysing a triglyceride or monoglyceride
US20050196766A1 (en) 2003-12-24 2005-09-08 Soe Jorn B. Proteins
DE602004030000D1 (de) 2003-01-17 2010-12-23 Danisco Verfahren zur in-situ-herstellung eines emulgators in einem nahrungsmittel
US7955814B2 (en) 2003-01-17 2011-06-07 Danisco A/S Method
US7906307B2 (en) 2003-12-24 2011-03-15 Danisco A/S Variant lipid acyltransferases and methods of making
GB0405637D0 (en) 2004-03-12 2004-04-21 Danisco Protein
EP2109670A1 (de) 2007-01-25 2009-10-21 Danisco A/S Herstellung einer lipid-acyltransferase aus transformierten bacillus licheniformis-zellen

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2035359A (en) * 1978-11-21 1980-06-18 Fuji Oil Co Ltd Producing a cacao butter substitute by transesterification of fats and oils
EP0035883A2 (de) * 1980-03-08 1981-09-16 Fuji Oil Company, Limited Verfahren zur enzymatischen Zwischenveresterung von Fett und hierzu verwendetes Enzym
EP0064855A1 (de) * 1981-05-07 1982-11-17 Unilever Plc Behandlung von Fetten
EP0126416A1 (de) * 1983-05-19 1984-11-28 Asahi Denka Kogyo Kabushiki Kaisha Reaktionsverfahren für die Umesterung von Fetten und Ölen
EP0140542A1 (de) * 1983-09-05 1985-05-08 Novo Nordisk A/S Immobilisierte Lipase-Zubereitung und deren Verwendung

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56127094A (en) * 1980-03-08 1981-10-05 Fuji Oil Co Ltd Enzymatic ester-exchange process
JPS578787A (en) * 1980-03-14 1982-01-18 Fuji Oil Co Ltd Esterification by enzyme
JPS5928482A (ja) * 1982-08-05 1984-02-15 Asahi Denka Kogyo Kk 油脂類のエステル交換反応方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2035359A (en) * 1978-11-21 1980-06-18 Fuji Oil Co Ltd Producing a cacao butter substitute by transesterification of fats and oils
EP0035883A2 (de) * 1980-03-08 1981-09-16 Fuji Oil Company, Limited Verfahren zur enzymatischen Zwischenveresterung von Fett und hierzu verwendetes Enzym
EP0064855A1 (de) * 1981-05-07 1982-11-17 Unilever Plc Behandlung von Fetten
EP0126416A1 (de) * 1983-05-19 1984-11-28 Asahi Denka Kogyo Kabushiki Kaisha Reaktionsverfahren für die Umesterung von Fetten und Ölen
EP0140542A1 (de) * 1983-09-05 1985-05-08 Novo Nordisk A/S Immobilisierte Lipase-Zubereitung und deren Verwendung

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3815961A1 (de) * 1987-05-11 1988-11-24 Kanegafuchi Chemical Ind Verfahren zur enzymatischen umesterung bei einem geringen wassergehalt
US5093256A (en) * 1989-02-22 1992-03-03 Shen Gwo Jenn Essentially purified, thermostable and alkalophilic lipase from bacillus sp. a30-1 atcc 53841
US5166069A (en) * 1989-02-22 1992-11-24 Michigan Biotechnology Institute Bacillus sp. A30-1 ATCC no. 53841
GB2236537A (en) * 1989-09-13 1991-04-10 Unilever Plc Transesterification
WO1991006661A1 (en) * 1989-11-03 1991-05-16 Opta Food Ingredients, Inc. Lipase-catalyzed in situ generation of mono- and di-glycerides
EP0652289A1 (de) * 1993-11-05 1995-05-10 Unilever Plc Statistische Umesterung von Triglyceridfetten
US7781001B2 (en) 1998-07-21 2010-08-24 Danisco A/S Foodstuff
US7718408B2 (en) 2003-12-24 2010-05-18 Danisco A/S Method
US7666618B2 (en) 2004-07-16 2010-02-23 Danisco A/S Lipolytic enzyme: uses thereof in the food industry
US8652809B2 (en) 2007-08-17 2014-02-18 Dupont Nutrition Biosciences Aps Method for producing ultra-heat treatment milk
EP3847895A1 (de) 2020-01-07 2021-07-14 Bunge Loders Croklaan B.V. Verfahren zur herstellung eines zufällig interesterifizierten fettprodukts
WO2021140109A1 (en) 2020-01-07 2021-07-15 Bunge Loders Croklaan B.V. Method of preparing a randomly interesterified fat product

Also Published As

Publication number Publication date
JPS6344892A (ja) 1988-02-25
PH23724A (en) 1989-11-03
JPH0338837B2 (de) 1991-06-11
EP0257388A3 (de) 1989-08-30
MY102463A (en) 1992-06-30

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