EP0245076A2 - Ernährungsfette - Google Patents

Ernährungsfette Download PDF

Info

Publication number
EP0245076A2
EP0245076A2 EP87303996A EP87303996A EP0245076A2 EP 0245076 A2 EP0245076 A2 EP 0245076A2 EP 87303996 A EP87303996 A EP 87303996A EP 87303996 A EP87303996 A EP 87303996A EP 0245076 A2 EP0245076 A2 EP 0245076A2
Authority
EP
European Patent Office
Prior art keywords
process according
oil
triglycerides
fat
rearrangement
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Withdrawn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
EP87303996A
Other languages
English (en)
French (fr)
Other versions
EP0245076A3 (de
Inventor
Harry Moore
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Original Assignee
Unilever PLC
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Unilever PLC filed Critical Unilever PLC
Publication of EP0245076A2 publication Critical patent/EP0245076A2/de
Publication of EP0245076A3 publication Critical patent/EP0245076A3/de
Withdrawn legal-status Critical Current

Links

Classifications

    • 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 edible fats and their preparation for use in particular in confectionery including chocolate, shortenings, margarine and other plastic emulsion food spreads.
  • unsaturated vegetable oils for example sunflower oil
  • unsaturated vegetable oils may be converted in the presence of saturated fatty acids themselves or alkyl esters thereof, to symmetrical disaturated triglycerides, particularly of palmitic and stearic acids, the presence of which in cocoa butter and other vegetable butters accounts for the sharp - melting and other physical attributes for which these expensive and often scarce products are so highly prized.
  • the most beneficial of these glycerides are the 2-oleoyl homologues.
  • the corresponding 2-linoleoyl and linoleneoyl disaturated triglycerides exhibit somewhat less satisfactory characteristics; being more highly unsaturated they are significantly softer and materially more susceptible to deterioration by oxidation.
  • the present invention provides a process for the preparation of edible fats suitable for use in confectionery and like edible compositions by rearrangement of unsaturated glyceride oils and fats to more highly saturated fats by contact as rearrangement catalyst with lipase enzyme and in the presence of saturated fatty acids or esters thereof, wherein the oil or fat exhibits a high oleate content and preferably consists substantially of 2-unsaturated triglycerides at least 90% of which are 2-oleoyl triglycerides.
  • the present invention also provides novel fats comprising symmetrical disaturated triglycerides of C16 and C18 fatty acids in which the saturated fatty acid residues are in random distribution between the 1 and 3-positions and the unsaturated fatty acid residues comprise at least 80% oleic acid residues, preferably at least 90% and more particularly at least 95% of such residues .
  • Such fats are obtained by the rearrangement processes of the present invention using as rearrangement catalyst a 1, 3-regiospecific lipase, as described in US patent 4275081.
  • High oleic sunflower varieties suitable for use on the present invention may be obtained by conventional plant breeding techniques, for example by crossing the naturally occurring high oleic varieties such as that reported by Horowitz and Winter (Nature 179:582 (1975)).
  • High oleic mutants produced by artificial means, such as the mutagen treatment of seed can also be used and the Pervenets variety (reported by Kharachenk in Fisiologiya Rastenii 26:1226 (1979)) is an example. Progenies derived from such mutants are known, eg. those reported by Fick.
  • sunflower seed is used from plant varieties giving oils with 10% or less eg.
  • oils suitable for use in the present invention include selected olive oil, shea olein, sal olein and cottonseed olein, including winterised cottonseed oil.
  • Enzyme rearrangement processes in accordance with the present invention are carried out in substantially non-aqueous and essentially water-immiscible liquid phase.
  • a small amount of water is nevertheless necessary to activate the catalyst initially. This may be achieved either by contacting the catalyst first with water or by including a little water in the feedstock in batchwiese operations.
  • a balance is required between the faster reaction rates provided by more water increasing the activity of the catalyst and correspondingly increased tendency to hydrolysis of the reactants and products, since the rearrangement process is reversible.
  • the water activity of the system is maintained at between 0.2 and 0.6.
  • the water activity of the system is maintained, preferably within these limits, by including a small amount of water in the feedstock supplied to the catalyst in a fixed bed.
  • the water activity is preferably maintained at a level of which the rearrangement reaction is substantially completed with a contact time less than 2 hours, to minimise the effect by isomerisation of partial glyceride by-products leading to the appearance in the product of 2-saturated triglycerides, where 1, 3-regiospecific catalysts are used to produce symmetrical disaturated 2-oleoyl triglycerides.
  • the rearrangement reaction may be carried out in the presence of a water-immiscible non-polar solvent eg. hexane or other hydrocarbon to maintain the reactants in liquid phase.
  • a water-immiscible non-polar solvent eg. hexane or other hydrocarbon
  • the concentration of reactants in the solvent is preferably from 20-50% by weight.
  • the reaction may be operated at moderately elevated temperatures for example 40 to 80°C, at which the catalyst selected remains active and the reactants are wholly in liquid phase.
  • the catalyst is preferably supported on an inert support for example Celite or other particulate siliceous, inert inorganic support or ion exchange medium, either organic for example a resin, or inorganic for example zeolitic.
  • the amount of lipase is preferably 0.01-0.1% by weight of the support. Lipase is present in commercially available products in an amount of approximately 1% and sufficient commercial product is used to achieve this concentration of lipase on the support.
  • Suitable 1, 3 regiospecific enzymes include Mucor miehei , Rhizopus , A. niger or other Aspergillus species.
  • the acidolysis reactant used with the sunflower or other oil or fat in accordance with the invention may be in the form of a free saturated fatty acid , preferably palmitic or stearic acid, or a mixture of both. Alternatively, they may be present as esters, preferably of short chain saturated mono hydric alcohols, for example methyl and ethyl palmitate and stearate. Preferably from 1 to 5 moles of acidolysis reactant per mole of oil is used, more preferably 3-5 moles per mole.
  • the rearranged triglyceride product of the invention is preferably recovered from the reactant mixture after first separating any free fatty acid and any reactant solvent this has been used, by fractional crystallisation at a temperature, preferably from 10-40°C, at which the unsaturated acid or ester by-products are liquid and can be separated from the crystallised product.
  • the fractionation may be effected from suitable solvent for example acetone.
  • these by-products may be distilled off, preferably at reduced pressure using conventional acid refining methods.
  • the by-products may be hydrogenated to the corresponding stearic acid or ester thereof and recycled for use as the acidolysis reactant.
  • a mixture of equal parts of high oleic sunflower oil and stearic acid was dissolved in twice its weight of hexane.
  • Half the feedstock obtained was saturated with water by passage through a column containing a bed of wet silica gel and was then recombined with the remainder of the feedstock.
  • the combined feedstock was pumped at a flow rate of 6 Kg per hour at 50°C, through a reactor column containing 1 Kg of interesterification catalyst consisting of Mucor miehei lipase supported on Celite, prepared as described in British patent 1577933 and pre-activated with 10% water prior to use. Residence time was approximately 15 minutes.
  • the free fatty acids were separated using a falling film evaporator and the reaction product fractionated at -5°C in acetone using a solvent to oil ratio 5:1, in a scraped-surface heat exchanger to recover a stearin fraction rich in StOSt.
  • the substantially greater SOS content of the stearine fraction and lower content of SLnS is apparent from Table 1.
  • the enzyme and shea stearines were evaluated for confectionery fats, both alone and in blends of equal parts of mid-fraction, by Jensen Cooling Curve determination in Table 2.
  • the enzymatically produced stearine exhibited excellent confectionery fat characteristics and was similar to shea stearine.
  • Example I was repeated using as feedstock the olein by-product recovered from Example I, the catalyst in this case being supported on a phenol-formaldehyde weak anion exchange resin.
  • the deacidified product was first fractionated in acetone with a solvent:oil ratio of 5:1 at a temperature of 0°C, to remove an olein fraction in 56% yield.
  • the stearine fraction remaining was then redispersed in acetone at a 3:1 ratio and a second stearine fraction separated in 10% yield overall at a temperature of 25°C, consisting substantially of saturated glycerides and leaving a mid-fraction recovered in 34% overall yield from the solvent.
  • the saturated glycerides of the upper stearine fraction result from the presence of partial glycerides in the recycled olein undergoing isomerisation followed by interesterification in the reactor.
  • a reactant mixture of high oleate sunflower oil (2.5 parts by wt) and myristic acid (1.0 parts by wt) dissolved in 100-120° petroleum ether (8 parts by wt) was saturated with water at 40°C by passage through a bed of acid washed celite (4.0g) containing 80% by wt of water.
  • the water saturated reaction mixture was pumped at 40°C using a flow rate of 15m/hr ⁇ 1 through a bed of catalyst (2.0g) consisting of Rhizopus japonicus lipase suppored on celite.
  • the catalyst prepared as described in our patent GB 1577933, contained 1700 lipase units per gm, and was activated with 10% water prior to use.
  • the mean residence time of the reactant mixture in the catalyst bed was approximately 15 mins.
  • the interesterification reaction product contained 58% triglyceride, 6% diglyceride and 36% free fatty aic.
  • the triglyceride fraction was isolated and analysed. The results given in Table 3 show that myristate was incorporated into the sunflower oil triglycerides and valuable SOS triglycerides were generated.
  • a mixture of high oleate sunflower oil (2.5 parts by wt) and methyl palmitate (2.4 parts by wt) dissolved in 100-120° petroleum ether (8 parts by wt) was reacted as described in Example 3 using a catalyst ved of Rhixopus niveus lipase supported on celite and a flow rate of 4ml hr ⁇ 1.
  • the catalyst contained 1500 lipase units per gm.
  • the mean residence time of the reactant mixture in the catalyst bed was approximately 1 hour.
  • the reaction product contained 50% triglyceride, 4% diglyceride, 43% methyl esters and 3% free fatty acid. Analysis of the triglyceride fraction showed that extensive interesterification occurred. Palmitate was incorporated into the sunflower oil triglycerides and valuable SOS triglycerides were produced (Table 1).

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Edible Oils And Fats (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Fats And Perfumes (AREA)
EP87303996A 1986-05-06 1987-05-05 Ernährungsfette Withdrawn EP0245076A3 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB08610979A GB2190394A (en) 1986-05-06 1986-05-06 Edible fats by rearrangement of sunflower oil
GB8610979 1986-05-06

Publications (2)

Publication Number Publication Date
EP0245076A2 true EP0245076A2 (de) 1987-11-11
EP0245076A3 EP0245076A3 (de) 1989-10-18

Family

ID=10597386

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87303996A Withdrawn EP0245076A3 (de) 1986-05-06 1987-05-05 Ernährungsfette

Country Status (6)

Country Link
EP (1) EP0245076A3 (de)
JP (1) JPS6317697A (de)
AU (1) AU596411B2 (de)
GB (1) GB2190394A (de)
SE (1) SE467860B (de)
ZA (1) ZA873239B (de)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1989003419A1 (en) * 1987-10-13 1989-04-20 The Lubrizol Corporation METHOD OF PRODUCING cis-9-OCTADECENOIC ACID COMPOSITIONS
EP0285422A3 (en) * 1987-04-03 1989-11-15 Fuji Oil Company, Limited Hard butter composition
EP0427309A3 (en) * 1989-11-09 1991-12-18 Unilever Nv Fats obtained from rapeseed
EP0519542A1 (de) * 1991-06-17 1992-12-23 Unilever N.V. Kombiniertes Fraktionierungs-, Raffinations- und Umesterungsverfahren
EP0652289A1 (de) * 1993-11-05 1995-05-10 Unilever Plc Statistische Umesterung von Triglyceridfetten
EP1040761A1 (de) * 1999-03-19 2000-10-04 Loders Croklaan B.V. Fettmischungen
US6229033B1 (en) 1998-05-11 2001-05-08 E. I. Du Pont De Nemours And Company Fat products from high stearic soybean oil and a method for the production thereof
US6277433B1 (en) 1999-03-19 2001-08-21 Loders Croklaan B.V. Fat mixtures
WO2007029015A1 (en) * 2005-09-08 2007-03-15 Loders Croklaan B.V. Process for producing triglycerides
CN101878821A (zh) * 2010-05-05 2010-11-10 江南大学 可可脂改良剂的生物合成
EP2251428A1 (de) 2009-05-11 2010-11-17 Loders Croklaan B.V. Verfahren zur Herstellung einer Triglyceridzusammensetzung
US8202712B2 (en) 2005-09-08 2012-06-19 Loders Croklaan B.V. Triglyceride process
CN102634547A (zh) * 2012-03-28 2012-08-15 江南大学 一种对称型甘油三酯的制备方法
US20130096331A1 (en) * 2007-12-20 2013-04-18 Dow Agrosciences Llc Interesterification of low saturate sunflower oil and related methods and compositions
WO2014097218A1 (pt) * 2012-12-19 2014-06-26 Universidade Federal De Minas Gerais - Ufmg Óleo de girassol (helianthus annuus) modificado enzimaticamente, processo de obtenção e uso dos seus derivados como antimicrobianos
WO2024030062A1 (en) * 2022-08-03 2024-02-08 Aak Ab (Publ) Enzymatic process for increasing the sos triglyceride content of a vegetable oil

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101314682B1 (ko) * 2010-04-22 2013-10-07 씨제이제일제당 (주) 카카오 버터 유사 하드버터의 제조 방법
JP2015533482A (ja) * 2012-09-07 2015-11-26 エイエイケイ、アクチボラグＡａｋａｂ ココアバター代用脂の製造方法

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1577933A (en) * 1976-02-11 1980-10-29 Unilever Ltd Fat process and composition
JPS5932119B2 (ja) * 1976-04-08 1984-08-06 不二製油株式会社 カカオバタ−代用脂の製造法
JPS5571797A (en) * 1978-11-21 1980-05-30 Fuji Oil Co Ltd Manufacture of cacao butter substitute fat
JPS5584397A (en) * 1978-12-20 1980-06-25 Ajinomoto Kk Fat and oil ester exchange using lipase
JPS5615643A (en) * 1979-07-17 1981-02-14 Fuji Oil Co Ltd Production of hard butter
EP0035883B1 (de) * 1980-03-08 1984-06-06 Fuji Oil Company, Limited Verfahren zur enzymatischen Zwischenveresterung von Fett und hierzu verwendetes Enzym
ATE22328T1 (de) * 1981-05-07 1986-10-15 Unilever Nv Behandlung von fetten.
CA1241227A (en) * 1981-07-08 1988-08-30 Alasdair R. Macrae Edible fat process
AU544682B2 (en) * 1981-11-18 1985-06-13 Fuji Oil Company Limited Method for modification of fats and oils
JP2841512B2 (ja) * 1989-08-07 1998-12-24 旭硝子株式会社 減圧脱泡装置の監視方法及びその装置

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0285422A3 (en) * 1987-04-03 1989-11-15 Fuji Oil Company, Limited Hard butter composition
WO1989003419A1 (en) * 1987-10-13 1989-04-20 The Lubrizol Corporation METHOD OF PRODUCING cis-9-OCTADECENOIC ACID COMPOSITIONS
EP0427309A3 (en) * 1989-11-09 1991-12-18 Unilever Nv Fats obtained from rapeseed
EP0519542A1 (de) * 1991-06-17 1992-12-23 Unilever N.V. Kombiniertes Fraktionierungs-, Raffinations- und Umesterungsverfahren
EP0652289A1 (de) * 1993-11-05 1995-05-10 Unilever Plc Statistische Umesterung von Triglyceridfetten
US6229033B1 (en) 1998-05-11 2001-05-08 E. I. Du Pont De Nemours And Company Fat products from high stearic soybean oil and a method for the production thereof
EP1040761A1 (de) * 1999-03-19 2000-10-04 Loders Croklaan B.V. Fettmischungen
US6277433B1 (en) 1999-03-19 2001-08-21 Loders Croklaan B.V. Fat mixtures
WO2007029015A1 (en) * 2005-09-08 2007-03-15 Loders Croklaan B.V. Process for producing triglycerides
US8183021B2 (en) 2005-09-08 2012-05-22 Loders Croklaan B.V. Process for producing triglycerides
US8202712B2 (en) 2005-09-08 2012-06-19 Loders Croklaan B.V. Triglyceride process
US20130096331A1 (en) * 2007-12-20 2013-04-18 Dow Agrosciences Llc Interesterification of low saturate sunflower oil and related methods and compositions
EP2251428A1 (de) 2009-05-11 2010-11-17 Loders Croklaan B.V. Verfahren zur Herstellung einer Triglyceridzusammensetzung
WO2010130395A1 (en) 2009-05-11 2010-11-18 Loders Croklaan B.V. Process for making a triglyceride composition
US8986941B2 (en) 2009-05-11 2015-03-24 Loders Croklaan B.V. Process for making a triglyceride composition
CN101878821A (zh) * 2010-05-05 2010-11-10 江南大学 可可脂改良剂的生物合成
CN102634547A (zh) * 2012-03-28 2012-08-15 江南大学 一种对称型甘油三酯的制备方法
WO2014097218A1 (pt) * 2012-12-19 2014-06-26 Universidade Federal De Minas Gerais - Ufmg Óleo de girassol (helianthus annuus) modificado enzimaticamente, processo de obtenção e uso dos seus derivados como antimicrobianos
WO2024030062A1 (en) * 2022-08-03 2024-02-08 Aak Ab (Publ) Enzymatic process for increasing the sos triglyceride content of a vegetable oil

Also Published As

Publication number Publication date
SE8701847L (sv) 1987-11-07
SE467860B (sv) 1992-09-28
SE8701847D0 (sv) 1987-05-05
AU596411B2 (en) 1990-05-03
JPH0430836B2 (de) 1992-05-22
JPS6317697A (ja) 1988-01-25
GB2190394A (en) 1987-11-18
AU7248187A (en) 1987-11-12
EP0245076A3 (de) 1989-10-18
ZA873239B (en) 1989-01-25
GB8610979D0 (en) 1986-06-11

Similar Documents

Publication Publication Date Title
EP0069599B1 (de) Verfahren zur Herstellung eines geniessbaren Fettes
AU596411B2 (en) Edible fats
US5508048A (en) Enzymatic transesterification starting from high erucic cruciferae oils
Gunstone Movements towards tailor-made fats
JPS6250115B2 (de)
Chong et al. Fractionation procedures for obtaining cocoa butter‐like fat from enzymatically interesterified palm olein
EP1928989B1 (de) Verfahren zur herstellung von triglyceriden
BE905066A (nl) Vetten en eetbare emulsies met een hoog gehalte aan cis-polyonverzadigde vetzuren.
CA1274117A (en) Edible fats
JP2012525857A (ja) トリグリセリド組成物を作製する方法
EP0199580B1 (de) Verfahren zur Herstellung von symmetrischen Triglyceriden
AU628644B2 (en) Enzymatic transesterification of tryglycerides
EP0185524B1 (de) Essbare Fette
EP1928988B1 (de) Triglyceridverfahren
ROUSSEAU Lipids: Theory and Practice

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE CH DE ES FR GB GR IT LI NL SE

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE CH DE ES FR GB GR IT LI NL SE

17P Request for examination filed

Effective date: 19891024

17Q First examination report despatched

Effective date: 19910619

RAP3 Party data changed (applicant data changed or rights of an application transferred)

Owner name: UNILEVER PLC

Owner name: UNILEVER N.V.

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Withdrawal date: 19940926

RIN1 Information on inventor provided before grant (corrected)

Inventor name: MOORE, HARRY