EP0185524B1 - Graisses comestibles - Google Patents

Graisses comestibles Download PDF

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Publication number
EP0185524B1
EP0185524B1 EP85309086A EP85309086A EP0185524B1 EP 0185524 B1 EP0185524 B1 EP 0185524B1 EP 85309086 A EP85309086 A EP 85309086A EP 85309086 A EP85309086 A EP 85309086A EP 0185524 B1 EP0185524 B1 EP 0185524B1
Authority
EP
European Patent Office
Prior art keywords
process according
fraction
fat
glycerides
triglycerides
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.)
Expired - Lifetime
Application number
EP85309086A
Other languages
German (de)
English (en)
Other versions
EP0185524A3 (en
EP0185524A2 (fr
Inventor
Alasdair Robin Macrae
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
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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, Unilever NV filed Critical Unilever PLC
Priority to AT85309086T priority Critical patent/ATE61390T1/de
Publication of EP0185524A2 publication Critical patent/EP0185524A2/fr
Publication of EP0185524A3 publication Critical patent/EP0185524A3/en
Application granted granted Critical
Publication of EP0185524B1 publication Critical patent/EP0185524B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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

Definitions

  • This invention relates to hard butters and their preparation from edible fats.
  • Processes for the production of cocoa butter substitutes and extender fats from these alternative sources generally include fractionation steps in which these more valuable glycerides are separated from others with less desirable melting attributes, notably trisaturated glycerides and mono-saturated and tri-unsaturated triglycerides, but also asymmetric disaturated glycerides, where these can be separated.
  • the separation is usually effected by fractional crystallization, particularly from a solvent such as acetone or hexane, the more highly saturated glycerides being removed in a higher-melting or stearin fraction, and the more highly unsaturated glycerides being removed in a lower-melting or olein fraction.
  • These less desirable fractions may constitute as much as half the original fat and command a much lower premium than the hard butter fraction.
  • the present invention proposes a process for the recovery of hard butter from vegetable fats by the interesterification of a triglyceride composition with another fatty acid moieties containing composition in the presence of a 1,3 - selective lipase enzyme, characterised by, in order to obtain the hard butter, the use of a vegetable fat containing substantial amounts of symmetrical disaturated triglycerides of C16 and C18 fatty acids, which fat is fractionally crystallised to recover the said glycerides and at least a more highly unsaturated oleine fraction, wherein this latter fraction is mixed with a substantially saturated glyceride composition and the mixture interesterified in the presence of the 1,3-selective lipase enzyme to yield further quantities of symmetrical disaturated triglycerides and if desired separating these from the product of by fractional crystallization.
  • the olein fraction consists of glycerides having an unsaturated fatty acid residue in the 2-position, all these are theoretically capable of conversion by interesterification under the influence of the enzyme catalyst to symmetrical disaturated triglycerides, provided only that sufficient glycerides are present in the blends, for example in the upper-melting or stearin fraction with which it is preferably combined, containing saturated fatty acid residues in the alpha or 1,3-positions that are vulnerable to the catalyst for effecting interesterification with the more highly unsaturated glycerides.
  • trisaturated glycerides may undergo interesterification with tri-unsaturated glycerides to provide 1-saturated di-unsaturated glycerides and these in turn to 1,3-disaturated glycerides, under the influence of the selective action of the catalyst.
  • the trisaturated glycerides themselves convert correspondingly to asymmetric disaturated mono-unsaturated glycerides and symmetric di-unsaturated glycerides, i.e. 1,3-diunsaturated, 2-saturated glycerides.
  • the interesterified glycerides may he separated as in conventional fractionation processes, to recover a fraction consisting essentially of symmetrical disaturated glycerides for use as a cocoa butter replacement fat.
  • the more highly unsaturated glycerides in the interesterification mixture including in particular the symmetrical 1,3-di-unsaturated glycerides, form a lower-melting oleine fraction.
  • Any unreacted trisaturated glycerides may be separated if necessary in a top fraction, and recycled for further interesterification with any asymmetric disaturated glycerides, whether these appear in a stearin or olein fraction separated from the symmetrical disaturated fraction.
  • the mixture of interesterified glycerides may be separately fractionated or recombined with feedstock in the fractionation step of the process.
  • the feedstock may be introduced into either unit and may thus be fractionated first, in admixture with the entire interesterification output, or interesterified first together with the recycled interesterified fractions from which the symmetrical disaturated glycerides have been removed.
  • a purge may also be necessary of the symmetrical di-unsaturated glycerides to avoid build-up of this intractable material in the recycled composition.
  • Rearrangement catalyst may also be used to convert this material and return it in a more tractable form, for example, a non-selective catalyst, a 2-selective catalyst, or one which is selectively active to saturated but not unsaturated fatty acid residues.
  • a particular advantage of continuous operation is that the interesterification need be of relatively short duration since the interesterification can be incomplete for each pass through the unit. Enzyme interesterification is generally substantially slower than interesterification under the influence of inorganic catalysts which are also used at much higher temperatures. By continuous recycling however, the residence time in the interesterification step need be sufficient only to provide a significant improvement in the yield of the desired glycerides, without necessarily reaching equilibrium.
  • the invention also includes recovery of the product from the rearrangement step, without fractionation or recycle, particularly for the preparation of hardstock fat which is then blended with liquid glyceride oils, to provide a composition suitable for margarine or other emulsion food spreads, or the fat may be used in ice-cream.
  • Fractionation steps carried out in accordance with the invention may be conventional, either by solvent fractionation using acceptable solvent, for example acetone, hexane or nitroparaffins or ambient gases in liquid condition under pressure. Fractionation may also at least in part be dry without solvents and may then be aided as in the so-called Lanza process, by the use of surfactant aqueous dispersions for facilitating separation of liquid and solid phases during fractionation. Preferably the fractionation is carried out however in acetone at temperatures from 15 to -5°C or in hexane at temperatures from 10°C to -20°C.
  • acceptable solvent for example acetone, hexane or nitroparaffins or ambient gases in liquid condition under pressure.
  • Fractionation may also at least in part be dry without solvents and may then be aided as in the so-called Lanza process, by the use of surfactant aqueous dispersions for facilitating separation of liquid and solid phases during fractionation.
  • the fractionation is carried out however in acetone
  • Suitable enzymes which are active to catalyse interesterification only in the outer positions of glyceride molecules include, for example, Aspergillus niger and Mucor michei. These enzyme catalysts ensure that the unsaturated fatty acid residue in the 2-position of the glycerides of the lower-melting fraction remain unaffected by the interesterification, to provide a foundation for the production in that reaction of the desired symmetrical disaturated glycerides for the mid-fraction. Enzyme catalysts are particularly preferred for this process, but other catalysts may of course be adopted provided they show selective interesterification at the alpha-positions only.
  • the interesterification reaction may be carried out in solvents which leave the catalyst unaffected, particularly hexane for enzyme catalysts, or without solvent and the reaction may be batchwise or continuous, the catalyst in the latter event being preferably fixed in a reaction vessel through which the reaction burden comprising the mixed upper- and lower-melting fractions are passed.
  • Enzyme catalysts may be pre-activated by contact with water and they may be supported on a suitable carrier, as described in our patent specification GB 1577933.
  • the water content may be obtained during the reaction, to predetermined limits in accordance with our patent specification (GB abandoned but EP 64855) by the use of humectants and/or other means for removing water from the reaction phase.
  • the water content is preferably not more than 2% of the reaction mass, including solvent, and particularly not more than 1%.
  • the water activity A W is preferably less than 50% during reaction.
  • Enzyme catalysts may also however be used in polyhydric alcohol solution to maintain a very low water content.
  • the water content is preferably low enough to minimise the extent of hydrolysis taking place with the production of partial glycerides. These may however be removed by selective adsorption means using silica-type adsorbents.
  • Suitable fats include in particular palm oil but also shea, sal, aceituno, mango, kokum or phulwara fat ,pentadesma oil and of course cocoa butter itself, may all be processed in accordance with the present invention.
  • Vegetable oils and fats are used since these contain an abundance of unsaturated fatty acid residues in the 2-position of their glycerides. Mixtures of oils and fats may be used and a fat which is deficient in trisaturated glycerides may be mixed with another containing them, or hydrogenated to provide sufficient for the interesterification reaction.
  • the oils are refined before use as feedstock in the present invention and both neutralised and un-neutralised oils and fats may be used.
  • the miscella containing 500ppm of water, was fed at 3 litres per hour through the reactor which contained 0.7 kg of catalyst.
  • the residence time in the reactor was approximately 30 minutes and the reaction was carried out at 55°C.
  • Solvent was distilled from the product which was then recrystallised from acetone, first at 20°C and then at 5°C to recover a mid-fraction, this is compared in the accompanying Table with a sample of mid-fraction obtained by crystallisation from unmodified palm oil.
  • the composition is also given in the Table of the feedstock blend and its components.
  • the olein and stearin fractions derived from the reaction product were found to be essentially similar in composition to these, the triglyceride analyses being determined by silver-phase HPLC methods.

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)
  • Fats And Perfumes (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)

Claims (9)

  1. Procédé de récupération de beurre dur à partir de graisses végétales par interestérification d'une composition de triglycéride avec une autre composition contenant des fractions acide gras en présence d'une enzyme lipase 1,3-sélective, caractérisé par, dans le but d'obtenir le beurre dur, l'utilisation d'une graisse végétale contenant des quantités substantielles de triglycérides di-saturés symétriques d'acides gras en C₁₆ et C₁₈, laquelle graisse est cristallisée de façon fractionnée pour recueillir lesdits glycérides et au moins une fraction oléine plus fortement insaturée, où on mélange cette dernière fraction avec une composition de glycéride essentielle-ment saturée et l'on interestérifie le mélange en présence d'une enzyme lipase 1,3-sélective pour donner des quantités supplémentaires de triglycérides di-saturés symétriques et, si on le désire, on les sépare du produit par cristallisation fractionnée.
  2. Procédé selon la revendication 1, dans lequel on recueille la composition de glycéride essentiellement saturée par cristallisation fractionnée à partir de ladite graisse végétale.
  3. Procédé selon la revendication 1 ou 2, comprenant les étapes de fractionnement et d'interestérification entre lesquelles on fait circuler la charge réactionnelle, où on introduit la charge contenant ladite graisse végétale et on prélève une fraction glycéride di-saturée symétrique.
  4. Procédé selon la revendication 2, dans lequel on enlève une fraction supplémentaire comprenant des triglycérides mono- et di-saturés 2-saturés.
  5. Procédé selon l'une quelconque des revendications précédentes dont au moins une partie est réalisée en solution dans un solvant organique.
  6. Procédé selon la revendication 5, dont seule la partie fractionnement est réalisée dans un solvant organique.
  7. Procédé selon la revendication 5 ou 6, dans lequel on utilise un solvant comprenant l'acétone ou une paraffine inférieure.
  8. Procédé selon l'une quelconque des revendications précédentes, dans lequel la graisse végétale comprend l'huile de Symplocos martinicensis,l'huile de Shorea robusta, le beurre de karité, l'huile de mangue, l'huile de mangoustan ou la graisse de phulwara.
  9. Procédé selon la revendication 2, dans lequel la graisse comprend l'huile de palme.
EP85309086A 1984-12-17 1985-12-13 Graisses comestibles Expired - Lifetime EP0185524B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT85309086T ATE61390T1 (de) 1984-12-17 1985-12-13 Essbare fette.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8431789A GB2170506B (en) 1984-12-17 1984-12-17 Edible fats
GB8431789 1984-12-17

Publications (3)

Publication Number Publication Date
EP0185524A2 EP0185524A2 (fr) 1986-06-25
EP0185524A3 EP0185524A3 (en) 1987-07-15
EP0185524B1 true EP0185524B1 (fr) 1991-03-06

Family

ID=10571300

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85309086A Expired - Lifetime EP0185524B1 (fr) 1984-12-17 1985-12-13 Graisses comestibles

Country Status (8)

Country Link
EP (1) EP0185524B1 (fr)
JP (1) JPS61179299A (fr)
AT (1) ATE61390T1 (fr)
AU (1) AU568035B2 (fr)
DE (1) DE3582030D1 (fr)
GB (1) GB2170506B (fr)
SE (1) SE8505956L (fr)
ZA (1) ZA859618B (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL8501957A (nl) * 1985-07-09 1987-02-02 Unilever Nv Vetten en eetbare emulsies in het bijzonder dieetprodukten met een hoog gehalte aan cis-poly-onverzadigde vetzuren.
US4883684A (en) * 1988-07-01 1989-11-28 The Procter & Gamble Company Functional hardstock fat composition
US5288619A (en) * 1989-12-18 1994-02-22 Kraft General Foods, Inc. Enzymatic method for preparing transesterified oils
EP0457401A1 (fr) * 1990-05-17 1991-11-21 Unilever N.V. Production d'une fraction intermédiaire par cristallisation fractionnée avec recyclage des fractions de stéarine et d'oléine vers interestérification
EP0519542A1 (fr) * 1991-06-17 1992-12-23 Unilever N.V. Procédé combiné de fractionnement, de raffinage et d'interestérification
DE69737169T2 (de) * 1996-06-26 2008-01-03 Loders Croklaan B.V. Nicht-temperierte Füllungsfette ohne Transgehalt
EP0882797B1 (fr) * 1997-06-04 2003-07-16 Loders Croklaan B.V. Préparation de triglycérides symétriques aba
CZ20031418A3 (cs) * 2000-11-21 2003-09-17 Unilever N. V. Emulzní pomazánka typu vody v oleji
CA2530123C (fr) * 2003-07-09 2012-05-01 The Nisshin Oillio Group, Ltd. Procede de production de triglycerides symetriques

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0079986A1 (fr) * 1981-11-19 1983-06-01 Fuji Oil Company, Limited Méthode de modification de graisses et d'huiles

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1418759A1 (de) * 1960-03-18 1969-05-08 E F Drew & Co Inc Verfahren und Vorrichtung zum Isolieren eines Hartfettproduktes aus einem Glyceridoel
JPS5571797A (en) * 1978-11-21 1980-05-30 Fuji Oil Co Ltd Manufacture of cacao butter substitute fat
US4364868A (en) * 1980-02-07 1982-12-21 Lever Brothers Company Cocoabutter replacement fat compositions
JPS57111398A (en) * 1980-12-29 1982-07-10 Asahi Denka Kogyo Kk Ester exchange process for oils and fats
CA1241227A (fr) * 1981-07-08 1988-08-30 Alasdair R. Macrae Production de matiere grasse comestible
AU544682B2 (en) * 1981-11-18 1985-06-13 Fuji Oil Company Limited Method for modification of fats and oils
IE54838B1 (en) * 1982-04-30 1990-02-28 Unilever Plc Improvements in and relating to interesterification of triglycerides of fatty acids

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0079986A1 (fr) * 1981-11-19 1983-06-01 Fuji Oil Company, Limited Méthode de modification de graisses et d'huiles

Also Published As

Publication number Publication date
JPS61179299A (ja) 1986-08-11
GB2170506A (en) 1986-08-06
EP0185524A3 (en) 1987-07-15
ATE61390T1 (de) 1991-03-15
GB2170506B (en) 1989-08-23
GB8431789D0 (en) 1985-01-30
AU568035B2 (en) 1987-12-10
DE3582030D1 (de) 1991-04-11
ZA859618B (en) 1987-08-26
EP0185524A2 (fr) 1986-06-25
SE8505956D0 (sv) 1985-12-16
AU5127585A (en) 1986-06-26
SE8505956L (sv) 1986-06-18

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