WO1983001782A1 - Raffinage de graisses - Google Patents

Raffinage de graisses Download PDF

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Publication number
WO1983001782A1
WO1983001782A1 PCT/GB1982/000327 GB8200327W WO8301782A1 WO 1983001782 A1 WO1983001782 A1 WO 1983001782A1 GB 8200327 W GB8200327 W GB 8200327W WO 8301782 A1 WO8301782 A1 WO 8301782A1
Authority
WO
WIPO (PCT)
Prior art keywords
process according
fat
adsorbent
solvent
refined
Prior art date
Application number
PCT/GB1982/000327
Other languages
English (en)
Inventor
Plc Unilever
Nv Unilever
Original Assignee
Merk, Werner
Prasch, Albert, Michael
Sen Gupta, Achintya, Kumar
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 Merk, Werner, Prasch, Albert, Michael, Sen Gupta, Achintya, Kumar filed Critical Merk, Werner
Priority to AU10123/83A priority Critical patent/AU556001B2/en
Priority to JP57503555A priority patent/JPS58501950A/ja
Publication of WO1983001782A1 publication Critical patent/WO1983001782A1/fr
Priority to FI832371A priority patent/FI832371L/fi
Priority to DK325683A priority patent/DK158839C/da

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/10—Refining fats or fatty oils by adsorption

Definitions

  • the field of the invention is the refining of fat, particularly but non-exclusively the refining of vegetable butters.
  • fats require purification in a refining process, to remove impurities and improve both the appearance and performance of the fat.
  • taste also is improved by refining.
  • the invention is particularly concerned with a class of fats known generally as vegetable butters from their relatively high melting characteristics, compared with the majority of fats from vegetable sources which are generally liquid at ambient temperatures and are usually described as vegetable oils.
  • Oils and fats may be classified into two distinct groups differing markedly both in their properties and stability and require very different approaches in detail to refining processes applied to them.
  • Those high in polyun ⁇ aturation, including linoleic and more highly unsaturated fatty acids, and prized accordingly for their dietetic value, may contain 40% or more of these acids in their glycerides, they are liquid at ambient temperature and are susceptible to the development of reversionary flavours after refining, owing to their susceptibility to oxidation arising from their high degree of unsaturation.
  • these high PUFA vegetable oils include soyabean containing 52% polyunsaturated fatty acids, cottonseed
  • vegetable butters In contrast, most animal fats are substantially less unsaturated. They are accordingly, high-melting and less prone to flavour reversion as are vegetable butters. Like most other vegetable fats, vegetable butters consist principally of triglycerides of predominantly C 16 and C 18 fatty acids, but vegetable butters contain more saturated fatty acids. These are distributed principally in the alpha- or 1- and 3-positions of the triglycerides which constitute the principal component of fats and in this vegetable butters closely resemble cocobutter and in their refined form are therefore used as cocoabutter substitutes since the close similarity of their structure is matched by similar melting performance including most importantly, organoleptic response. Examples of vegetable butters include cocobutter itself with only 4% linoleic acid, shea (10%), sal (2.8%) mango kernel (5%) and mowrah (up to 18%), with palm oil (10%).
  • a miscella is made of the fat or oil in a suitable organic solvent, usually a hydrocarbon such as hexane, and the solution brought into contact with an appropriate adsorbent material of suitable particle size.
  • a suitable organic solvent usually a hydrocarbon such as hexane
  • the process necessitates removal of the solvent from the raffinate solution and is therefore expensive to operate.
  • the cost of the process may also be prohibitively high if the effective life of the adsorbent is short.
  • the removal of the small quantities of polar compounds present may have a dramatic effect, particularly on the melting characteristics of vegetable butters and is not readily achieved by alternative methods.
  • the invention is particularly useful therefore in reducing the cost of achieving high quality fats for edible purposes such as chocolate manufacture and also for pharmaceutical application by enhancing the effective life of adsorbents used for producing such fats.
  • USP 2, 976, 156 discloses a method of refining liquid vegetable oils by contact with alumina adsorbent in which it is recommended that bleaching treatment can be omitted.
  • USP 3,955,004 discloses a similar process to that of USP 2,976,156 and in addition discloses as adsorbent mixtures of silica and alumina.
  • the oils which include coconut, palm kernel and palm oil, are dissolved in a suitable solvent. After contact with the adsorbent, the refined oil is separated from the solvent and bleached.
  • French Patent 990704 discloses bleaching a solution of glyceride oil and subjecting the solution to silica treatment. None of these references reveals the necessity for combining the application of adsorption and bleaching steps with regeneration as provided for by the present invention and applied to vegetable butters to be fractionated.
  • USP 4,284,580 describes the fractionation of triglyceride mixtures by selective adsorption on surfacealuminated silica gel adsorbent. The process disclosed in this reference relies upon differential adsorption characteristics exhibited by different degrees of unsaturation between the many triglycerides of glyceride oils and fats in order to obtain fractions of different Iodine Values.
  • USP 2,589,097 describes the removal of reversionary flavours from soyabean and similar highly unsaturated oils, which may first be bleached, using column adsorption treatment.
  • European Patent Application 53016 published 2nd June 1982 describes refining sal fat by contact with a specially prepared particulate adsorbent in a column.
  • This invention relates to fat refining, particularly but not exclusively to refining vegetable butters.
  • Fats may be refined by contact, in a solution or miscella of a non-polar solvent, with an adsorption agent, usually packed in a column and based on silica and/or alumina activated by heat treatment.
  • the adsorption agent selectively retains polar impurities, for example partial glycerides and colouring matter, and oxidised compounds which are highly polar, whereas the triglycerides constituting the principal components of the fats remain unabsorbed in a raffinate from which the purified fat is recovered by removing the solvent.
  • the absorption agents become less effective with prolonged and/or repeated use, as polar compounds accumulate on them. Desorption of these polar compounds by treatment with polar solvents is incompletely effective with the more tenacious polar compounds absorbed from vegetable butters such as shea, sal and others.
  • regeneration is facilitated by subjecting the fat or the fat miscella to pretreatment by contact with bleaching earth and/or active carbon, to adsorb the more highly polar compounds before treatment with the adsorption agent, preferably packed in a column through which the miscella is percolated.
  • the less highly polar compounds, e.g. diglycerides, adsorbed by the adsorption agent may then be readily removed in a subsequent desorption step, e.g.
  • the refined fat may be separated from the raffinate, for example by distilling off the non-polar solvent, or by fractional crystallisation, preferably to recover a fat fraction having a slip melting point of at least 35°C.
  • lauric fats e.g. palm kernel and coconut oil
  • about 1 /3 of the triglycerides of the fats with which the invention is chiefly concerned are symmetrical, disaturated C 16 /C 18 triglycerides. Generally they contain less than 20% linoleic acid and, for the most part, not more than 10% and are low in polyunsaturated fatty acids generally.
  • Such fats are usually expelled or extracted from tropical or sub-tropical fruit, either the fruit seeds or whole fruit. Although sometimes cultivated in plantations, as for palm oil, usually the fruit grows wild and is collected at irregular intervals in the forests after having fallen. Due to the prevailing elevated temperature and the moisture content of the earth, extensive enzymic reaction can occur, converting the natural triglycerides of the fats contained in the fruit seeds or in the pericarp by hydrolysis to mono- and diglycerides and free fatty acids. Other common reactions encountered in the fruit are hydroperoxidation, epoxidation and hydroxylation of the unsaturated fatty acid radicals contained in the triglycerides of the fat.
  • the solvent in the fat miscella is preferably hexane or other inert aliphatic hydrocarbon compositions, preferably with a boiling point below 100oC to facilitate evaporation from the miscella without exposing the fat to excessively high temperatures.
  • the fat in the miscella may be in crude form or undergo some preliminary refining beforehand, preferably neutralisation.
  • Regeneration comprises desorption and reactivation, preferably effected in two steps.
  • a polar organic solvent which, preferably comprises a monohydric fatty alcohol containing up to 6 carbon atoms and particularly methanol, ethanol and isopropanol, and alcohol-hydrocarbon mixtures, preferably aliphatic, which may be miscible or immiscible, preferably azeotropic mixtures to facilitate removal from the regenerated adsorbent by evaporation.
  • residual polar solvent e.g.
  • methanol used for the desorption operation is driven out of the column by heating and preferably a volatile aliphatic hydrocarbon, e.g. hexane either in the vapour phase or as a superheated liquid.
  • a volatile aliphatic hydrocarbon e.g. hexane either in the vapour phase or as a superheated liquid.
  • the formation of azeotropic mixtures is also helpful in this case.
  • the first step is called “desorption” and the second step “reactivation”.
  • adsorption and desorption are preferably carried out at temperatures from 15 to 75 °C, more preferably not in excess of 60°C, but pretreatment in particular may be carried out at temperatures from 30 to 110 °C and adsorption and desorption at 40 to 80°C.
  • Adsorption is preferably effected in particular at 30 to 60°C, particularly approximately between 20 and 50%.
  • Reactivation is preferably carried out between 50 to 170°C.
  • Substantially less bleaching aid or active carbon is used in the pre-treatment step than adsorption agent, from 0.5 to 5% by weight of the fat being adequate for the former, but with preferably a fat:adsorbent ratio from 10:1 to 1:1 by weight of the fat.
  • both the pretreatment and adsorption steps are applied to the same solution of fat.
  • Suitable bleaching earths for use in the invention include activated Fuller's earth, for example Tonsil and Fulmont, Lucilite, Kieselklare of Degussa. Granulated or non-granulated active carbon, e.g. Norit, may alternatively or in addition be used.
  • Bleaching earths are usually acid-activated natural earths of structures typified by Montmorillonit and Bentonit. Acid treatment increases their propensity for adsorption of highly polar organic compounds including highly polar pigments, e.g. chlorophyll.
  • These earths are not suitable for the adsorption of bulk amounts of diglycerides etc, but very useful in the preliminary treatment step for the removal of small amounts of highly polar organic compounds prior to the treatment of the fat with adsorbents like silica gel or Al 2 O 3 .
  • These highly polar compounds otherwise prevent the regeneration of the adsorbents like silica gel and make their reuse difficult, if not impossible.
  • Active carbon also adsorbs highly polar compounds both by surface adsorption (e.g. pigments etc) and also by -electron interaction (e.g. aromatic compounds, polyene compounds, etc). All active carbons, both granulated and non-granulated, are suitable for this purpose and may be used in conjunction with bleaching earths.
  • the adsorption agent may comprise silica gel, alumina or mixtures thereof including co-precipitates.
  • aluminas include gibbsite and bayerite and among proprietary examples include Aluminiumoxid 504C.
  • Suitable silica gels include Sorbsil of Messrs J Crosfield & Sons Limited, Warrington, England and Kieselgel-M of Messrs Herrmann, Cologne, Germany.
  • adsorption is effected by percolating the miscella through a column packed with the adsorbent and with a length:diameter ratio of 5:1 to 1:2, particularly approximately equal diameter and length, with a residence time in the column of 5 to 30 minutes, especially 15 minutes.
  • Adsorbents suitable for use in the process of the invention preferably exhibit a specific surface area of 300 to 500 m 2 /g, a pore volume of 0.7 to 1.5 mls/g, an averaoge pore diameter of 30 to 2000 ⁇ , preferably 60 to 180 A, a weight:volume ratio of 0.2:0.5 g/ml and pH of 6.5 to 7.5.
  • silica gel adsorbent used in this invention contains more than 95% SiO 2 with not more than approximately 4 to 8% of volatiles removed at 140oC after 4 hours.
  • Particle size by sieve analysis should preferably include not more than approximately 5% of 0.3 mm and not more than 25% of 0.2 mm.
  • Particulars of the gel are as follows:- Specific surface area 450 m 2 /g, pore volume 0.73 mls/g, average pore diameter 60 ⁇ weight:volume ratio 0.43 g/ml, pH 7.2, SiO 2 99.0%, volatiles as above 2.4%, sieve analysis 2% of 0.2 mm, 75% of 0.1 mm, 18% of 0.063 mm and 4.5% of
  • the same fat and the same gel was used for a similar series of experiments in which the miscella pretreatment with bleaching earth and active carbon was omitted. After 5 regeneration cycles the eluate fats and the used silica gels were compared with each other.
  • Results appear in the accompanying Table 1, in which the Lovibond measurements were made in a 1" cell for the crude fat and a 2" cell for the treated samples.
  • the spent silica column was then washed down at 80°C under pressure with an azeotrope mixture of isopropanol and hexane in a weight ratio of 22:78, to desorb and remove the material adsorbed on the silica.
  • the column was then reactivated for reuse by passing down hexane at 180oC and 13-bar.
  • the reactivated silica column was used again to refine a fresh batch of neutralised illipe, pre-treated as described, the whole cycle of refining, desorption and reactivation being repeated 15 times.
  • Neutralised illipe from the same batch was similarly refined by treatment with silica but without the pre-treatment.
  • the silica progressively lost its adsorptive capacity with repeated reuse. This was shown by the increasing diglyceride content of the refined fat and its increasing colour and also by the considerable drop in stabilised dilatation values D of the fat at 32.5oC.
  • Table 2 shows that the miscella pre-treatment purifies the neutralised fat to such an extent that after subsequent silica treatment the spent silica can be regenerated successfully by desorbing with a mixture of isopropanol and hexane and reactivated by superheated hexane.
  • Such a regenerated silica gel can be reused for satisfactory diglyceride removal from the illicher fat. Omission of the pre-treatment eventually renders the spent silica non-regenerable, as evidenced by total failure to adsorb diglycerides after limited reuse.
  • a solution of neutralised shea nut fat in twice its weight of hexane was bleached at 80oC with 2% bleaching earth "Tonsil ACCFF" from Messrs S ⁇ dchemie, Kunststoff, Germany.
  • the filtered solution was passed through a column as before, but packed with silica "Kieselgel M” from Messrs Herrmann, Cologne, Germany, using half as much gel as fat by weight and a refined fat recovered by evaporating the solvent from the treated solutions.
  • the spent silica was desorbed in the column by washing with a mixture of 85 vol % hexane and 15 vol % methanol at 50°C and reactivated by passing hexane vapour under pressure at 90oC inlet temperature through the column, until methanol was completely driven out.
  • the column was reactivated and reused 5 times, the diglyceride content being determined of the fat recovered after each use.

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Microbiology (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Fats And Perfumes (AREA)
  • Amplifiers (AREA)

Abstract

Des graisses, spécialement pour la préparation de succédanés du beurre de cacao, sont raffinées en les mettant en contact avec une solution organique avec un agent d'adsorption, de préférence les graisses étant entassées dans une colonne au travers du fond de laquelle la solution est filtrée, les graisses étant prétraitées avec une terre de blanchiment de charbon actif. Ceci améliore la longévité de l'adsorbant qui peut être régénéré plusieurs fois sans perdre de son efficacité.
PCT/GB1982/000327 1981-11-18 1982-11-16 Raffinage de graisses WO1983001782A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
AU10123/83A AU556001B2 (en) 1981-11-18 1982-11-16 Fat refining
JP57503555A JPS58501950A (ja) 1981-11-18 1982-11-16 脂肪の精製
FI832371A FI832371L (fi) 1981-11-18 1983-06-29 Rengoering av fett
DK325683A DK158839C (da) 1981-11-18 1983-07-14 Fremgangsmaade til raffinering af fedt

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8134725811118 1981-11-18
GB8134725 1981-11-18

Publications (1)

Publication Number Publication Date
WO1983001782A1 true WO1983001782A1 (fr) 1983-05-26

Family

ID=10525968

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1982/000327 WO1983001782A1 (fr) 1981-11-18 1982-11-16 Raffinage de graisses

Country Status (9)

Country Link
EP (1) EP0079799B1 (fr)
JP (1) JPS58501950A (fr)
AT (1) ATE17746T1 (fr)
AU (1) AU556001B2 (fr)
CA (1) CA1188707A (fr)
DE (1) DE3268894D1 (fr)
DK (1) DK158839C (fr)
FI (1) FI832371L (fr)
WO (1) WO1983001782A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2458113C1 (ru) * 2011-10-03 2012-08-10 Общество с ограниченной ответственностью Горнодобывающая Компания "Недра Поволжья" Отбеливающая земля для очистки и отбелки растительных масел
CN113845974A (zh) * 2021-07-30 2021-12-28 丰益(上海)生物技术研发中心有限公司 提升油脂煎炸性能的油脂精炼方法

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4734226A (en) * 1986-01-28 1988-03-29 W. R. Grace & Co. Method for refining glyceride oils using acid-treated amorphous silica
CH666160A5 (fr) * 1985-07-05 1988-07-15 Nestle Sa Procede de traitement du beurre de cacao.
GB2189233A (en) * 1986-04-15 1987-10-21 Kheoh Aik Law Enterprises Pte Reviving of spent earth from edible oil refining
US5231201A (en) * 1986-05-14 1993-07-27 W. R. Grace & Co.-Conn. Modified caustic refining of glyceride oils for removal of soaps and phospholipids
DE69225578T2 (de) * 1992-02-19 1998-09-10 Nestle Sa Verfahren zum Entfärben von Fettsäureester und Nahrungsmittel- oder kosmetische Zubereitung diesen enthaltend
ITRM20010695A1 (it) * 2001-11-26 2003-05-26 Sigma Tau Ind Farmaceuti Uso della propionil l-carnitina o di un suo sale farmacologicamente accettabile per la preparazione di un medicamento per il trattamento del
EP3872156A1 (fr) 2011-10-07 2021-09-01 Neste Oil Oyj Procédé amélioré pour la fabrication de composants de combustible liquide à partir de sources renouvelables

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2573509A (en) * 1947-11-19 1951-10-30 Lever Brothers Ltd Treatment of fatty oils
FR2241613A1 (fr) * 1973-08-24 1975-03-21 Unilever Nv

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS533568A (en) * 1976-06-30 1978-01-13 Asahi Denka Kogyo Kk Cacao fat substitute
US4284580A (en) * 1980-01-02 1981-08-18 The Procter & Gamble Company Fractionation of triglyceride mixture

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2573509A (en) * 1947-11-19 1951-10-30 Lever Brothers Ltd Treatment of fatty oils
FR2241613A1 (fr) * 1973-08-24 1975-03-21 Unilever Nv

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 71, no. 12, 22 September 1969 (Columbus, Ohio, US) C. Srinivasulu et al.: "Salseed, Shorea robusta. I.", abstract no. 51473e, pages 95,96; & Indian Oil Soap J. 1969, 34(7), 147-50 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2458113C1 (ru) * 2011-10-03 2012-08-10 Общество с ограниченной ответственностью Горнодобывающая Компания "Недра Поволжья" Отбеливающая земля для очистки и отбелки растительных масел
CN113845974A (zh) * 2021-07-30 2021-12-28 丰益(上海)生物技术研发中心有限公司 提升油脂煎炸性能的油脂精炼方法

Also Published As

Publication number Publication date
FI832371A0 (fi) 1983-06-29
EP0079799B1 (fr) 1986-01-29
EP0079799A1 (fr) 1983-05-25
DK325683A (da) 1983-07-14
AU556001B2 (en) 1986-10-16
FI832371L (fi) 1983-06-29
ATE17746T1 (de) 1986-02-15
CA1188707A (fr) 1985-06-11
DK158839C (da) 1990-12-17
JPS58501950A (ja) 1983-11-17
DK325683D0 (da) 1983-07-14
DK158839B (da) 1990-07-23
JPS6244040B2 (fr) 1987-09-17
DE3268894D1 (en) 1986-03-13
AU1012382A (en) 1983-06-01

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