WO1993019144A1 - Esters d'acides gras - Google Patents

Esters d'acides gras Download PDF

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Publication number
WO1993019144A1
WO1993019144A1 PCT/EP1993/000529 EP9300529W WO9319144A1 WO 1993019144 A1 WO1993019144 A1 WO 1993019144A1 EP 9300529 W EP9300529 W EP 9300529W WO 9319144 A1 WO9319144 A1 WO 9319144A1
Authority
WO
WIPO (PCT)
Prior art keywords
process according
esters
urea
polyunsaturated fatty
fatty acid
Prior art date
Application number
PCT/EP1993/000529
Other languages
English (en)
Inventor
Martin Ronald Eskdale
Jan Janssen
Neil Macfarlane
Original Assignee
F. Hoffmann-La Roche Ag
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 F. Hoffmann-La Roche Ag filed Critical F. Hoffmann-La Roche Ag
Publication of WO1993019144A1 publication Critical patent/WO1993019144A1/fr

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
    • C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
    • C11C1/08—Refining
    • C11C1/10—Refining by distillation
    • 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
    • C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
    • C11C1/007—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids using organic solvents
    • 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

Definitions

  • the present invention relates to polyunsaturated fatty acid esters (PUFA esters), more particularly it relates to the enrichment of particular valuable and desired PUFA esters in mixtures containing such esters in lower concentrations.
  • PUFA esters polyunsaturated fatty acid esters
  • GLA As is it well known, GLA, EPA and DHA are the accepted terms for
  • ⁇ -linolenic acid (C18:3 (n-6)), eicosapentaenoic acid (C20:5 (n-3)), docosahexaenoic acid (C22:6 (n-3)).
  • the first mentioned acid occurs in vegetable oil
  • the second and the third acid occur in marine oils.
  • the novel process enables to separate the esters in question primarily from saturated fatty acid esters, mono unsaturated fatty acid esters and other PUFA esters.
  • the process of treating the PUFA-esters with urea is conveniently carried out at temperatures between ca. 0°C and ca. 40°C, preferably in a range of ca. 20°C to ca. 25°C.
  • the polar solvent is conveniently a lower alkanol, e.g. a C2-4- alcohol, in particular a C2 or 3-alcohol, e.g. ethanol, isopropanol, or a lower alkyl ketone, e.g. acetone. To a lesser extent, also methanol is feasible.
  • a lower alkanol e.g. a C2-4- alcohol, in particular a C2 or 3-alcohol, e.g. ethanol, isopropanol, or a lower alkyl ketone, e.g. acetone.
  • methanol is feasible.
  • the concentration of the polar solvent is conveniently ca. 8 % to ca. 15%, preferably ca. 10%, of the total fatty arid esters. But also lower concentrations, e.g. 5% are feasible.
  • the hydrocarbon solvent is conveniently pentane, hexane or heptane, but also cyclohexane is feasible.
  • the ratio by weight of fatty arid esters to urea is of from ca. 1:0,5 to ca. 1:4, preferably ca. 1:1,0 to ca. 1:3.
  • the concentration of the polyunsaturated fatty acid esters to be enriched is ca. 18 to ca. 30 % in the starting material.
  • the insoluble urea complexes formed are simply removed, e.g. by centrifugation or filtration.
  • the urea used can conveniently be recycled, e.g. by treatment of the separated insoluble urea complexes with a two phase solvent system.
  • the hydrocarbon solvent is evaporated from the liquid phase containing the enriched polyunsaturated fatty arid esters in a manner known per se, e.g. in vacuo and preferably using columns, preferably columns with low pressure drops, e.g. such as suitable for high vacuum destinations, e.g. Sulzer columns, or thin film evaporators, preferably working step-wise, using a two evaporator chain, including conveniently the use of a falling film evaporator.
  • the product obtained is finally distilled, e.g. using short path distillation, in order to remove any high boiling products.
  • the ester mixture conveniently used as starting material is obtained by cleavage of the triglycerides of marine or vegetable oil, e.g. borage oil, and trans-esterification, through alkaline catalysis, in the presence of ethanol, followed by removing the ethanol and the base in a manner known per se, e.g. by distillation and separation of the two phase system.
  • the starting oil is conveniently obtained, and refined by conventional means, e.g. by removal of the free fatty acids from the triglycerides, if necessary, followed by neutralisation, bleaching, deodorisation, etc. of the triglycerides.
  • the novel process can also be applied to unrefined oils.
  • the concentration of the polyunsaturated fatty arid esters to be enriched is ca. 18 to ca. 30 % of the mixture.
  • the concentration of the esters of vegetable origin is ca. 18-25 %
  • the concentration of the esters of marine origin is ca.
  • esters originate from a vegetable oil, these are concentrated to ca. 50 %, wherein the esters stemming from marine oil are concentrated to ca. 65%.
  • a further aspect of the present invention allows to enrich the esters stemming from marine oil actually up to even ca. 80%.
  • Step a) and b) are carried out prior to the urea treatment of the present invention. They enable to obtain ester concentrations of ca. 55 to ca. 65 %, preferably ca. 60 %.
  • a thin film evaporator or a falling film equipment is conveniently used, the pressure is conveniently between ca. 1 and ca. 20 mbar, preferably ca. 10 mbar, and the temperature is conveniently between ca. 40 and ca. 120°C, preferably ca. 50°C.
  • step b) a thin fil evaporater is conveniently used, the pressure at the top of the column is conveniently between ca. 0,05 and ca. 0,2 mbar, and the temperature is between ca. 170° and 240°, preferably ca. 190°C.
  • the column has conveniently at least 3, preferably ca. 10 stages. • foraTT ⁇ lR 1
  • 4,5 1 ethanol are added and the suspension is mixed, namely for 30 hours and under nitrogen atmosphere.
  • the insoluble urea inclusion complexes are centrifiiged (25°C), and these urea products are washed with hexane.
  • the hexane phases are distilled, using a 0.5 m 2 evaporator, at 65°C, and at a pressure of 300 mbar, at a feed of 20 kg/hour.
  • the bottom product is distilled once more, in order to remove any remaining solvent at 65°C/25 mbar, feed: 15 kg/hour:
  • the GLA content of the product is now 50% as determined gas chromatographically.
  • the resulting concentrate has a PUFA-content (EPA, DPA and
  • 100 g of the Sambay bottom product are mixed with 10 g ethanol and added to a suspension of 120 g urea in 600 ml hexane.
  • the hexane phase is evaporated to remove the solvent from the concentrate.
  • the obtained final concentrate shows 78 weight-% EPA, DPA and DHA-ethyl esters.

Landscapes

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

Abstract

Cette invention concerne des esters d'acides gras polyinsaturés (esters AGPI) et plus particulièrement l'apport supplémentaire d'esters AGPI spécifiques recherchés et intéressants dans des mélanges contenant ces esters dans de faibles concentrations. Cet apport est effectué au moyen d'un traitement spécifique à l'urée des esters concernés.
PCT/EP1993/000529 1992-03-18 1993-03-09 Esters d'acides gras WO1993019144A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9205880.9 1992-03-18
GB929205880A GB9205880D0 (en) 1992-03-18 1992-03-18 Low energy pufa enrichment

Publications (1)

Publication Number Publication Date
WO1993019144A1 true WO1993019144A1 (fr) 1993-09-30

Family

ID=10712372

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1993/000529 WO1993019144A1 (fr) 1992-03-18 1993-03-09 Esters d'acides gras

Country Status (3)

Country Link
GB (1) GB9205880D0 (fr)
IS (1) IS3986A (fr)
WO (1) WO1993019144A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001051598A1 (fr) * 2000-01-11 2001-07-19 Monsanto Technology Llc Procede de production d'un melange enrichi d'esters d'acides gras polyinsatures
WO2009006317A1 (fr) * 2007-06-29 2009-01-08 Martek Biosciences Corporation Production et purification d'esters d'acides gras polyinsaturés
ITMI20100961A1 (it) * 2010-05-27 2011-11-28 Erredue Spa Miscele ricche in esteri di acidi grassi omega-3, loro composizioni e loro processo di preparazione
EP2627423A1 (fr) * 2010-10-13 2013-08-21 Cognis IP Management GmbH Dispositif et procédé de distillation de substances sensibles à la température

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2785151A (en) * 1952-10-14 1957-03-12 Manuel H Gorin Process for treating tall-oil with urea, and particularly a new form of expanded urea

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2785151A (en) * 1952-10-14 1957-03-12 Manuel H Gorin Process for treating tall-oil with urea, and particularly a new form of expanded urea

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch, Week 68, Derwent Publications Ltd., London, GB; Class D, AN 66-30961F *
DATABASE WPIL Section Ch, Week 8246, 1982 Derwent Publications Ltd., London, GB; Class D, AN 82-98542E *
DATABASE WPIL Section Ch, Week 8301, 1983 Derwent Publications Ltd., London, GB; Class D, AN 83-00823K *
DATABASE WPIL Section Ch, Week 8914, 1989 Derwent Publications Ltd., London, GB; Class D, AN 89-102945 *
PATENT ABSTRACTS OF JAPAN vol. 014, no. 456 2 October 1990 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001051598A1 (fr) * 2000-01-11 2001-07-19 Monsanto Technology Llc Procede de production d'un melange enrichi d'esters d'acides gras polyinsatures
WO2009006317A1 (fr) * 2007-06-29 2009-01-08 Martek Biosciences Corporation Production et purification d'esters d'acides gras polyinsaturés
CN101796014A (zh) * 2007-06-29 2010-08-04 马泰克生物科学公司 多不饱和脂肪酸酯的制备和纯化
AU2008269989B2 (en) * 2007-06-29 2014-02-27 Dsm Ip Assets B.V. Production and purification of esters of polyunsaturated fatty acids
ITMI20100961A1 (it) * 2010-05-27 2011-11-28 Erredue Spa Miscele ricche in esteri di acidi grassi omega-3, loro composizioni e loro processo di preparazione
EP2627423A1 (fr) * 2010-10-13 2013-08-21 Cognis IP Management GmbH Dispositif et procédé de distillation de substances sensibles à la température

Also Published As

Publication number Publication date
IS3986A (is) 1993-09-19
GB9205880D0 (en) 1992-04-29

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