WO1990009980A1 - Procede pour produire des glycerides d'acides gras - Google Patents

Procede pour produire des glycerides d'acides gras Download PDF

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Publication number
WO1990009980A1
WO1990009980A1 PCT/EP1990/000285 EP9000285W WO9009980A1 WO 1990009980 A1 WO1990009980 A1 WO 1990009980A1 EP 9000285 W EP9000285 W EP 9000285W WO 9009980 A1 WO9009980 A1 WO 9009980A1
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WO
WIPO (PCT)
Prior art keywords
fatty acid
fatty acids
omega
transesterification
double bonds
Prior art date
Application number
PCT/EP1990/000285
Other languages
German (de)
English (en)
Inventor
Alfred Struve
Horst Eierdanz
Gerhard Wollmann
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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 Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Publication of WO1990009980A1 publication Critical patent/WO1990009980A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/587—Monocarboxylic acid esters having at least two carbon-to-carbon double bonds

Definitions

  • the invention relates to a process for the production of fatty acid glycerides in which at least 40, in particular at least 50% by weight of the fatty acid residues are derived from fatty acids with 18 to 22 carbon atoms and more than three olefinic double bonds, in particular from omega-3 fatty acids , by transesterification of fatty acid methyl or fatty acid ethyl esters, in which at least 40, in particular at least 50% by weight of the fatty acid residues are derived from the fatty acids with at least three olefinic double bonds, in particular the omega-3 fatty acids, with glycerol in the presence of basic Catalysts under protective gas and heating.
  • Fatty acid mixtures with a high content of more than three olefinic double bonds i.e. More than triply unsaturated fatty acids, especially on so-called omega-3 fatty acids, which contain eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA), including their derivatives such as alkyl esters and glycerides, have recently been used for the prophylaxis of cardiovascular diseases.
  • omega-3 fatty acids which contain eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA), including their derivatives such as alkyl esters and glycerides
  • omega-3 fatty acids are natural components of marine fats and oils, particularly fish oils; however, their share of fats and oils varies greatly depending on their origin. Fish oils with Higher proportions of omega-3 fatty acids rarely contain more than about 30% by weight of these fatty acids. Now, however, higher levels of omega-3 fatty acids are desirable for the prophylactic consumption of fish oil in order to avoid an unnecessary intake of ballast fat.
  • Various methods have been proposed for increasing the content of the fatty acids mentioned in fish oil preparations. Thus, in Chemistry and Industry from March 7, 1988, pp.
  • JP-A 62 153 249 describes the production of EPA glycerides from the corresponding ethyl esters, again by transesterification with fats and using sodium methylate as a catalyst.
  • omega-3 fatty acids are relatively sensitive to alkali because of their numerous double bonds; the isomerization of double bonds observed with sodium methylate as a catalyst at higher temperatures leads to a loss of valuable omega-3 fatty acids.
  • the removal of the sodium methylate or the soaps thus formed from the resulting by ümest proceedings GlyceridgemiBel ⁇ is complicated. According to the process described, concentrations of omega-3 fatty acid glycerides which are not as readily obtainable as when the ethyl esters were transesterified with free glycerol.
  • DE-A 37 16 950 discloses a process for the preparation of triglycerides by transesterification of fatty acid esters with glycerol in the presence of anhydrous sodium carbonate as a catalyst.
  • sodium carbonate in particular in the form of a solution in glycerol, is also a fairly strong base, it has now surprisingly been found that it is suitable for reacting omega-3 fatty acid esters with glycerol without isomerizations of the fatty acids present to any appreciable extent Double bonds occur.
  • the removal of the catalyst after the transesterification is also very easy here.
  • the invention is directed to a process of the type mentioned at the outset, in which anhydrous sodium carbonate is used as the basic catalyst.
  • the glycerin required for the transesterification serves as a solvent and as a reactant.
  • the starting compounds of the process of the invention ie methyl or ethyl ester mixtures with a content of at least 40, in particular at least 50% by weight, based on the total content of the fatty acids bound as methyl or ethyl esters, of more than triunsaturated 18 fatty acids having up to 22 carbon atoms, in particular omega-3 fatty acids are expediently obtained from fish oil qualities with a relatively high proportion of more than triple unsaturated fatty acids bound as glycerides.
  • These fish oils are first described, for example, in JAOCS, Vol. 40, 197-198 (1962 ) or described in US Pat. No.
  • the omega-3 fatty acid esters are then enriched by distillation.
  • the enrichment product obtained is the starting product of the process of the invention.
  • methyl or ethyl omega-3 fatty acids enriched in other ways, such as can be obtained, for example, with the urea enrichment described above.
  • the aforementioned ethyl esters are preferably used as the starting product.
  • the fatty acid residues of the starting and end products of the process of the invention which are not derived from the fatty acids having more than three olefinic double bonds or from the omega-3 fatty acids, are essentially residues of saturated and / or unsaturated fatty acids with 12 up to 30 carbon atoms in fish oils, e.g. Herring, sardine and menhaden oil occur as natural components of the same.
  • the transesterification is preferably carried out at temperatures in the range from 150 to 200 ° C., in particular from 170 to 190 ° C.
  • the methyl or ethyl alcohol released in this process is continuously removed from the reaction mixture by distillation, in particular under slightly reduced pressure. Any excess methyl or ethyl ester to be added is added as the reaction proceeds. To terminate the reaction, it can be advantageous to increase the vacuum considerably, for example up to about 10 hPa.
  • the reaction temperature of a maximum of 200 ° C. should not be exceeded in order to avoid isomerizations.
  • the reaction product of the transesterification is purified by filtering off the sodium carbonate, which is insoluble in the triglycerides obtained according to the invention. It may also be advantageous to add up to 5% by weight, based on the reaction mixture, of bleaching earth before the filtration. After filtering, the excess methyl or ethyl ester is distilled off at temperatures up to about 200 ° C. in a high vacuum, for example at 0.001 to 5 hPa, preferably in a thin film evaporator under conditions of short path distillation.
  • the fatty acid composition in the fish oil determined by gas chromatography, in% by weight, based on the methyl ester, was as follows (only the most important ingredients are given here; the fatty acids are indicated by their carbon number m and the number of double bonds n (C m . N ) marked).
  • the pre-purified transesterification product (distillate I) was then fractionated in a high vacuum on a 40 cm long column which was filled with ceramic saddle bodies.
  • the shorter-chain ethyl esters up to the chain length C ⁇ g in the acid residue (distillate II; boiling point 102-161 ° C / approx. 0.1 hPa; 494 g (53%)) were largely distilled off.
  • Glycerin / sodium carbonate feed were still 20 g (0.06 mol) of distillate III as a 10% excess within one hour added dropwise to complete the conversion of the glycerol. After a further hour, the vacuum was set to 10 hPa; the temperature was then kept at 180 ° C. for a further 1.5 h.
  • the degree of implementation was around 85%.
  • the product was stable to cold; Even after standing at 6 ° C for a long time, only an extremely small amount of crystals separated out.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Fats And Perfumes (AREA)

Abstract

Dans le procédé décrit, au moins 40 % en poids, notamment au moins 50 % en poids, des résidus d'acides gras sont dérivés d'acides gras avec 18 à 22 atomes de carbone et plus de trois liaisons doubles oléfiniques, en particulier d'acides gras oméga-3, par transestérification de mélanges d'esters méthyliques d'acides gras ou d'esters éthyliques d'acides gras, les résidus d'acides gras ayant une composition correspondante, avec de la glycérine en présence de catalyseurs basiques sous atmosphère contrôlée. Il ne se produit aucune isomérisation notable des doubles liaisons présentes dans les acides gras si on utilise du carbonate de sodium anhydre comme catalyseur de base.
PCT/EP1990/000285 1989-03-03 1990-02-21 Procede pour produire des glycerides d'acides gras WO1990009980A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP3906853.6 1989-03-03
DE19893906853 DE3906853A1 (de) 1989-03-03 1989-03-03 Verfahren zur herstellung von fettsaeureglyceriden

Publications (1)

Publication Number Publication Date
WO1990009980A1 true WO1990009980A1 (fr) 1990-09-07

Family

ID=6375479

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1990/000285 WO1990009980A1 (fr) 1989-03-03 1990-02-21 Procede pour produire des glycerides d'acides gras

Country Status (4)

Country Link
EP (1) EP0461167A1 (fr)
JP (1) JPH04503823A (fr)
DE (1) DE3906853A1 (fr)
WO (1) WO1990009980A1 (fr)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0291870A2 (fr) * 1987-05-20 1988-11-23 Henkel Kommanditgesellschaft auf Aktien Procédé de préparation de triglycérides

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0291870A2 (fr) * 1987-05-20 1988-11-23 Henkel Kommanditgesellschaft auf Aktien Procédé de préparation de triglycérides

Also Published As

Publication number Publication date
JPH04503823A (ja) 1992-07-09
DE3906853A1 (de) 1990-09-06
EP0461167A1 (fr) 1991-12-18

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