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
• • 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
  • C11B3/12—Refining fats or fatty oils 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
  • 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

• the invention is in the field of food supplements and relates to a process for the production of raw materials for the production of conjugated linoleic acid.
• the polyunsaturated ⁇ -3 and ⁇ -6 fatty acids such as -unolenic acid and linoleic acid are among the essential fatty acids for mammals and humans.
• linoleic acid there are other isomeric octadecadienoic acids in nature. These are characterized by conjugated double bonds on the C atoms 9 and 11, 10 and 12 and 11 and 13.
• conjugated linoleic acids abbreviation: CLA - conjugated linoleic acid
• CLA has a high antioxidant effect, which, for example, can inhibit lipid peroxidation.
• conjugated linoleic acid in animal feeding and in this connection also in human nutrition is e.g. B. known from WO 96/06605.
• EP 0579 901 B reports on the use of conjugated linoleic acid to avoid weight loss or a reduction in weight gain or of annoexia caused by immune stimulation in humans or animals.
• WO 94/16690 is concerned with improving the efficiency of food utilization in animals by administering an effective amount of conjugated linoleic acid.
• CLA is obtained by a so-called conjugation of intermediate products containing linoleic acid, ie products containing a carboxylic acid function with 18 C atoms and 2 double bonds in the 9 and 12 positions, both of which are in the cis configuration.
• the pure CLA is often obtained by saponification of oils containing linoleic acid [WO 96/06605, EP 0902082 A1].
• the disadvantage of these processes is the high proportion of undesired isomers. These can in turn be separated by enzymatic esterification, as described in WO 97/18320.
• the corresponding esters can also be used as precursors. State of the art here is the production of the corresponding esters by esterification of the fatty acids with methanol or ethanol.
• the literature describes that, in particular, the methyl and ethyl esters of linoleic acid are suitable as starting materials for a gentle conjugation [WO 99/47135].
• WO 99/47135 describes a process for the preparation of conjugated linoleic acid in which an esterification or transesterification takes place under non-aqueous conditions, in which the alkyl ester obtained is subsequently isomerized in a further step.
• the object of the present invention was to provide raw materials for the production of conjugated linoleic acid (CLA), e.g. To produce methyl or ethyl linoleate from intermediate products rich in linoleic acid, with the provisos that
• the process should also be economical, i.e. be feasible with high yields and on an industrial scale.
• the invention relates to a process for the production of raw materials for the production of conjugated linoleic acid, which is characterized in that
• a linoleic triglyceride e.g. Sunflower oil, preferably safflower oil, preferably refined safflower oil, transesterified with methanol, preferably ethanol.
• Sunflower oil preferably safflower oil, preferably refined safflower oil
• methanol preferably ethanol.
• transesterification takes place under mild conditions, without the use of inert gas or ethylene or propylene glycol.
• the fatty acid glycerides to be used as starting materials according to the invention can be the usual natural vegetable or animal fats or oils. These include, for example, linola oil, sunflower oil and particularly preferably safflower oil.
• the main components of these fats and oils are glycerides of various types of fatty acids, which contain considerable amounts of impurities such as aldehyde compounds, phospholipid compounds and free fatty acids. These materials can be used directly or after prior purification.
• These are fatty acid mixtures which contain at least 60, preferably more than 70, particularly preferably more than 75% by weight of conjugated linoleic acid. The implementation takes place without the use of inert gas under controlled conditions.
• the reaction is preferably carried out at a temperature in the range from 80 to 120 ° C., preferably 85 to 100 ° C., particularly preferably 88 to 95 ° C. carried out.
• the glycerol obtained during the reaction is continuously drawn off via a coalescence separator and approximately two thirds of the total amount of catalyst are added continuously during the reaction.
• Suitable catalysts are alkali metal and / or alkaline earth metal alcoholates or hydroxides, in particular sodium methoxide and / or sodium glycerate and particularly preferably sodium ethylate.
• the reaction proceeds over 4 to 7 hours, preferably 5 to 6 hours.
• the reaction mixture is neutralized with citric acid. Taking into account the reaction products that are preferably used, the process is particularly preferably used to produce a safflower ethyl ester with a low content of undesired isomers.
• the distillation of the transesterified reaction mixture serves to separate off glycerides, free glycerin and soaps.
• the reaction product also gets a more attractive color.
• the content of palmitic acid can also be reduced and the content of linoleic acid increased during product distillation.
• the excess ethanol is distilled off.
• free glycerol accumulated during ethanol distillation is separated off via the separator.
• the temperature is raised to 150 to 200 ° C., preferably 160 to 180 ° C., under a vacuum of 1 to 3 mbar. 5 to 10% lead are removed and the product is distilled to 5 to 10% residue.
• fractional distillation can preferably be used.
• CLA Conjugated Linoleic Acid
• conjugated linoleic acid is preferably the main isomers 9cis, lltrans octadecadienoic acid and 10trans, 12cis as well as any isomer mixtures which are usually obtained in the production of conjugated linoleic acid.
• the raw materials produced by the process according to the invention should already contain a high proportion of the preferred isomers.
• the method according to the invention is used to produce raw materials for the production of conjugated linoleic acid (CLA).
• CLA conjugated linoleic acid
• the low proportion of undesired isomers in the crude product saves further steps for separating and purifying isomers in the production of the CLA.
• the CLA produced from the raw materials can be used in all those areas which are already known from the literature for conjugated linoleic acid, for example in foods, preferably so-called "functional foods” and in pharmaceuticals, in particular as a supporting agent in the treatment of tumors or for treatment by people suffering from catabolic conditions.
• Example 1 (transesterification).
• the experimental setup for the transesterification consisted of a 2 l reactor (double jacket) with a reflux condenser, coalescence separator in the recycling circuit and a vacuum pump. 1500 g of safflower oil, 240 g of ethanol, 47 g of sodium ethylate in the form of a 20% by weight ethanolic solution (in some cases added subsequently during the reaction) and citric acid, likewise in a 20% by weight ethanolic solution, were used as starting materials. The reaction was carried out at ambient pressure. To this end, the linole-rich oil was introduced, warmed to 60 ° C. and ethanol and about a third of the amount of Na ethylate were added.
• the reactor contents were heated to a reaction temperature of about 90 ° C. and the reaction was operated under reflux. With the circulation pump running (circulation rate 8 l / h), the resulting glycerol phase was drawn off during the reaction and continuously every 30 min. 4 g of catalyst solution are metered in. The reaction time was 5.5 hours.
• the reaction mixture was then neutralized with citric acid.
• a distillation was connected to separate glycerides, free glycerin and soaps. The excess ethanol was removed at a vacuum of 100-300 mbar.
• additional free glycerol which was obtained by the ethanol distillation, was removed by circling over the separator. The bottom temperature was then raised to 160-180 ° C.
• Comparative Example VI Esterification
• the test set-up for the esterification (operation according to the bubble reactor principle) consisted of a heatable reactor with a distillate cooler and trap attached, bottom temperature measurement and control via a heater, immersion tube for N 2 entry, glass frit and Dosimat for ethanol metering and a vacuum pump.
• 2.5 g of p-toluenesulfonic acid and sodium hydroxide solution in the form of a 6% strength by weight aqueous solution were used as starting materials.
• the reaction was run at ambient pressure.
• Table 3 shows a comparison of the isomers and CLA from the reaction product of the transesterification and the esterification, taking into account the different oleic acid / linoleic acid ratio in the raw materials used:

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• 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)
• General Chemical & Material Sciences (AREA)
• Microbiology (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Fats And Perfumes (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

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• 2000
  • 2000-09-18 DE DE10046402A patent/DE10046402B4/de not_active Expired - Fee Related
• 2001
  • 2001-09-08 ES ES01972028T patent/ES2252296T3/es not_active Expired - Lifetime
  • 2001-09-08 CA CA2422804A patent/CA2422804C/fr not_active Expired - Lifetime
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  • 2001-09-08 WO PCT/EP2001/010377 patent/WO2002022768A1/fr active IP Right Grant
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  • 2001-09-08 DE DE50108194T patent/DE50108194D1/de not_active Expired - Lifetime
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• 2003
  • 2003-03-17 NO NO20031225A patent/NO20031225L/no not_active Application Discontinuation

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