EP1319057B1 - Procede de fabrication de produits bruts pour l'obtention d'acide linoleique conjugue - Google Patents

Procede de fabrication de produits bruts pour l'obtention d'acide linoleique conjugue Download PDF

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Publication number
EP1319057B1
EP1319057B1 EP01972028A EP01972028A EP1319057B1 EP 1319057 B1 EP1319057 B1 EP 1319057B1 EP 01972028 A EP01972028 A EP 01972028A EP 01972028 A EP01972028 A EP 01972028A EP 1319057 B1 EP1319057 B1 EP 1319057B1
Authority
EP
European Patent Office
Prior art keywords
linoleic acid
reaction
ethanol
transesterification
conjugated linoleic
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
EP01972028A
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German (de)
English (en)
Other versions
EP1319057A1 (fr
Inventor
Albert Strube
Uwe HÖMMERICH
Bernhard Gutsche
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.)
Cognis IP Management GmbH
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Cognis IP Management GmbH
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Publication of EP1319057A1 publication Critical patent/EP1319057A1/fr
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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
    • 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 dietary supplements and concerns a process for producing raw materials for the production of conjugated linoleic acid.
  • the polyunsaturated ⁇ -3 and ⁇ -6 fatty acids such as ⁇ -linolenic acid, linoleic acid count to the essential for mammals and humans fatty acids.
  • ⁇ -linolenic acid linoleic acid
  • linoleic acid There are other isomeric octadecadienoic acids in nature. Draw these by conjugated double bonds at the C atoms 9 and 11, 10 and 12 as well as 11 and 13 off.
  • conjugated linoleic acids abbreviation: CLA - conjugated linoleic acid
  • CLA CLA-like lipid peroxidation
  • Shultz et al. reported the inhibitory effect on the in vitro growth of human cancer cells. Carcinogenesis 8, 1881-1887 (1987) and Cancer Lett. 63, 125-133 (1992).
  • CLA has a high antioxidant effect, which, for example, the lipid peroxidation can be inhibited. Atherosclerosis 108, 19-25 (1994).
  • conjugated linoleic acid in animal feed and in this context also in the human diet is z. B. from WO 96/06605 known.
  • EP 0579 901 B reports on the use of conjugated linoleic acid for preventing weight loss or a reduction in weight gain or of annorexia 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 linoleic acid-containing precursors, i.e. Products containing a carboxylic acid function with 18-carbon atoms and 2 9- and 12-position double bonds, both in the cis configuration.
  • linoleic acid-containing precursors i.e. Products containing a carboxylic acid function with 18-carbon atoms and 2 9- and 12-position double bonds, both in the cis configuration.
  • there Care must be taken during the conjugation reaction that only the two main CLA isomers (9cis, 11trans and 10trans, 12cis) arise, whose effect in the above described literature is described.
  • a mixture of isomers, such as CLA which is known for technical purposes is used, so in the paint production such.
  • Edenor®UKD 6010 Manufacturer: Cognis, Dusseldorf
  • the pure CLA is often obtained by saponification of linoleic acid-containing oils [WO 96/06605, EP 0902082 A1]. Disadvantage of these methods is the high proportion of undesired isomers. These can in turn be separated by enzymatic esterification, as described in WO 97/18320 . In order to better control the content of isomers, it is also possible to use the corresponding esters as precursors.
  • the state of the art here is the production of the corresponding esters by esterification of the fatty acids with methanol or ethanol. It is described in the literature that suitable starting materials for gentle conjugation are in particular the methyl and ethyl esters of linoleic acid [WO 99/47135] .
  • a linoleic triglyceride e.g. Sunflower oil, preferably safflower oil, preferably refined safflower oil transesterified with ethanol.
  • a linoleic triglyceride e.g. Sunflower oil, preferably safflower oil, preferably refined safflower oil transesterified with ethanol.
  • esterification with linoleic acid is surprising to observe that almost no unwanted pre-conjugations and isomerizations occur.
  • the transesterification takes place under mild conditions, without the use of inert gas or ethylene or propylene glycol instead.
  • the fatty acid glycerides to be used according to the invention as starting materials 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 ingredients These fats and oils are glycerides of various types of fatty acids that considerable amounts of impurities such as aldehyde compounds, phospholipid compounds and contain free fatty acids. These materials can be direct or be used after prior purification.
  • the reaction is preferably carried out at a temperature in the Range of 80 to 120 ° C, preferably 85 to 100 ° C, particularly preferably 88 to 95 ° C. carried out.
  • the glycerol accumulating during the reaction is passed through a coalescence separator withdrawn continuously and about two thirds of the total amount of catalyst are added continuously during the reaction.
  • Suitable as catalysts alkali and / or alkaline earth metal alkoxides or hydroxides, especially sodium methoxide and / or sodium glycerate, and more preferably sodium ethylate.
  • the Reaction proceeds over 4 to 7 hours, preferably 5 to 6 hours.
  • the transesterification the reaction mixture is neutralized with citric acid.
  • the process is particularly preferred for the preparation of a safflorethyl ester with a low content on undesired isomers.
  • the distillation of the transesterified reaction mixture is used to separate off any resulting Glycerides, free glycerin and soaps.
  • the reaction product gets as well a more appealing color.
  • the content of palmitic acid and the content of linoleic acid be increased.
  • a vacuum of 100 to 300 mbar distilled off the excess ethanol.
  • free glycerol is separated via the separator.
  • the temperature to 150 to 200 ° C, preferably 160 raised to 180 ° C. 5 to 10% flow are taken and the product up on Distilled 5 to 10% residue.
  • a fractional distillation can be used.
  • a batch distillation from a reactor with attached Carry out column which causes the C16 content in the feed distillate increases, or to carry out the distillation in two stages, whereby about 5 to 10% by volume of the forerun from the fractionation column decreases and the main run over the top of the column distilled.
  • the content of C16 in the main run can be decrease from an initial value of 6.5 to 0.7% by weight while at the same time the amount of C18: 2 increases from 75.5 to 81.4 wt .-%.
  • CLA Conjugated linoleic acid
  • conjugated linoleic acid are preferably the main isomers 9cis, 11trans octadecadienoic acid and 10trans, 12cis and also any isomer mixtures, as they usually occur in the production of conjugated linoleic acid.
  • the raw materials produced by the process according to the invention should already have a high Contain proportion of preferred isomers.
  • the process of the invention is used to produce raw materials for recovery of conjugated linoleic acid (CLA).
  • CLA conjugated linoleic acid
  • the low proportion of unwanted isomers in Crude product saves further steps for isomer separation and purification during production 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, hereby in particular as a supportive agent in the treatment of tumors or for treatment of persons suffering from catabolic states.
  • Example 1 (transesterification).
  • the experimental setup for the transesterification consisted of a 2 l reactor (double jacket) with reflux condenser, coalescence separator in the recycle loop and vacuum pump.
  • As starting materials 1500 g of safflower oil, 240 g of ethanol, 47 g of sodium ethylate in the form of a 20 wt .-% ethanolic solution (sometimes added later during the reaction) and citric acid, also used in a 20 wt .-% ethanolic solution).
  • the reaction was carried out at ambient pressure. To this was added the linoleic oil, heated to 60 ° C and added to ethanol and about one-third of the amount of Na-ethylate.
  • the reactor contents were heated to about 90 ° C reaction temperature and the reaction was operated under reflux. Under running circulation pump (circulation rate 8 l / h), the resulting glycerol phase was withdrawn during the reaction and continuously every 30 min. about 4 g of catalyst solution added. The reaction time was 5.5 h. The reaction mixture was then neutralized with citric acid. For the separation of glycerides, free glycerol and soaps, a distillation was connected. At 100-300 mbar vacuum, the excess ethanol was removed. In addition, by separating out through the separator additional free glycerol, which was obtained by the ethanol distillation, separated.
  • the bottom temperature was then raised to 160-180 ° C at a vacuum of 1-3 mbar, taken 5-10% forerun and then the main run distilled to 5-10% residue.
  • the determination of the isomers and fatty acid fractions was carried out by a chromatographic method.
  • a 120m long silica column 120m * 0.25mm Permabond® FFAP - 0.25 ⁇ m, reference: Macherey Nagel) was used with hydrogen as carrier gas.
  • composition of the product is shown in Table 1: Composition of feed oil and distillate fraction (data as% by weight) isomer use oil distillate fraction C 16: 0 6.01 0.99 C 18: 0 2.80 3.10 C18: 1 c9 13.25 14.31 C 18: 2 c9, c12 74.74 76.69
  • Comparative Example C1 esterification
  • the experimental set-up for the esterification consisted of a heatable 2 l reactor with attached distillate cooler and trap, bottom temperature measurement and control via heater mushroom, immersion tube for N 2 entry, glass frit and Dosimat for ethanol addition and a vacuum pump.
  • 1000 g of sunflower oil fatty acid (Edenor® Sb, Cognis GmbH Germany) 1000 g of ethanol (continuously added), 2.5 g of p-toluenesulfonic acid and sodium hydroxide in the form of a 6 wt .-% aqueous solution used.
  • the reaction was operated at ambient pressure.
  • composition of the product is shown in Table 2: Composition of feed oil and distillate fraction (data as% by weight) isomer use oil distillate fraction C18: 1 t9 ⁇ 0.05 0.49 C18: 1 t10 nb 0.31 C18: 1 t11 nb 0.40 c18: 1 c11 0.74 0.78 C18: 2 t9, t12 0.06 1.54 C18: 2 c9, t12 0.66 1.04
  • 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 / linoleic acid ratio in the raw materials used: Comparison transesterification / esterification Safflorethyl ester by transesterification (according to the invention) Safflower ethyl ester by esterification (comparative example) C 16/0 7.20 7.08 C 16/1 0.05 0.16 C 18/0 2.60 2.47 C 18 / 19t nn 0.53 C18 / 1 10t nn 0.41 C18 / 1 11t nn 0.46 C 18/1 9c 11,99 10.08 C 18/1 11c 0.60 0.95 C 18/2 9t, 12t 0.03 1.77 C 18/2 9c, 12t 1.49 1.30 C 18/2 9t, 12c nn 0.56 C 18/2 9c, 12c 75.03 73.12 Unidentified or larger C 18 1.01 1.21 Total

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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)

Claims (7)

  1. Procédé de fabrication de matières premières pour l'obtention d'acide linolique conjugué,
    caractérisé en ce qu'
    (a) on transestérifie des triglycérides, qui contiennent au moins 60 % en poids d'acide linolique, avec de l'éthanol à une température de 80 à 120°C, et
    (b) le mélange de transestérification ainsi obtenu est soumis à une distillation.
  2. Procédé selon la revendication 1,
    caractérisé en ce qu'
    on utilise de l'huile de tournesol en tant que triglycéride.
  3. Procédé selon les revendications 1 et/ou 2,
    caractérisé en ce qu'
    on utilise de l'huile de carthame en tant que triglycéride.
  4. Procédé selon au moins l'une quelconque des revendications 1 à 3,
    caractérisé en ce qu'
    on ajoute en continu du méthylate de sodium en tant que catalyseur pendant la réaction.
  5. Procédé selon au moins l'une quelconque des revendications 1 à 4,
    caractérisé en ce qu'
    (a) on fait chauffer une huile riche en acide linolique à une température de 50 à 70°C et on ajoute de l'éthanol ainsi que de l'éthylate de sodium,
    (b) on chauffe ensuite la totalité du contenu du réacteur à une température de 80 à 120°C, et
    (c) on conduit la réaction à reflux pendant 5 à 6 heures tout en séparant la phase glycérol produite, pendant que l'on ajoute la solution de catalyseur en continu, et
    (d) on neutralise ensuite le mélange réactionnel avec de l'acide citrique.
  6. Procédé selon au moins l'une quelconque des revendications 1 à 5,
    caractérisé en ce qu'
    après la transestérification, on sépare les glycérides restants, le glycérol libre et les savons ,
    (a) en séparant par distillation l'éthanol excédentaire sous un vide de 100 à 300 mbars et
    (b) en distillant ensuite, sous un vide de 1 à 3 mbar et à une température de 150 à 200°C, le produit restant jusqu'à l'obtention d'un résidu de 5 à 10 %.
  7. Procédé selon au moins l'une quelconque des revendications 1 à 6,
    caractérisé en ce qu'
    on soumet le mélange de transestérification obtenu à une distillation fractionnée.
EP01972028A 2000-09-18 2001-09-08 Procede de fabrication de produits bruts pour l'obtention d'acide linoleique conjugue Expired - Lifetime EP1319057B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10046402 2000-09-18
DE10046402A DE10046402B4 (de) 2000-09-18 2000-09-18 Verfahren zur Herstellung von Rohstoffen für die Gewinnung von konjugierter Linolsäure
PCT/EP2001/010377 WO2002022768A1 (fr) 2000-09-18 2001-09-08 Procede de fabrication de produits bruts pour l'obtention d'acide linoleique conjugue

Publications (2)

Publication Number Publication Date
EP1319057A1 EP1319057A1 (fr) 2003-06-18
EP1319057B1 true EP1319057B1 (fr) 2005-11-23

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EP01972028A Expired - Lifetime EP1319057B1 (fr) 2000-09-18 2001-09-08 Procede de fabrication de produits bruts pour l'obtention d'acide linoleique conjugue

Country Status (9)

Country Link
US (1) US6762313B2 (fr)
EP (1) EP1319057B1 (fr)
JP (1) JP2004529211A (fr)
AT (1) ATE310790T1 (fr)
CA (1) CA2422804C (fr)
DE (2) DE10046402B4 (fr)
ES (1) ES2252296T3 (fr)
NO (1) NO20031225L (fr)
WO (1) WO2002022768A1 (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10225117A1 (de) * 2002-06-06 2004-01-08 Cognis Deutschland Gmbh & Co. Kg Verfahren zur Herstellung von konjugierter Linolsäure
AU2003299920A1 (en) * 2003-12-23 2005-08-03 Stepan Company Production and purification of esters of conjugated linoleic acids
US7767713B2 (en) * 2004-08-05 2010-08-03 Palo Alto Investors Linoleic acid active agents for enhancing probability of becoming pregnant
KR101282098B1 (ko) * 2005-02-04 2013-07-04 안칭 중창 바이오테크놀로지 컴파니 리미티드 지방산 제조 방법
US20080113067A1 (en) * 2005-10-17 2008-05-15 Monoj Sarma Protein-Containing Food Product and Coating for a Food Product and Method of Making Same
US20070087085A1 (en) * 2005-10-17 2007-04-19 Bunge Oils, Inc. Protein-containing food product and coating for a food product and method of making same
EP1957063B1 (fr) 2005-12-05 2010-08-25 Stepan Company Procede pour preparer de l'acide linoleique conjugue et ses derives a partir d'acide ricinoleique
US20070148311A1 (en) * 2005-12-22 2007-06-28 Bunge Oils, Inc. Phytosterol esterification product and method of make same
JP5282951B2 (ja) * 2008-10-01 2013-09-04 国立大学法人山口大学 脂肪酸アルキルエステルの製造方法
CN105481682A (zh) * 2014-09-19 2016-04-13 浙江医药股份有限公司新昌制药厂 一种以植物油为原料纯化制备高含量共轭亚油酸的方法

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Publication number Priority date Publication date Assignee Title
ZA816488B (en) 1980-09-18 1982-09-29 Chemical Services Pty Ltd Liquid fuel
DE4124517A1 (de) 1991-07-24 1993-01-28 Battelle Institut E V Verfahren zur destillativen aufkonzentrierung von reaktiven fettsaeuren und deren estern
EP0535290B1 (fr) 1991-09-02 1994-11-30 Primavesi, Markus Procédé et installation pour la production continue d'esters d'acides gras
US5554646A (en) 1992-04-29 1996-09-10 Wisconsin Alumni Research Foundation Method for reducing body fat in animals
US5430066A (en) 1992-04-29 1995-07-04 Wisconsin Alumni Research Foundation Methods for preventing weight loss, reduction in weight gain, and anorexia due to immune stimulation
US5428072A (en) 1992-04-29 1995-06-27 Wisconsin Alumni Research Foundation Method of increasing the efficiency of feed conversion in animals
DK0866874T4 (da) 1995-11-14 2005-07-11 Loders Croklaan Bv Fremgangsmåde til fremstilling af materialer med höjt indhold af isomerer af konjugeret linolsyre
CA2246085C (fr) 1997-09-12 2004-04-27 Krish Bhaggan Production de matieres riches en isomeres conjugues de residus d'acides gras a longue chaine polyinsaturee
US6015833A (en) * 1998-03-17 2000-01-18 Conlinco., Inc. Conjugated linoleic acid compositions
US7078051B1 (en) * 1998-08-11 2006-07-18 Natural Asa Conjugated linoleic acid alkyl esters in feedstuffs and food
US6410761B1 (en) 1998-03-17 2002-06-25 Conlinco, Inc. Conjugated linoleic acid compositions and methods of making same

Also Published As

Publication number Publication date
ES2252296T3 (es) 2006-05-16
EP1319057A1 (fr) 2003-06-18
US20030181522A1 (en) 2003-09-25
ATE310790T1 (de) 2005-12-15
CA2422804A1 (fr) 2003-03-18
CA2422804C (fr) 2011-08-02
DE50108194D1 (de) 2005-12-29
DE10046402B4 (de) 2006-04-20
WO2002022768A1 (fr) 2002-03-21
US6762313B2 (en) 2004-07-13
NO20031225D0 (no) 2003-03-17
DE10046402A1 (de) 2002-04-04
NO20031225L (no) 2003-03-17
JP2004529211A (ja) 2004-09-24

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