WO2006101473A1 - Procédé et catalyseurs pour la conjugaison de doubles liaisons dans les acides gras et les dérivés d'acides gras - Google Patents

Procédé et catalyseurs pour la conjugaison de doubles liaisons dans les acides gras et les dérivés d'acides gras Download PDF

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WO2006101473A1
WO2006101473A1 PCT/US2005/008639 US2005008639W WO2006101473A1 WO 2006101473 A1 WO2006101473 A1 WO 2006101473A1 US 2005008639 W US2005008639 W US 2005008639W WO 2006101473 A1 WO2006101473 A1 WO 2006101473A1
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Prior art keywords
metal alkoxide
metal
poly
fatty acid
glycol
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PCT/US2005/008639
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English (en)
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Joseph C. Rongione
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Stepan Company
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0252—Nitrogen containing compounds with a metal-nitrogen link, e.g. metal amides, metal guanidides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0201—Oxygen-containing compounds
    • B01J31/0204—Ethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0201—Oxygen-containing compounds
    • B01J31/0211—Oxygen-containing compounds with a metal-oxygen link
    • B01J31/0212—Alkoxylates
    • 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
    • C11C3/14—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by isomerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/12—Sodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/13—Potassium

Definitions

  • the invention relates to a process for the manufacture of conjugated fatty acids or their derivatives, in particular long chain polyunsaturated fatty acids, using an improved catalyst system that isomerizes the fatty acids and their derivatives in a more efficient and cost-effective manner.
  • the improved catalyst system includes a metal alkoxide or metal amide catalyst chelated with an appropriate chelating agent or a metal alkoxide formed from another metal
  • conjugated polyenes conjugated dienes and trienes are the most prevalent.
  • conjugated isomers of long chain polyunsaturated fatty acids are known for their health enhancing qualities, when used in food products.
  • researchers have shown that ingestion of conjugated polyenes may inhibit tumor growth, prevent heart disease, and reduce body fat.
  • conjugated long chain polyunsaturated fatty acids are conjugated linoleic acids (CLAs).
  • CLAs conjugated linoleic acids
  • CLAs originally isolated from the fat and milk of ruminants, refer to a mixture of positional and geometric isomers of linoleic acids, which are unsaturated fatty acids considered essential to the human diet and found preferentially in dairy products and meat.
  • CLA(s) is a general or collective term used to describe one or a mixture of conjugated octadecadienoic fatty acids.
  • FFA free fatty acids
  • FAME fatty acid methyl esters
  • CLA reportedly has antidiabetic properties, leads to reduced carcinogenesis and atherosclerosis, and increases bone and lean muscle mass.
  • CLAs have generated much interest in the academic and business communities because of their nutritional, therapeutic, and pharmacological properties, and have exhibited impressive physiological effects in animal studies.
  • CLAs are a mixture of positional isomers of linoleic acid (C18:2) having conjugated double bonds.
  • the cis-9, trans-11 (c9,tll) and trans- 10, cis-12 (tl ⁇ ,cl2) isomers are present in greatest abundance in typical CLA compositions, but it is not absolutely certain which isomers are responsible for the biological and heightened nutritional activity previously observed. From labeled uptake studies, it has been noted that the c9,tll-isomer appears to be somewhat preferentially taken up and incorporated into the phospholipid fraction of animal tissues, and to a lesser extent the tlO,cl2-isomer. (See Ha, et.
  • conjugated fatty acids typically are present in animal fats only at a level of about 0.5 percent. See U.S. Pat. 6,479,683 (Albany, et al.). In plant sources, conjugated fatty acids do not occur widely. Thus, investigators continue to seek ways to obtain conjugated fatty acids by partial or total synthesis.
  • conjugated fatty acids and their derivatives are of great technical and commercial interest and, therefore, many attempts have been made to isomerize unconjugated fatty acids to conjugated ones.
  • Linoleic acid can be expressed as an all-cis-9,12- octadecadienoic acid, or a c9,cl2-octadecadienoic acid, where c indicates the cis- configuration (the orientation that typically occurs in linoleic acid derived from natural sources) and the numbers 9 and 12 indicate the position of the double bonds relative to the carboxyl carbon of the acyl chain (-COOH).
  • linoleic acid can be expressed in the (n-6) or omega (oo) system as 18:2 (n-6) or 18:2 ⁇ 6, where (n-6) or ⁇ 6 indicates the position of the first double bond beginning from the methyl end.
  • Previously known methods to produce conjugated unsaturated compounds include, for example, hydrogenation of fats using a variety of catalysts. Such methods, however, often lead to incomplete isomerization and unwanted side reactions, such as polymerization and intramolecular cyclization.
  • Other known methods include isomerization with an excess of alkali metal hydroxide in an aqueous or alcoholic medium, which leads to a quantitative isomerization. See, e.g., U.S. Pat. No. 2,343,644 (Cawley).
  • the rearrangement of the double bonds of linoleic acids to conjugated positions can occur during treatment with catalysts such as nickel or alkali at high temperatures, and during autooxidation. It is theoretically possible that eight geometric isomers of 9,11 and 10,12 octadecadienoic acid (c9,cll; c9,tll; t9,cll; t9,tll; cl ⁇ ,cl2; cl ⁇ ,tl2; tl ⁇ ,cl2 and tl ⁇ ,tl2) could result from the isomerization of c9,cl2-octadecadienoic acid.
  • U.S. Pat. No. 6,420,577 (Reaney, et al.) describes a process for making CLAs by reacting a linoleic acid-rich oil with a base, in the presence of a catalytic amount of such a base, in an aqueous medium via simultaneous saponification and quantitative isomerization.
  • Polyethylene glycol is used in the process as a phasing aid at the end of the process.
  • this process utilizes a heightened temperature (>170 0 C). Higher temperatures lead to the formation of undesirable CLA isomers, including the trans, trans-CLA isomers.
  • U.S. Pat. No. 6,160,140 (Bhaggan, et al.) describes the conversion of a linoleic acid-containing oil, free fatty acid, or alkyl ester to CLA by treating it with a base in an alcohol solution, where the alcohol has at least 3 carbons and at least 2 hydroxyl groups.
  • the allegedly preferred embodiment of the Bhaggan patent utilities potassium hydroxide in propylene glycol.
  • the use of solvent in the conjugation (isomerization) step gives rise to the potential formation of unwanted CLA-alcohol esters (e.g., CLA-propylene glycol esters) as well as reduces overall process productivity by lowering reactor efficiency and adding processing steps for solvent removal.
  • U.S. Pat. No. 3,162,658 (Baltes, et al.) provides for the use of alkali metal hydrocarbyl alcoholates or alkali metal amides to isomerize esters of unconjugated polyethylene acids such as linoleic acids.
  • This patent appears to indicate metal alkoxides and their effectiveness in isomerizing esters of unconjugated polyethylene acids.
  • the patent further appears to indicate that potassium alcoholates may be useful as isomerization catalysts for technical purposes not only because of their adequate catalytic activity, but also for their partial solubility. According to the Baltes patent, decreasing cation size decreases catalytic effectiveness.
  • U.S. Pat. No. 3,984,444 (Ritz, et al.) describes the isomerization of an ester of an alcohol having 1 to 12 carbon atoms and a fatty acid or its methyl ester having 10 to 24 carbon atoms with isolated double bonds (to the corresponding compound having conjugated double bonds) using alkaline metal alcoholates in strongly polar aprotic solvents.
  • solvents in the conjugation step is undesirable because it gives rise to the potential formation of unwanted CLA-alcohol esters (e.g., CLA-propylene glycol esters) and reduces process efficiency.
  • One objective of the presently described technology is to improve catalytic effectiveness of metal alkoxides or amides used to isomerize unconjugated fatty acids, especially those having less effective metal ions.
  • Another objective of the presently described technology is to exchange the less effective counter ions of metal alkoxide or amides with more effective counter ions.
  • Still another objective of the presently described technology is to provide a system which can avoid the use of a solvent in the conjugation step of the isomerization process to reduce or eliminate the potential formation of unwanted CLA-alcohol esters (e.g., CLA-propylene glycol esters).
  • CLA-alcohol esters e.g., CLA-propylene glycol esters
  • a further objective of the presently described technology is to economically generate metal alkoxides that are not commercially available or are relatively expensive to produce conventionally.
  • a still further objective of the present technology is to decrease the cost to produce conjugated fatty acids and their derivatives, most notably CLAs and their derivatives.
  • the presently described technology provides a process to improve the performance of a suitable catalyst system for conjugating unsaturated fatty acids or their derivatives by providing a metal alkoxide or amide catalyst comprising a cation; providing a chelating agent; and chelating the cation of the metal alkoxide or metal amide catalyst with the chelating agent.
  • the chelated metal alkoxide or amide has an improved catalytic effectiveness to isomerize unconjugated fatty acids and/or their derivatives (e.g., fatty acid esters).
  • the chelating step can be performed before the metal alkoxide or amide catalyst is added to a composition containing an unconjugated fatty acid and/or a derivative of the fatty acid, or can be performed in situ by first adding the chelating agent to the composition containing unconjugated fatty acid starting material and then adding the metal alkoxide or amide catalyst to the reaction mixture.
  • the presently described technology provides a process for the formation of a second metal alkoxide for conjugating unsaturated fatty acids or their derivatives from a first metal alkoxide by exchanging cations between the first metal alkoxide and a salt of the second metal by dissolving the salt of the second metal in a first solvent to make a first solution; mixing the first metal alkoxide with the first solution; forming a salt of the first metal and an anion from the first solution; and forming a second solution comprising the second metal alkoxide.
  • a catalytically more effective metal alkoxide can be obtained from a less effective metal alkoxide .
  • currently commercially unavailable or expensive metal alkoxides can also be obtained in a more cost-effective manner.
  • the first metal is sodium and the second metal is an alkali, alkaline earth or transition metal other than sodium.
  • conjugated linoleic acid(s) or “CLA(s)” refers to any conjugated linoleic acid or octadecadienoic free fatty acid. It is intended that this term encompass all positional and geometric isomers of linoleic acid with two conjugated carbon-carbon double bonds at any position in the respective molecule.
  • a CLA differs from an ordinary linoleic acid in that an ordinary linoleic acid has double bonds at carbon atoms 9 and 12 while a CLA has conjugated double bonds.
  • CLAs include, but are not limited to, cis- and trans- isomers ("E/Z isomers") of the following positional isomers: 2,4- octadecadienoic acid, 4,6-octadecadienoic acid, 6,8-octadecadienoic acid, 7,9- octadecadienoic acid, 8,10-octadecadienoic acid, 9,11-octadecadienoic acid, 10,12-octadecadienoic acid, and 11,13-octadecadienoic acid.
  • E/Z isomers of the following positional isomers: 2,4- octadecadienoic acid, 4,6-octadecadienoic acid, 6,8-octadecadienoic acid, 7,9- octadecadienoic acid, 8,10-octadecadienoic acid, 9,11-octadecadienoic
  • CLA(s) encompasses a single isomer, a selected mixture of two or more isomers, and a non-selected mixture of isomers obtained from natural sources, as well as synthetic and semi-synthetic CLAs.
  • CLA derivatives refers to moieties of CLAs recognized by one skilled in the art as structures that can be readily converted to carboxylic acids. Examples of such moieties are carboxylic acids, salts of carboxylic acids, carboxylic anhydrides, amides, carboxylic esters, ortho esters, 1,3-dioxolanes, dioxanones, oxazoles and hydrazides.
  • esters include any and all positional and geometric isomers of CLA bound through an ester linkage to an alcohol or any other chemical group including, but not limited to physiologically acceptable, naturally occurring alcohols (e.g., methanol, ethanol, or propanol). Therefore, an ester of CLAs or an esterified CLA or a CLA ester may contain any of the positional and geometric isomers of CLAs.
  • undesirable isomers of CLAs includes, but is not limited to, cll,tl3-; tll,cl3-; tll,tl3-; cll,cl3-; c8,tl ⁇ -; t8,tl ⁇ -; and c8,cl ⁇ - isomers of octadecadienoic acids, but does not include tl ⁇ ,cl2- and c9,t 11 -isomers of octadecadienoic acids.
  • Undesirable isomers may also be referred to as "minor isomers" of CLAs as these isomers are generally produced in low amounts when CLAs are synthesized by alkali isomerization.
  • the term “c” encompasses a chemical bond in the cis orientation
  • the term “t” refers to a chemical bond in the trans orientation. If a positional isomer of CLA is designated without a “c” or a "t", then that designation includes all four possible isomers.
  • 10,12 octadecadienoic acid encompasses cl ⁇ ,tl2-; tl ⁇ ,cl2-; tl ⁇ ,tl2-; and cl ⁇ ,cl2- octadecadienoic acid, while tlO,cl2-octadecadienoic acid or tlO,cl2-CLA refers to just the single isomer.
  • oil refers to a free flowing liquid containing long chain fatty acids (e.g., linoleic acids and CLAs) or other long chain hydrocarbon groups, which can comprise triglycerides of CLAs and linoleic acids.
  • the long chain fatty acids include, but are not limited to, the various isomers of CLAs.
  • CLAs or linoleic acids
  • triglycerides may contain CLAs (or linoleic acids) at any or all of the three positions on the triglyceride backbone.
  • a triglyceride of CLA may contain any of the positional and geometric isomers of CLAs.
  • a "linoleic acid-rich/containing" (or “CLA- rich/containing”) material is a material — which can be an oil, an ester, a salt or other derivatives thereof — that is rich in or contains linoleic residues (or CLA residues).
  • a “linoleic acid residue” (or “CLA residue”) means a component which has a fatty carbon chain length and isomer distribution that resembles linoleic acids (or CLAs).
  • the presently described technology relates to a process to manufacture conjugated fatty acids and/or their derivatives, in particular long chain polyunsaturated fatty acids (e.g., CLAs) or their derivatives using an improved catalyst system.
  • the improved catalyst system includes a metal alkoxide or amide catalyst chelated with an appropriate chelating agent or a suitable metal alkoxide (e.g., potassium alkoxide) formed from another alkoxide (e.g., sodium alkoxide).
  • isomerization of nonconjugated fatty acids and their derivatives can be performed at a lower temperature with minimal or no solvent, which improves both productivity and isomer ratio.
  • An ensuing saponification reaction can be performed in an aqueous medium at significantly lower temperature than the conventional art (e.g., 75 °C vs. 200 0 C), and thereby removing the need for a pressure vessel, improving process safety, and decreasing environmental hazards while still preserving desirable product isomer ratios.
  • Some of the salt can be pre-formed in the reaction mix, which can significantly decrease the reaction time.
  • the isomerization step is typically catalyzed by a base in a nonaqueous system, and the catalyst can be an alkali, alkaline earth or transition metal alkoxide salt of an alkyl group alcohol, i.e., alkyl alcoholates, or an alkali, alkaline earth or transition metal amide.
  • the catalyst can be an alkali, alkaline earth or transition metal alkoxide salt of an alkyl group alcohol, i.e., alkyl alcoholates, or an alkali, alkaline earth or transition metal amide.
  • Examples of metal alkoxide catalysts useful in the performance of the presently described technology are alcoholates of monohydric alcohols with 1-18 carbon atoms of the alkali, alkaline earth or transition metals.
  • Such alkali, alkaline earth or transition metal alkoxides include, but are not limited to alcoholates of methyl, ethyl, propyl, butyl, tertiary butyl, lauryl, stearyl, oleyl, or benzyl alcohols.
  • the specific metal alkoxides set forth in this paragraph except those derived from benzyl alcohol can be termed as alkali, alkaline earth or transition metal alcoholates.
  • Alkali, alkaline earth or transition metal alcoholates can also be called "alkali,” “alkaline earth” or "transition metal hydrocarbyl alcoholates.”
  • Cesium, rubidium, potassium, sodium, calcium, lithium, magnesium, copper, iron or zinc alkoxides or amides can be utilized, for example, along with mixtures of such alkoxides or amides, in the presently described technology.
  • Alkali, alkaline earth or transition metal alkoxide salts of lower alkyl group alcohols (about 1-6 carbons) are preferred.
  • Sodium methoxide is likely the least expensive to acquire among the metal alcoholates that are suitable for the isomerization of unconjugated fatty acids according to the presently described technology.
  • potassium alkoxides e.g., potassium methoxide
  • potassium methoxide the more expensive potassium alkoxides
  • Many other known metal alkoxides, including sodium methoxide, are viewed in the prior art as less effective than potassium alkoxides.
  • some conventional isomerization process descriptions provide that decreasing cation size decreases catalytic effectiveness.
  • a composition comprising an unconjugated fatty acid and/or a derivative thereof, for example an alkyl linoleate composition, is treated with a metal alcoholate and a chelating agent at temperatures low enough to suppress formation of undesirable isomers, but sufficient to cause rearrangement of the double bonds.
  • the chelating agent can be washed from the conjugated fatty aid derivative solution by using any conventional washing technique known in the art.
  • the unconjugated fatty acid derivatives in accordance with the presently described technology can include, but are not limited to esters, amides, carboxylic acids, salts of carboxylic acids, carboxylic anhydrides, ortho esters, 1,3-dioxolanes, dioxanones, oxazoles and hydrazides of various unconjugated fatty acids.
  • Suitable chelating agents include, but are not limited to polyethers and polyether derivatives.
  • the molecular weight of the polyethers and polyether derivatives used as chelating agents in the presently described technology range from about 150 to about 8000 atomic mass units.
  • the charge quantity of the chelating agent is from about 0.5% to about 25%, alternatively from about 0.5% to 9%, alternatively from about 0.75% to about 6% of the weight of the unconjugated fatty acid and/or its derivative.
  • the chelating agent in accordance with at least one embodiment of the presently described technology is a nitrogen-containing compound such as triethanolamine or tris[2-(2-methoxyethoxy)ethyl]amine.
  • the chelating agent e.g., a polyether
  • the isomerization catalyst e.g., a metal alkoxide or amide
  • the chelating agent and the isomerization catalyst are premixed; then the mixture comprising the chelated isomerization catalyst is added to the composition comprising the unconjugated fatty acid and/or its derivative in an isomerization reaction vessel.
  • the catalyst loading can be from about 0.3% to about 7% by weight, alternatively from about 0.3% to about 4% by weight, alternatively from about 0.5% to about 3 % by weight, based on the weight of the fatty acid and/or its derivative in the composition.
  • the metal alkoxide or amide catalyst When being added directly to the unconjugated fatty acid composition or being mixed with the chelating agent to form a premix, can be delivered as a solid or as a solution, for example, in the conjugate alcohol of the metal alkoxide when a metal alkoxide is used.
  • the isomerization step can be performed at temperatures low enough to suppress formation of undesirable CLA isomers, but sufficient to cause rearrangement of the double bonds. Such temperatures can be at or below about 140 °C, alternatively between about 90 0 C to about 130 0 C, alternatively between about 110 0 C to about 120 0 C, and alternatively at about 120 0 C.
  • the catalyst either before or after chelated with the chelating agent, can be added to the composition of the fatty acid and/or its derivative at about 140 0 C or below.
  • no solvent is added for the isomerization step.
  • the catalyst for the isomerization step may be added in a solvent, but the starting composition of the unconjugated fatty acid and/or its derivative is not dissolved in a solvent. Relative to the fatty acid or its derivative quantity, the catalyst solvent may be present in a minimal and/or negligible amount at any given time since the catalyst solvent is distilled from the reactor soon after it is added.
  • solvent By avoiding the use of solvent in the isomerization step, the potential formation of unwanted isomers, e.g., CLA-alcohol esters, can be reduced or prevented and process efficiency is improved.
  • the process of the invention can optionally, although less preferably, be carried out in the presence of solvents which do not interfere with the overall conjugation reaction.
  • solvents which are used preferably in an amount of from about 10 to about 50 percent, alternatively from about 15 to about 40 percent, alternatively from about 20 to 30 percent based on the weight of the starting fatty acid material, are for example, methyl, ethyl, isopropyl, butyl, amyl alcohol, pentane, hexane, heptane, heptylene-(l), octylene-1, benzene, toluene, or a combination thereof.
  • a second metal alkoxide can be formed from a first metal alkoxide, e.g., a sodium alkoxide, and a salt of the second metal, e.g., a carboxylate or halide of the first metal, by for example, the precipitation of the salt of the first metal, e.g., a sodium carboxylate or halide from the cation exchange solvent.
  • a first metal alkoxide e.g., a sodium alkoxide
  • a salt of the second metal e.g., a carboxylate or halide of the first metal
  • the newly formed solution containing the second metal alkoxide can then be used to conjugate double bonds of a fatty acid and/or its derivative in a manner similar to that as described above.
  • the first metal in accordance with this embodiment of the present technology is sodium
  • the second metal is an alkali, alkaline earth or transition metal other than sodium.
  • the salts of the second metals include, but are not limited to aliphatic carboxylate (C 1 -C 12 ) salts of calcium, magnesium, potassium, lithium, copper or zinc and halides of calcium, magnesium, iron, copper or zinc.
  • halide counter ions in the salts of the second metals include, but are not limited to chloride, bromide and iodide ions.
  • the salt of the second metal is preferably first dissolved in a first solvent. More preferably, the first solvent used to dissolve the salt of the second metal is capable of causing the salt of the first metal and the anion from the salt of the second metal or another anion from the first solution to precipitate.
  • the first metal alkoxide can be added to the salt of the second metal dissolved in the first solvent as a solid, as a solution in the first solvent or as a solution in a second solvent.
  • suitable solvents for the presently described technology include, but are not limited to aliphatic alcohols having from about 1 to about 6 carbons, aliphatic polyols having from about 1 to about 6 carbons and from about 2 to about 6 hydroxyls, dimethylformamide and tetrahydrofuran.
  • Methyl esters derived from safflower oil (175 g, 0.594 mol) i.e., methyl linoleate
  • a 25% solution of potassium methoxide (15.2 g, 0.054 mol) in methanol at 110 0 C.
  • 97.6% of the available methyl linoleate had been isomerized to conjugated linoleic acid methyl ester (CLME).
  • CLME conjugated linoleic acid methyl ester
  • Methyl esters derived from safflower oil (176 g, 0.598 mol) were treated with a 25% solution of sodium methoxide (13.7 g, 0.063 mol) in methanol at 110 0 C. After a 1-hour feed and a 3-hour hold period of time at 110 0 C, only 2.5% of the available methyl linoleate had been isomerized to CLME. The fatty acid distribution was determined by GC.
  • Methyl esters derived from safflower oil (504 g, 1.71 mol) and poly(ethylene glycol) (35.5g, 0.09 mol, avg. MW 400) were combined and heated to 120 0 C. Mo this solution was fed a 25% solution of sodium methoxide (56.3 g, 0.261 mol) in methanol at 120 0 C. After 8 hours of time at 120 0 C, 98% of the available methyl linoleate had been isomerized to CLME. The fatty acid distribution was determined by GC.
  • Methyl esters derived from sunflower oil 100.13 g, 0.346 mol
  • poly(ethylene glycol) (1.12g, 0.0028 mol, avg. MW 400) were combined and heated to 120 0 C.
  • a methanolic solution of potassium methoxide (KOMe) 25 wt.%, 1.2 g
  • KOMe potassium methoxide
  • KOMe solution (1.45 g; 2.65 g total, 0.0094 mol; 0.66 wt% based on starting ester) was then added. After 1.5 hours of time, the residual methyl linoleate was determined to be 0.5%.
  • the KOMe loading represents 32% of the typical industry standard charge. Free fatty acid for this sample after workup was 1.7%. Typical values for material made with higher catalyst loadings range from 8-10%. The fatty acid distribution was determined by GC.

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Abstract

La présente invention concerne un procédé de fabrication d'acides gras conjugués ou de leurs dérivés, en particulier des acides gras polyinsaturés à longue chaîne (par exemple les CLA) ou leurs dérivés, en employant un système catalytique amélioré qui isomérise les acides gras et leurs dérivés d'une façon efficace et rentable. Le système catalytique amélioré inclut un catalyseur de type alkoxyde métallique ou amide chélaté par un agent chélatant approprié ou un alkoxyde métallique formé à partir d'un autre alkoxyde métallique au cours du procédé décrit par l'invention.
PCT/US2005/008639 2005-03-15 2005-03-15 Procédé et catalyseurs pour la conjugaison de doubles liaisons dans les acides gras et les dérivés d'acides gras WO2006101473A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130204022A1 (en) * 2009-10-12 2013-08-08 Elevance Renewable Sciences, Inc. Methods of refining and producing isomerized fatty acid esters and fatty acids from natural oil feedstocks

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4434310A (en) * 1982-01-13 1984-02-28 Chemische Werke Huels Aktiengesellschaft Process for the isomerization of isolated double bonds to conjugated double bonds in optionally substituted cyclooctadienes
WO2001051597A2 (fr) * 2000-01-12 2001-07-19 Her Majesty In Right Of Canada As Represented By The Minister Of Agriculture Procede de preparation commerciale de formes isomeriques preferees d'acides gras conjugues non combines a un ester avec des systemes de solvants contenant des solvants de polyether alcool
US6420577B1 (en) * 1999-12-01 2002-07-16 Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of Agriculture Method for commercial preparation of conjugated linoleic acid
US6479683B1 (en) * 2001-03-06 2002-11-12 Ag Processing Inc Process for conjugating fatty acid esters
EP1526126A1 (fr) * 2003-10-23 2005-04-27 Bioghurt Biogarde GmbH & Co. KG. Procédé pour la préparation de d'esters d'acides gras conjugués, polyinsaturés

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4434310A (en) * 1982-01-13 1984-02-28 Chemische Werke Huels Aktiengesellschaft Process for the isomerization of isolated double bonds to conjugated double bonds in optionally substituted cyclooctadienes
US6420577B1 (en) * 1999-12-01 2002-07-16 Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of Agriculture Method for commercial preparation of conjugated linoleic acid
WO2001051597A2 (fr) * 2000-01-12 2001-07-19 Her Majesty In Right Of Canada As Represented By The Minister Of Agriculture Procede de preparation commerciale de formes isomeriques preferees d'acides gras conjugues non combines a un ester avec des systemes de solvants contenant des solvants de polyether alcool
US6479683B1 (en) * 2001-03-06 2002-11-12 Ag Processing Inc Process for conjugating fatty acid esters
EP1526126A1 (fr) * 2003-10-23 2005-04-27 Bioghurt Biogarde GmbH & Co. KG. Procédé pour la préparation de d'esters d'acides gras conjugués, polyinsaturés

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130204022A1 (en) * 2009-10-12 2013-08-08 Elevance Renewable Sciences, Inc. Methods of refining and producing isomerized fatty acid esters and fatty acids from natural oil feedstocks
US9382502B2 (en) * 2009-10-12 2016-07-05 Elevance Renewable Sciences, Inc. Methods of refining and producing isomerized fatty acid esters and fatty acids from natural oil feedstocks

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