WO2011136903A1 - Procédé de préparation d'acides gras à chaîne ramifiée saturée - Google Patents

Procédé de préparation d'acides gras à chaîne ramifiée saturée Download PDF

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WO2011136903A1
WO2011136903A1 PCT/US2011/031266 US2011031266W WO2011136903A1 WO 2011136903 A1 WO2011136903 A1 WO 2011136903A1 US 2011031266 W US2011031266 W US 2011031266W WO 2011136903 A1 WO2011136903 A1 WO 2011136903A1
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fatty acids
phosphine
catalyst
process according
mixtures
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PCT/US2011/031266
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English (en)
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Helen Ngo
Thomas A. Foglia
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The United States Of America As Represented By The Secretary Of Agriculture
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Priority claimed from US12/767,083 external-priority patent/US20110263884A1/en
Priority claimed from US12/774,347 external-priority patent/US8748641B2/en
Application filed by The United States Of America As Represented By The Secretary Of Agriculture filed Critical The United States Of America As Represented By The Secretary Of Agriculture
Publication of WO2011136903A1 publication Critical patent/WO2011136903A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/36—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by hydrogenation of carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton

Definitions

  • the present invention relates to a process for preparing saturated branched chain fatty acids or alkyl esters thereof involving subjecting unsaturated fatty acids having 10 to 25 carbon atoms, alkyl esters thereof or mixtures thereof to a skeletal isomerization reaction in the presence of water or a lower alcohol at a temperature of about 240°C to about 280°C using a combination of a stericly hindered Lewis base and zeolite as a Bronsted or Lewis acid catalyst, and isolating saturated branched chain fatty acids or alkyl esters thereof or mixtures thereof from the reaction mixture obtained by the skeletal isomerization reaction.
  • the yield of said saturated branched chain fatty acids is >70 wt%.
  • the stericly hindered Lewis base is a tertiary amine or phosphine with linear or branched Ci to C 6 alkyl or phenyl groups attached thereto.
  • polylactide polymers and 1 ,3 -propanediol important intermediates for polymer syntheses, are derived from biomass sugars by fermentation and are cost competitive with petroleum-based materials (Carole, T.M., et al, Applied Biochem. and Biotech., 113-116: 871-885 (2004)).
  • Vegetable oils also are promising candidates as replacemenst for petroleum- based materials since they have excellent lubricity properties (Swern, D., Baily's Industrial Oil and Fat Products, Third Edition, John Wiley & Sons, New York). Although these oils themselves have some commercial use, it is limited due to the presence of double bonds within their fatty acid alkyl chains which lead to oxidative stability problems when used at high temperature. Over the past decades, numerous chemical methods including electrophilic, nucleophilic, oxidative, and metal-catalyzed reactions have been developed that convert the common fatty acids found in natural fats and oils to novel oleochemical compounds that have improved and/or new properties over the starting fatty acids.
  • Saturated branched-chain fatty acid isomers commonly referred to as isostearic acids
  • isostearic acids are derived from unsaturated fats and oils as a mixture of mono-methyl branched fatty acids (2, Figure 1).
  • Such mixtures of fatty acids are of commercial interest because they are liquid at low-temperatures, have good lubricity properties, and have good oxidative stabilities because of their lack of double bonds.
  • Isostearic acid type products are currently used in the formulation of cosmetics, body washes, lubricants and fuel additives, surfactants, soaps, and coatings. Approximately 100 million pounds of these acids are consumed globally each year.
  • sbc-FAs 2 are obtained as coproducts from reactions that predominantly produce dimer fatty acids (6, Figure 1).
  • the typical yields of sbc-FAs 2 are 25-50 wt%, and their isolation and purification from the dimer acid 6 are labor-intensive.
  • New processes that give higher yields and higher selectivity of sbc-FAs at a lower cost and with improved ease of isolation from other coproducts would be highly advantageous; such processes would expand their present use and/or open new outlets for these type of fatty acids.
  • a process for preparing saturated branched chain fatty acids or alkyl esters thereof involving subjecting unsaturated fatty acids having 10 to 25 carbon atoms, alkyl esters thereof or mixtures thereof to a skeletal isomerization reaction in the presence of water or a lower alcohol at a temperature of about 240°C to about 280°C using a combination of a stericly hindered Lewis base and zeolite as a Bronsted or Lewis acid catalyst, and isolating saturated branched chain fatty acids or alkyl esters thereof or mixtures thereof from the reaction mixture obtained by the skeletal
  • the stericly hindered Lewis base is a tertiary amine or phosphine with linear or branched Ci to C 6 alkyl or phenyl groups attached thereto.
  • Figure 1 shows products produced from zeolite-catalyzed isomerization of oleic acid as described herein.
  • the present invention concerns a process for preparing saturated branched- chain fatty acids or alkyl esters thereof.
  • the process involves the steps of subjecting an unsaturated fatty acid or ester having 10 to 25 carbon atoms, or mixtures of unsaturated fatty acids or esters to a skeletal isomerization reaction in the presence of water or a lower alcohol at a temperature of about 240° to about 280°C (e.g., 240°-280°C) using a combination of a sterically hindered Lewis base and a zeolite as a Bronsted or Lewis acid catalyst; the reaction time is generally about 4 to about 8 hours (e.g., 4-8 hours) and the amount of Lewis base utilized is generally about 2.5 wt% to about 20 wt% (e.g., 2.5 wt% to 20 wt%) to zeolite).
  • the isomerized fatty acid mixture is then subjected to hydrogenation to remove remaining double bonds within the fatty acid or ester chains to produce saturated branched-chain fatty acid or ester mixtures.
  • the zeolite catalysts used in the process has a linear pore structure with a pore size that is small enough to retard oligimerization of unsaturated fatty acids or esters but sufficiently large enough to allow diffusion of the fatty acids or alkyl esters thereof into the zeolite structure where fatty acid or ester chain isomerization is catalyzed,
  • the branched chain fatty acids or alkyl esters or mixtures thereof are then isolated from the reaction mixture and the isomerized fatty acid or ester or mixtures thereof hydrogenated to remove residual unsaturation yield the desired saturated branched-chain fatty acid or ester mixture.
  • the yield of the saturated branched-chain fatty acids is typically >70 wt%.
  • the sterically hindered Lewis base is, for example, a tertiary amine or phosphine with linear or branched Ci to C 6 alkyl or phenyl groups attached thereto.
  • both branched chain fatty acids and alkyl esters thereof can be produced because both can be isomerized simultaneously.
  • the isomerization of unsaturated fatty acid case is included in the present invention.
  • the unsaturated fatty acid used as the starting material is generally a fatty acid having unsaturated bonds and a total carbon number of 10 to 25, preferably a total carbon number of 16 to 22. Considering industrial applications, it is preferable that the major component of the starting material has an average carbon number of 18. Unsaturated fatty acids having a total carbon number of this range are useful as starting materials for the synthesis of sbc-FAs for use in cosmetic bases, fiber treating agents, lubricating oil additives, etc.
  • any unsaturated fatty acid may be used as long as one or more such bonds are present in the molecule.
  • the number of unsaturated bonds is generally 1 to 3, preferably 1.
  • Octadecenoic acid is the most preferable.
  • the presence of an unsaturated bond in the molecule causes the formation of a carbocation as an intermediate, thereby facilitating the skeletal isomerization reaction. If a saturated fatty acid is used in large quantities as a starting material, formation of this intermediate carbocation is hampered, thereby making it difficult for isomerization to proceed.
  • Unsaturated fatty acids include oleic acid, palmitoleic acid, erucic acid, elaidic acid, linoleic acid, linolenic acid, and undecenoic acid, which can be derived from beef tallow, palm oil, safflower oil, sunflower oil, tall oil, rapeseed oil, soybean oil, or the like.
  • the mixture that may be used as the starting material is a mixture containing two or more of these unsaturated fatty acids, or a mixture containing one or more of these unsaturated fatty acids and one or more saturated fatty acids such as palmitic and stearic acids, various esters of the aforementioned unsaturated fatty acids, and the like.
  • the content of the above-mentioned unsaturated fatty acids is generally not less than about 40% by weight (e.g., not less than 40%> by weight), preferably not less than 80%> by weight (e.g., not less than 80%> by weight) in view of reaction rate and yield.
  • the above- described starting material contains about 40 to about 100% by weight (e.g., 40 to 100% by weight) of octadecenoic acids, such as oleic acid and elaidic acid.
  • Alkyl esters of unsaturated fatty acids having a total carbon number of 10 to 25 used as a starting material are those corresponding to the above-described unsaturated fatty acids. That is, alkyl esters of the unsaturated fatty acids exemplified above are used. Although the alkyl moiety is not subject to limitation as to carbon number, its carbon number is normally 1 to 3, preferably 1. Specific examples of alkyl esters include methyl esters, ethyl esters, propyl esters, and butyl esters of the above-mentioned unsaturated fatty acids, with preference given to methyl esters.
  • a mixture that contains at least one alkyl ester of the above-described fatty acids is used. Specifically, it is a mixture of one or more alkyl esters of these unsaturated fatty acids, or a mixture containing at least one alkyl ester of these unsaturated fatty acids and saturated fatty acids, various esters, etc.
  • the content of alkyl esters of the above-mentioned unsaturated fatty acids is normally not less than about 40% by weight (e.g., not less than 40% by weight), preferably not less than 80%) by weight (e.g., not less than 80%> by weight) in view of reaction rate and yield.
  • the above- described starting material be alkyl esters of unsaturated fatty acids containing about 40 to about 100%) (e.g., 40 to 100%) by weight) by weight of alkyl esters of octadecenoic acid, such as methyl oleate and methyl elaidate, or a mixture thereof.
  • the present invention utilizes a combination of (1) zeolite as a Bronsted or Lewis acid catalyst and (2) a stericly hindered Lewis base.
  • the Lewis base has a molecular size larger than the largest dimension of the open channels of the zeolite; the Lewis base interacts with the external active sites on the surface of the zeolite framework but because of their molecular size have limited access to the active sites within the zeolite channels.
  • Such bases can neutralize the external acidic sites on the surfaces of the zeolite framework but because of their size cannot access the interior acidic sites in the channels.
  • the Lewis base may be an amine, phosphine, triarylphosphine, dialkylarylphosphine, trialkylphosphine, or mixtures thereof.
  • the phosphine may be methylphosphine, butylphosphine, dibutylphosphine, tributylphosphine, phenylphosphine, diphenylphosphine, or mixtures thereof.
  • the triarylphosphine may be triphenylphosphine, diphenylphosphine, tri-p-tolylphosphine, tri(o-tolyl)phosphine, tri-m- tolylphosphine, trixylyl-phosphine, tris(p-ethylphenyl)phosphine, tris(p- methoxyphenyl)phosphine, tris(4-fluorophenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(dimethylamino)phosphine, tris(trimethylsilyl)phosphine, triisopropylphosphine, or mixtures thereof.
  • the dialkylarylphosphine may be di-n-butylphenylphosphine,
  • the trialkylphosphine may be tri-n- butylphosphine, tricyclohexylphosphine, tri-n-octylphosphine, trimethyphosphine,
  • the amine may be dimethylamine, trimethylamine, diethylamine, triethylamine, diisopropylamine, triisopropylamine, triphenylamine, diphenylamine, or mixtures thereof.
  • Zeolite used for the present invention has a linear pore structure of pore size which is small enough to retard dimerization and large enough to allow diffusion of branched chain fatty acids or alkyl esters thereof.
  • Significant by-product formation due to dimerization is undesirable because it results in decreased yield of branched chain fatty acids, etc.
  • insufficient diffusion of branched chain fatty acids, etc. is also undesirable because it results in decreased apparent catalyst activity.
  • the mean pore size of zeolite is normally about about 4 to about 9 Angstroms (e.g., 4 to 9), preferably about 5 to about 8 Angstroms (e.g., 5 to 8), and more preferably about 6 to about 7 Angstroms (e.g., 6 to 7), varying depending on the total carbon number of branched chain fatty acids, etc.
  • the term "linear pore structure" as used herein is a structure wherein pores are formed by at least linear continuous pathways.
  • any zeolite can be used, as long as it meets the above requirements.
  • ferrierite type zeolite and mordenite type zeolite are preferred from the viewpoint of pore size, heat resistance, acid resistance, and acid properties.
  • the former is available only as a synthetic substance; the latter is available both as a natural substance and as a synthetic substance.
  • ferrierite type zeolite as used herein is a zeolite composed of two-dimensional aluminum-silica network structure, with interconnecting channels between the 8-membered-ring (MR) and 10-MR structures (Bekkem, H. V., Introduction to Zeolite Science and Practice, 2nd Edition, Elsevier, New York, NY, 2001, pp.
  • the channels of commercially available Ferrierites typically contain an alkali metal (Na or K) or ammonium (NH 4 ) cation.
  • K-containing Ferrierite with a silica/alumina (Si/Al) molar ratio of 17.5.
  • the mordenite type zeolite the highest in silicon content among naturally- occurring zeolites, is a zeolite composed of oxygen 12-membered ring wherein the pores are formed mainly by tunnel-like pore pathways (Shokubai Koza, Vol. 10, edited by the Catalysis Society of Japan, Kodansha Ltd. (1986)).
  • these zeolites can be synthesized by hydrothermal synthesis (J.C.S., 2158 (1948)), they are also commercially available.
  • a zeolite of the sodium type, or the like may be used in the reaction after being converted into the proton type by ion exchange.
  • the Si/Al molar ratio of zeolite is preferably about 3 to about 300 (e.g., 3 to 300), more preferably about 5 to about 100 (e.g., 2 to 100).
  • the ratio is preferably not less than about 3 (e.g., not less than 3) in view of catalytic activity, and not more than about 300 (e.g., not less than 300) in view of yield.
  • silica/alumina ratio (molar) can easily be determined by atomic absorption photometry. Zeolite may be used in the reaction after a pretreatment by ion-exchange, drying or burning.
  • the reaction is carried out in the presence of water or a lower alcohol.
  • This is to suppress acid anhydride formation due to dehydration or dealcoholation of the starting material. This suppression is attributable to acid point modification of zeolite, such as conversion of Lewis acid point into Bronsted acid point.
  • water when the starting material is unsaturated fatty acids; and an alcohol when the starting material is esters of unsaturated fatty acids.
  • the lower alcohol used is exemplified by alcohols having 1 to 4 carbon atoms. Specifically, methanol, ethanol, propanol, butanol etc. are preferred, with a greater preference given to those having the same alkyl group as that of the starting fatty acid esters to be isomerized.
  • the isomerization reaction step in the present invention is carried out using the above-described starting material, zeolite, etc.
  • the reaction be carried out at about 240° to about 280°C (e.g., 240° to 280°C) in the presence of about 0.1 to about 30 parts by weight (e.g., 0.1 to 30 parts by weight) of zeolite and about 0.5 to about 5 parts by weight (e.g., 0.5 to 5 parts by weight) of water or a lower alcohol, based on about 100 parts by weight (e.g., 100 parts by weight) of the above-described unsaturated fatty acids and/or alkyl esters thereof.
  • the reaction is carried out at about 240° to about 280°C (e.g., 240° to 280°C) in the presence of about 1 to about 20 parts by weight (e.g., 1 to 20 parts by weight) of zeolite and about 1 to about 3 parts by weight (e.g, 1 to 3 parts by weight) of water or a lower alcohol, based on about 100 parts by weight (e.g., 100 parts by weight) of the above-described unsaturated fatty acids and/or alkyl esters thereof.
  • about 1 to about 20 parts by weight e.g., 1 to 20 parts by weight
  • zeolite e.g., 1 to 20 parts by weight
  • water or a lower alcohol e.g., a lower alcohol
  • the reaction may be carried out in a closed system where the reaction pressure is generally about 2 to about 50 kgf/cm 2 (e.g., 2 to 50 kgf/cm 2 ). This is to prevent vaporization of water, alcohols and other low boiling substances in the system including those substances contained in a catalyst.
  • the reaction normally takes about 1 to about 10 hours (e.g., 1 to 10 hours). If this problem is overcome, the reaction time can be shortened to several minutes or even several seconds. Also, continuous reaction becomes possible. Excessively long reaction time tends to cause thermal decomposition, resulting in decreased yield.
  • the reaction apparatus used is preferably an autoclave, because a pressurized reaction system is preferred.
  • the atmosphere in the autoclave is preferably replaced with nitrogen or argon.
  • the product obtained by the above-described isomerization reaction contains branched chain unsaturated fatty acids and/or esters thereof, when the starting material is an ester of an unsaturated fatty acids, in a high yield.
  • the product further contains polymeric fatty acids, such as dimer acids (polymeric fatty acid esters, when the starting material is esters of unsaturated fatty acids).
  • the branched chain fatty acids, etc. thus obtained normally have alkyl side chains of 1 to 4 carbon atoms. They are obtained as a mixture of many isomers with different branching positions.
  • branched chain saturated fatty acids (esters of branched chain saturated fatty acids, when the starting material is esters of unsaturated fatty acids) can be obtained as follows. Namely, removal of catalyst zeolite and polymeric materials by filtration or distillation, the residue is hydrogenated in an autoclave by a known method, such as the method using a hydrogenation catalyst (e.g., nickel or palladium/carbon), to yield a mixture of crude branched chain saturated fatty acids (esters of branched chain fatty acids, when the starting material is esters of unsaturated fatty acids).
  • a hydrogenation catalyst e.g., nickel or palladium/carbon
  • the crude product is purified by removing linear chain components by a known method, such as the compression method, the Emerson method, and the Henkel method (U.S. Pat. No. 2,293,674; U.S. Pat. No. 2,421,157; U.S. Pat. No. 2,800,493; J. Am. Oil Chem. Soc, 45, 471 (1968)) or recrystallization method, to yield branched chain saturated fatty acids (esters of branched chain saturated fatty acids, when the starting material is esters of unsaturated fatty acids) of high purity.
  • a known method such as the compression method, the Emerson method, and the Henkel method (U.S. Pat. No. 2,293,674; U.S. Pat. No. 2,421,157; U.S. Pat. No. 2,800,493; J. Am. Oil Chem. Soc, 45, 471 (1968)) or recrystallization method, to yield branched chain saturated fatty acids (esters of branched chain
  • the yield of the saturated branched chain fatty acids is generally > about 70 wt% (e.g., ⁇ 70 wt%); preferably > about 71 wt% (e.g., >_1 ⁇ wt%); preferably > about 72 wt% (e.g., ⁇ 72 wt%); preferably > about 73 wt% (e.g., ⁇ 73 wt%); preferably > about 74 wt% (e.g., > 74 wt%); preferably > about 75 wt% (e.g., ⁇ 75 wt%); preferably > about 76 wt% (e.g., ⁇ 76 wt%); preferably > about 77 wt% (e.g., ⁇ 77 wt%); preferably > about 78 wt% (e.g., ⁇ 78 wt%); preferably > about 79 wt% (e.g., ⁇ 79 wt%).
  • the yield of dimers is generally ⁇ about 15 wt% (e.g., ⁇ 15 wt%); preferably ⁇ about 14 wt% (e.g., ⁇ 14 wt%), ⁇ about 13 wt% (e.g., ⁇ 13 wt%), ⁇ about 12 wt% (e.g., ⁇ 12 wt%), ⁇ about 11 wt% (e.g., ⁇ 11 wt%), ⁇ about 10 wt% (e.g., ⁇ 10 wt%), ⁇ about 9 wt% (e.g., ⁇ 9 wt%), ⁇ about 8 wt% (e.g., ⁇ 8 wt%), ⁇ about 7 wt% (e.g., ⁇ 7 wt%), ⁇ about 6 wt% (e.g., ⁇ 6 wt%), ⁇ about 5 wt% (e.g., ⁇ about 14 wt% (e.
  • the oleic acids 1 used in this study were a commercially available material (PrioleneTM 6936: 92.3 wt% oleic (C18: l), 3.1 wt% linoleic (CI 8:2), 0.4 wt% linolenic (C18:3), 4.2 wt% saturated fatty acids); a gift from Croda International Co. (Gouda, The Netherlands)) and a laboratory grade oleic acid (91.2 wt.% C18:l, 6.1 wt.% C18:2, 2.7 wt.%> saturated fatty acids), from Aldrich Chemical (Milwaukee, WI).
  • Triphenylphosphine TPP
  • hydrochloric acid HC1
  • sulfuric acid H 2 SO 4
  • acetone hexane
  • MeOH methanol
  • Mordenite HSZ-640HOA, protonated (H + ), 17.5-19.5 mol/mol Si0 4 /A10 4
  • Zeolite Ferrierite HSZ-720KOA, potassium (K + ), 17.5 mol/mol Si0 4 /A10 4
  • All other reagents used were of the highest purity available from commercial suppliers.
  • K -Ferrierite zeolite was ion-exchanged using the procedure described by Ngo et al. (Ngo, H.L., et al, Eur. J. Lipid Sci. Technol.,108: 214-224 (2007)) but with some parts of the procedure modified.
  • K -Ferrierite zeolite (100g) was triturated with 300mL of IN HCl and lOOmL of deionized water at 55°C for ⁇ 20 h.
  • the proton exchanged K + -zeolite was centrifuged (3000 xg), washed by resuspention in deionized water (500mL x 5).
  • the supernatant tested with pH paper.
  • the pH of the supernatant solution was neutral after the fifth wash.
  • the solid was dried in an oven at 115°C for 20 h. Approximately 90g of white solid was obtained.
  • the ion-exchange treatment converted the K -zeolite into a H - zeolite (the K -zeolite solid does not catalyze the isomerization reaction).
  • the reactor was filled with N 2 to ⁇ 7.03 kgf/cm 2 and then heated to the desired temperature (240°C to 280°C) while mixing the contents.
  • the pressure at the desired temperature was 14 to 28 kgf/cm 2 .
  • the reactor was cooled to room temperature, the pressure was released, and H -Ferr solids were removed by vacuum filtration using hexane and 0.45 ⁇ HA membrane filterTM (Millipore Co, Billerica, MA).
  • reaction liquid was hydrogenated using 5 wt% palladium on carbon (Pressure Chemical Co., Pittsburgh, PA) as catalyst to give a mixture of sbc-FA products.
  • sbc-FAME sbc-fatty acid methyl esters
  • HP Hewlett Packard
  • GC gas chromatography instrument
  • GC-MS HP 5890 GC-mass spectrometry
  • MALDI-ToF matrix-assisted laser desorption/ionization-time of flight
  • NMR nuclear magnetic resonance
  • ICP-AES inductively coupled plasma atomic emission spectroscopy
  • GC was used to determine the weight percent compositions of the crude sbc-FA products ( Figure 1).
  • GC-MS was used to determine the molecular ions of the monomeric C18-components (2, 3, 4 and 5).
  • Mass spectra of the C36- methyl ester dimer 6 were acquired by MALDI-ToF.
  • NMR and ICP-AES were used to determine whether any phosphorous compounds were leached into either the aqueous phase or oil products, respectively.
  • Zeolite Catalyst Regeneration The used H + -Ferr catalyst (2.5g) recovered from the isomerization process was transferred into a 150mL centrifuge flask with IN HC1 (5mL) and deionized water (lOOmL). The suspension was stirred at 55°C for 24 h, cooled to room temperature and centrifuged (3000 x g). The aqueous phase was decanted into a vacuum filtration device with a 0.45 ⁇ HA membrane filter to capture the residual fine solid particles in the aqueous phase that did not settle to the bottom of the flask during centrifugation.
  • the solids in the centrifuge flask were resuspended in deionized water (lOOmL), mixed well, and centrifuged. This step was repeated once more and the supernatant tested with pH paper. The pH of the supernatant solution was neutral after the second wash.
  • the light brown H + -zeolites were dried at 115° C for 20 h before reuse.
  • GC was used to determine the wt% composition of products in the crude isomerized reaction mixtures after hydrogenation and methylation.
  • GC was equipped with a capillary inlet injector (on column mode) and flame ionization detector.
  • the capillary column used was a HP Agilent DB5-HT column (30 m x 0.1 mm x 0.32 ⁇ ) attached to an Alltech Co., (State College, PA) deactivated fused silica guard column (2 m x 0.32 ⁇ ).
  • Helium was the carrier gas set at constant flow of 6 mL/min.
  • the detector temperature was set at 390°C.
  • One of our goals was to modify the zeolite catalyst in such a way so as to retain its activity while also enhancing its selectivity.
  • formation of the dimer acids 6 from oleic acid 1 arises via a bimolecular reaction that is catalyzed primarily by the Bronsted acid sites located on the external surfaces of the H-Ferr particles, whereas formation of the monomer products sbc-FAs 2, hydroxystearic acid 4, and ⁇ -stearolactone 5 was postulated to be catalyzed by all Bronsted acid sites.
  • the stearic acid 3 was also found in the product mixture because of two reasons: 1) 2.7 - 4.2 wt% of 3 was already present in the starting fatty acids and 2) if the reactions gave low conversions of oleic acid, thus hydrogenation of the oleic acid would further enhance the amount of stearic acid 3.
  • Lewis base for example one that was sufficiently bulky enough to be unable to penetrate deeply into the internal zeolite structure, we hypothesized that the acidic sites within the channels of the zeolite would remain active. If this could be accomplished, then such modification would not significantly affect the activity of skeletal isomerization of oleic acid 1 that occurs within the interiors of the zeolite framework.
  • the used zeolite catalyst was then transferred into a centrifuge flask containing dilute hydrochloric acid, heated at 55°C for 24 h, recovered by centrifugation, washed with deionized water, dried in an oven to remove residual water at 115°C for ⁇ 20h, and reused to produce sbc-FA products.
  • the reactions were performed with 5 wt% H-Ferr at 260°C for 4 h. This higher catalyst loading was needed because the reuse reactions were run at shorter reaction times.
  • 7.5 wt% TPP to H-F en- catalyst was added to the reaction mixture to ensure that sufficient TPP was available to coat the external acid sites (Table 3, entry 1).
  • the present invention concerns (in part) the following:
  • a process for preparing saturated branched chain fatty acids or alkyl esters thereof comprising (or consisting essentially of or consisting of) subjecting unsaturated fatty acids having 10 to 25 carbon atoms, alkyl esters thereof or mixtures thereof to a skeletal isomerization reaction in the presence of water or a lower alcohol at a temperature of about 240°C to about 280°C using a combination of a stericly hindered Lewis base and zeolite as a Bronsted or Lewis acid catalyst, and isolating saturated branched chain fatty acids or alkyl esters thereof or mixtures thereof from the reaction mixture obtained by the skeletal isomerization reaction; wherein the yield of said saturated branched chain fatty acids is >70 wt%; wherein said stericly hindered Lewis base is a tertiary amine or phosphine with linear or branched Ci to C 6 alkyl or phenyl groups attached thereto.
  • Lewis base is selected from the group consisting of amine, phosphine, triarylphosphine, dialkylarylphosphine, trialkylphosphine, and mixtures thereof.
  • phosphine is selected from the group consisting of methylphosphine, butylphosphine, dibutylphosphine, tributylphosphine, phenylphosphine, diphenylphosphine, and mixtures thereof.
  • triarylphosphine is selected from the group consisting of triphenylphosphine, diphenylphosphine, tri-p-tolylphosphine, tri(o- tolyl)phosphine, tri-m-tolylphosphine, trixylyl-phosphine, tris(p-ethylphenyl)phosphine, tris(p- methoxyphenyl)phosphine, tris(4-fluorophenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(dimethylamino)phosphine, tris(trimethylsilyl)phosphine, triisopropylphosphine, and mixtures thereof.
  • dialkylarylphosphine is selected from the group consisting of di-n-butylphenylphosphine, dicyclohexylphenylphosphine, and mixtures thereof.
  • trialkylphosphine is selected from the group consisting of tri-n- butylphosphine, tricyclohexylphosphine, tri-n-octylphosphine, trimethyphosphine,
  • triphenylamine diphenylamine, and mixtures thereof.
  • the above process further comprising (or consisting essentially of or consisting of) a step wherein branched unsaturated fatty acids or alkyl esters thereof obtained by the skeletal isomerization reaction are hydrogenated to yield branched saturated fatty acids or alkyl esters thereof.
  • said process further comprises (or consists essentially of or consists of) recycling said catalyst by washing said catalyst with a solvent and heating said catalyst in an acid solution, recovering said catalyst, washing said catalyst with deionized water, and drying said catalyst.
  • said solvent is a polar solvent or non-polar solvent.
  • said catalyst is heated in an acid solution at about 55°C (e.g., 55°C) for about 24 hours (e.g., 24 hours).
  • said catalyst is dried at about 115°C (e.g., 115°C) for about 20 hours (e.g., 20 hours).
  • the process, wherein the recycled catalyst has about 2 to about 5% (e.g., 2 to 5%) loss of activity and selectivity.

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention a pour objet un procédé de préparation d'acides gras à chaîne ramifiée saturée ou de leurs esters d'alkyle impliquant la soumission d'acides gras insaturés contenant 10 à 25 atomes de carbone, de leurs esters d'alkyle et de mélanges de ceux-ci à une réaction d'isomérisation du squelette en présence d'eau ou d'un alcool inférieur à une température d'environ 240 °C à environ 280 °C en utilisant une association de base de Lewis gênée sur le plan stérique et d'un zéolite en tant que catalyseur d'acide de Bronsted ou de Lewis, et l'isolement d'acides gras à chaîne ramifiée saturée ou de leurs esters d'alkyle ou de mélanges de ceux-ci à partir du mélange réactionnel obtenu par la réaction d'isomérisation du squelette. Le rendement desdits acides gras à chaîne ramifiée saturée est ≥ 70 % en poids. La base de Lewis gênée sur le plan stérique est une amine tertiaire ou une phosphine avec des groupes alkyle en C1 à C6 linéaires ou ramifiés ou phényle qui lui sont attachés.
PCT/US2011/031266 2010-04-26 2011-04-05 Procédé de préparation d'acides gras à chaîne ramifiée saturée WO2011136903A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US12/767,083 US20110263884A1 (en) 2010-04-26 2010-04-26 Process for Preparing Saturated Branched Chain Fatty Acids
US12/767,083 2010-04-26
US12/774,347 US8748641B2 (en) 2010-05-05 2010-05-05 Process for preparing saturated branched chain fatty acids
US12/774,347 2010-05-05

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014064418A2 (fr) * 2012-10-25 2014-05-01 Croda International Plc Procédé
US8796480B2 (en) 2011-04-28 2014-08-05 Croda International Plc Process for producing monobranched fatty acids or alkyl esters
WO2015144232A1 (fr) * 2014-03-27 2015-10-01 Amril Ag Catalyseurs et procédés d'isomérisation du squelette des acides gras insaturés
CN110127095A (zh) * 2019-05-09 2019-08-16 承德乾隆醉酒业有限责任公司 一种过滤白酒灌装线产生杂酒的制酒装置及其步骤工艺
WO2020064601A1 (fr) 2018-09-25 2020-04-02 Croda International Plc Catalyseur et son utilisation dans l'isomérisation d'acides gras

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US5026933A (en) * 1987-10-07 1991-06-25 Mobil Oil Corporation Olefin oligomerization with surface modified zeolite catalyst
US5677473A (en) * 1994-05-18 1997-10-14 Kao Corporation Process for the preparation of branched chain fatty acids and alkyl esters thereof
US7119216B2 (en) * 2001-03-26 2006-10-10 Dow Global Technologies Inc. Metathesis of unsaturated fatty acid esters or unsaturated fatty acids with lower olefins
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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8796480B2 (en) 2011-04-28 2014-08-05 Croda International Plc Process for producing monobranched fatty acids or alkyl esters
US8987488B2 (en) 2011-04-28 2015-03-24 Croda International, Plc Process for producing monobranched fatty acids or alkyl esters
WO2014064418A2 (fr) * 2012-10-25 2014-05-01 Croda International Plc Procédé
WO2014064418A3 (fr) * 2012-10-25 2014-08-07 Croda International Plc Procédé
KR20150074125A (ko) * 2012-10-25 2015-07-01 크로다 인터내셔날 피엘씨 모노분지형 지방산 또는 그것의 알킬 에스테르의 제조 방법
JP2016501836A (ja) * 2012-10-25 2016-01-21 クローダ インターナショナル パブリック リミティド カンパニー 単分岐脂肪酸又はそのアルキルエステルの製造方法
US9771543B2 (en) 2012-10-25 2017-09-26 Croda International Plc Process for producing monobranched fatty acids or alkyl esters thereof
KR102055798B1 (ko) * 2012-10-25 2019-12-13 크로다 인터내셔날 피엘씨 모노분지형 지방산 또는 그것의 알킬 에스테르의 제조 방법
WO2015144232A1 (fr) * 2014-03-27 2015-10-01 Amril Ag Catalyseurs et procédés d'isomérisation du squelette des acides gras insaturés
WO2020064601A1 (fr) 2018-09-25 2020-04-02 Croda International Plc Catalyseur et son utilisation dans l'isomérisation d'acides gras
CN110127095A (zh) * 2019-05-09 2019-08-16 承德乾隆醉酒业有限责任公司 一种过滤白酒灌装线产生杂酒的制酒装置及其步骤工艺

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