WO2009133846A1 - Procédé de production d’ester alkylique d’acide gras et catalyseur pour la production de ce dernier - Google Patents

Procédé de production d’ester alkylique d’acide gras et catalyseur pour la production de ce dernier Download PDF

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WO2009133846A1
WO2009133846A1 PCT/JP2009/058268 JP2009058268W WO2009133846A1 WO 2009133846 A1 WO2009133846 A1 WO 2009133846A1 JP 2009058268 W JP2009058268 W JP 2009058268W WO 2009133846 A1 WO2009133846 A1 WO 2009133846A1
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fatty acid
carbonate
catalyst
acid alkyl
alkyl ester
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PCT/JP2009/058268
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English (en)
Japanese (ja)
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公寿 福永
晶子 西田
友里恵 岑
昌平 福田
公一 柏木
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国立大学法人山口大学
宇部興産株式会社
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Priority to JP2010510115A priority Critical patent/JPWO2009133846A1/ja
Publication of WO2009133846A1 publication Critical patent/WO2009133846A1/fr

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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
    • B01J31/0239—Quaternary ammonium compounds
    • 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
    • B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
    • 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
    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • C—CHEMISTRY; METALLURGY
    • 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
    • C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
    • B01J2231/4288—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using O nucleophiles, e.g. alcohols, carboxylates, esters

Definitions

  • the present invention relates to a method for producing fatty acid alkyl ester useful as a raw material for producing soap, a synthetic raw material such as higher alcohol, and the like, and a catalyst for producing fatty acid alkyl ester.
  • Fatty acid alkyl esters are widely used as raw materials for producing soaps, synthetic raw materials such as higher alcohols and surfactants, and as fuels.
  • fatty acid glycerides and methanol are alkali metal hydroxides such as sodium hydroxide and potassium hydroxide.
  • transesterification in the presence of an alkali metal catalyst such as alkali metal alcoholates such as sodium methylate, sodium ethylate and the like (Patent Document 1).
  • the method of using an alkyl carbonate instead of methanol is known, and it can manufacture by performing transesterification in the presence of the said alkali metal catalyst (patent documents 2 and 3). It is also known that fatty acid methyl esters obtained by these methods, or mixtures containing fatty acid methyl esters can be used as fuel.
  • the alkali metal used as the catalyst is dissolved in a mixture containing the produced fatty acid alkyl ester.
  • this alkali metal remains and is used as a fuel for a diesel engine, it is accumulated as a deposit on the metal part of the fuel system parts, and the fuel flow rate is reduced to cause a reduction in output and deterioration of exhaust gas. For this reason, in order to remove an alkali metal, several water-washing processes are needed separately, and there exists a problem that the problem of wastewater treatment and manufacturing cost become high.
  • an object of the present invention is to provide a manufacturing method of fatty acid alkyl ester which can manufacture fatty acid alkyl ester with a high yield, without using an alkali metal catalyst, and a catalyst for manufacturing fatty acid alkyl ester.
  • the present inventors have achieved high yield without using an alkali metal catalyst by using an organic base carbonate catalyst as a catalyst for producing fatty acid alkyl ester.
  • fatty acid alkyl esters can be produced. That is, the present invention is to produce a fatty acid alkyl ester by reacting a triglyceride represented by Chemical Formula 7 with an alkyl carbonate represented by Chemical Formula 8 or an alcohol represented by Chemical Formula 9 in the presence of an organic base carbonate. It is a manufacturing method of fatty acid alkyl ester characterized by the above.
  • a fatty acid alkyl ester used in producing a fatty acid alkyl ester by reacting a triglyceride represented by Chemical Formula 7 with an alkyl carbonate represented by Chemical Formula 8 or an alcohol represented by Chemical Formula 9
  • the catalyst is characterized in that an organic base carbonate is a main component.
  • the present invention it is possible to provide a method for producing a fatty acid alkyl ester capable of producing a fatty acid alkyl ester with a high yield without using an alkali metal catalyst, and a catalyst for producing a fatty acid alkyl ester. it can. More specifically, when an alcohol is used, the washing process can be simplified because the alkali metal does not dissolve. When alkyl carbonate is used, the reaction can be carried out at normal pressure.
  • the triglyceride represented by Chemical Formula 7 is one having R 1 , R 2 and R 3 containing 6 to 24 carbon atoms
  • R 1 , R 2 and R 3 may be saturated aliphatic or mono-, di- or tri-unsaturated aliphatic.
  • R 1 , R 2 and R 3 may contain a hydroxy group.
  • triglycerides various ones such as those contained in natural fats and oils such as vegetable oils and animal oils and those chemically synthesized can be used, and biomass is particularly preferable.
  • the triglyceride may be refined, or unrefined one such as vegetable oil or animal oil may be used directly.
  • vegetable oil and animal oil fish oil, animal oil such as beef tallow and pork fat, safflower oil, sunflower oil, linseed oil, soybean (soybean oil), rapeseed oil, cottonseed oil, olive oil, palm oil, corn oil,
  • vegetable oils such as sesame oil, castor oil and rice oil.
  • These fats and oils may use only 1 type, and may mix and use 2 or more types.
  • these oils and fats may be waste oils (waste oil) such as tempura oil.
  • Alkyl carbonate represented by formula 8 may be one R 4 and R 5 are to be an alkyl group having 1 to 24 carbon atoms, even number of carbon atoms in R 4 and R 5 are the same, or different good.
  • alkyl carbonates symmetrical carbonates such as dimethyl carbonate (dimethyl carbonate), diethyl carbonate (diethyl carbonate) and dipropyl carbonate, asymmetric carbonates such as methyl ethyl carbonate, methyl propyl carbonate and ethyl propyl carbonate, etc. may be used. Is preferred, and dimethyl carbonate is particularly preferred.
  • the alcohol represented by Chemical Formula 9 may be any alcohol as long as R 4 is an alkyl group having 1 to 24 carbon atoms.
  • R 4 is an alkyl group having 1 to 24 carbon atoms.
  • a primary alcohol such as methanol, ethanol, propanol and butanol
  • a secondary alcohol such as isopropanol and sec-butanol
  • a tertiary alcohol such as tert-butanol
  • methanol and ethanol Primary alcohols are particularly preferred.
  • a fatty acid alkyl ester represented by Chemical Formulas 10 to 15 can be obtained.
  • a triglyceride represented by Chemical Formula 7 is reacted with an alcohol represented by Chemical Formula 9
  • fatty acid alkyl esters represented by Chemical Formulas 10 to 12 can be obtained.
  • R 1 to R 5 are the same as Chemical Formulas 7 to 9.
  • R 4 and R 5 are in this range, fatty acid alkyl esters represented by Chemical Formulas 10 to 15 obtained by transesterification can be favorably used for various applications.
  • R 4 and R 5 are more than this, the viscosity becomes high and the volatility becomes low, which is not preferable.
  • the transesterification reaction can be carried out under conditions such as closed and high temperature conditions, and the temperature conditions are preferably carried out at 50 ° C. or higher.
  • the temperature condition is excessively lower than 50 ° C., the yield of fatty acid alkyl ester decreases.
  • a more preferable temperature range is 50 to 100 ° C.
  • the organic base carbonate bis quaternary ammonium carbonate comprising an organic base and carbonic acid, or quaternary comprising an organic base and monoalkyl carbonic acid Ammonium monoalkyl carbonate.
  • organic base alkylamines, pyridine, pyridines such as 4-N, N-dimethylaminopyridine, aniline, anilines such as N, N-dimethylaniline, imidazoles, imidazolines, pyrazoles, pyrazolines, Pyrroles, pyrrolines, 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] undec-7-ene and the like.
  • organic base carbonate include bisquaternary ammonium carbonate shown in Chemical formula 16 and quaternary ammonium monoalkyl carbonate shown in Chemical formula 17.
  • R 1 to R 3 each independently represent a hydrocarbon group having 1 to 12 carbon atoms or a hydrocarbon group having a hydroxyl group
  • R 4 has 1 to 24 carbon atoms, preferably carbon
  • R 1 to R 3 contain a hydrocarbon group having 1 to 12 carbon atoms, and any two or three of R 1 to R 3 are It forms a heterocycle via a carbon, oxygen or nitrogen atom.
  • Specific examples in which three of R 1 to R 3 form a heterocyclic ring through a carbon or nitrogen atom include the following Chemical Formula 18 and Chemical Formula 19 and the like.
  • organic base carbonates include bisquaternary ammonium carbonates and quaternary ammonium monoalkylcarbonates. Specifically, bistriethylmethylammonium carbonate, bis (1-methyl-4-dimethylaminopyridinium) Carbonate, bis (1,1-dimethylpyrrolidinium) carbonate, bis (4,4-dimethylmorpholinium) carbonate, bis (1-ethyl-1-methylpyrrolidinium) carbonate, triethylmethylammonium Monomethyl carbonate, 1-methyl-4- (N, N-dimethylamino) pyridinium monomethyl carbonate, N, N-dimethylmorpholine monomethyl carbonate, N, N-dimethylaminopiperidinium monomethyl carbonate, tetramethyl ammonium Monomethyl carbonate, diethyldimethyl ammonium monomethyl carbonate, Li octylmethylammonium monomethyl carbonate, triethyl methyl ammonium monomethyl carbonate, and N- (2-hydroxy
  • Bis quaternary ammonium carbonates and quaternary ammonium monoalkyl carbonates can be obtained by known methods.
  • bis quaternary ammonium carbonate is a mixture of 1 mol of dialkyl carbonate and 1 mol or more of organic amine in a stirring autoclave at a reaction temperature of 100 to 180 ° C. and a reaction pressure of 0.5 to 3 MPaG (G represents a gauge pressure)
  • the reaction time may be 1 hour or more
  • the quaternary ammonium monoalkyl carbonate may be a mixture of 1 mol of dialkyl carbonate, 0.5 mol or more of organic amine, and 1 mol or more of methanol. It can be obtained by reacting at 100 to 180 ° C., a reaction pressure of 0.5 to 3 MPaG, and a reaction time of 1 hour or more.
  • organic base carbonate those separated from the produced fatty acid alkyl ester and the alkyl carbonate represented by Chemical Formula 2 or the alcohol represented by Chemical Formula 3 may be used after the reaction, and repeated use Can.
  • the fatty acid alkyl ester represented by Chemical Formulas 10 to 15 produced can be used for various applications such as fuel, high quality soap and raw material of higher alcohol.
  • waste oil or the like is used as the raw material triglyceride in the fatty acid alkyl ester production process according to the present invention
  • a known filter such as a filter press
  • known filter media such as activated clay, diatomaceous earth, zeolite, activated carbon, acid clay, bentonite, silica adsorbent, silica-alumina compound, calcium carbonate, bone ash, perlite, cellulose, magnesia, alumina, gypsum and the like. it can.
  • the amount of the filter medium can be appropriately set according to the type of waste oil, the amount of impurities contained in the waste oil, and the like.
  • the filtration is carried out using a known filter medium of The amount of the filter medium varies depending on the condition of the produced fuel but is 1 to 20% by mass of the produced fuel.
  • one or more acids and water selected from the group consisting of phosphoric acid, phosphorous acid, hypophosphoric acid, hypophosphorous acid, pyrophosphoric acid, metaphosphoric acid, sulfuric acid, pyrosulfuric acid, carbon dioxide gas, hydrochloric acid, acetic acid, oxalic acid and water Add, mix, neutralize and wash. After the washing water is allowed to stand and separated, the organic layer is heated under reduced pressure to distill off excess alkyl carbonate and water.
  • the method for producing a fatty acid alkyl ester and the catalyst for producing a fatty acid alkyl ester according to the present invention since an alkali metal catalyst is not used, several separate water washing steps are not required to remove an alkali metal. As only one washing step or a filtration step using activated white earth treatment etc., the problem of waste water treatment and the problem of increase in manufacturing cost do not occur.
  • the method of producing fatty acid alkyl ester by transesterification reaction of fatty acid glyceride and alkyl carbonate using conventional alkali metal catalyst has low catalytic activity of alkali metal, and therefore, the boiling point of alkyl carbonate or more in high pressure reactor such as autoclave The reaction is carried out at a temperature higher than atmospheric pressure. In addition, 10 to 40% by mass of fatty acid ester of glycerin carbonate is contained. When the reaction is performed near the boiling point of the alkyl carbonate under atmospheric pressure conditions, 25.6 mass% of fatty acid ester of fatty acid alkyl carbonate is contained (Patent Document 3).
  • the organic base carbonate has high catalytic activity so that the reaction can be carried out under normal pressure, and the content of fatty acid ester of glycerin carbonate is It can be reduced as much as possible.
  • the fatty acid ester of fatty acid alkyl carbonate can be suppressed to 5 mass% or less.
  • the reaction can be allowed to proceed under mild conditions of lower temperature and atmospheric pressure by using an organic base carbonate having high activity than in the case of using a conventional alkali metal catalyst, and further The content of fatty acid ester of fatty acid alkyl carbonate can be reduced, which is very useful.
  • a fatty acid alkyl ester having a small acid value and a favorable color tone can be obtained by using an organic base carbonate as a catalyst.
  • a rice oil consisting of the constituent fatty acid contents shown in Tables 1 and 2 (as a raw material triglyceride) (a specific gravity of 0.917 ml / g, saponification, manufactured by Tsukino Food Industry Co., Ltd.) Value (molecular weight): 898, acid value: 0.36 mg-KOH / g, palm oil (manufactured by Fuji Oil Co., Ltd., iodine value: 51.3 g / 100-g, acid value: 0.18 mg-KOH / g g) was used.
  • the chemical compositions of soybean oil, rapeseed oil and waste cooking oil used in the examples are shown in Tables 3 to 5, respectively.
  • bistriethylmethylammonium carbonate was produced as an example of the catalyst for fatty acid alkyl ester production according to the present invention. That is, a rotor is placed in a 300 ml sus autoclave (made by pressure resistant glass industry), and 100 g (1.1 mol) of dimethyl carbonate (made by Ube Industries, Ltd.) and 50.1 g (0. 5 mol) were charged and reacted for 8 hours at a reaction temperature of 130 ° C. After separating and collecting the lower layer, excess dimethyl carbonate and triethylamine were distilled off under reduced pressure to obtain 34.5 g of the objective bistriethylmethylammonium carbonate. At this time, the pressure was 0.3 MPa G. Hereinafter, this was designated as catalyst A.
  • the 1 H-NMR and 13 C-NMR analyzes of the catalyst A were as shown in Table 6.
  • Example 1 fatty acid alkyl ester was produced using catalyst A.
  • 10.0 g (11.14 mmol) of rice oil, 5.0 g (137.0 mmol) of methanol (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.32 g (1.1 mmol) of catalyst A were weighed and added to a 50 ml reaction vessel.
  • the rotor was rotated by a magnet stirrer under nitrogen flow, and the reaction was carried out at a reaction temperature of 60 ° C. and atmospheric pressure for 2 hours.
  • methanol was distilled off under reduced pressure.
  • the upper layer was washed with 5 ml of purified water. After the lower aqueous layer was separated and removed, the water was distilled off at 70 ° C. under reduced pressure to obtain 10.0 g of a fatty acid methyl ester as an object.
  • the obtained target substance was subjected to qualitative and quantitative analysis using gas chromatography (manufactured by Shimadzu Corporation) and TLC-FID method (Mitsubishi Chemical Yatron MK-5 type) using Chromatorod III.
  • TLC-FID method using Chromatorod III The content rate of the fatty acid alkyl ester after the reaction was measured by thin chromatography with Iatroscan (TLC-FID) (Mitsubishi Chemical Yatron MK-5 type). The measurement conditions are shown in Table 7.
  • the chroma rod is an SIII silica gel sintered thin layer bar, the pore diameter is 60 angstroms, and the particle size is 5 ⁇ m.
  • the yield of fatty acid methyl ester was the total of methyl stearate, methyl palmitate, methyl oleate, methyl linolenate and methyl linoleate.
  • the retention time of the peaks of methyl stearate, methyl palmitate, methyl oleate, methyl linolenate and methyl linoleate was determined with a standard product (methyl stearate, methyl palmitate: 0.07 to 0.130 min, oleic acid Methyl, methyl linolenate, methyl linoleate: 0.150 to 0.250 min).
  • the content of fatty acid methyl ester was 97.6% by mass. Further, as a result of quantitative analysis of elements by inductively coupled plasma emission spectrometry (ICP-AES), metal ions such as Na and K were not detected.
  • ICP-AES inductively coupled plasma emission spectrometry
  • Example 2 Next, as Example 2, fatty acid alkyl ester was produced using catalyst A.
  • 10.0 g (11.14 mmol) of rice oil, 10.0 g (111.0 mmol) of dimethyl carbonate (manufactured by Ube Industries, Ltd.) and 0.32 g (1.1 mmol) of catalyst A are weighed and added to a 50 ml reaction vessel.
  • the rotor was rotated by a magnet stirrer under a nitrogen stream, and reaction was performed at a reaction temperature of 90 ° C. and atmospheric pressure for 1.5 hours. After cooling to room temperature, dimethyl carbonate was distilled off under reduced pressure.
  • the catalyst A accumulated in the lower layer was separated and removed to obtain 11.1 g of a mixture containing fatty acid methyl ester as a main component.
  • the target product thus obtained was subjected to quantitative analysis using gas chromatography (manufactured by Shimadzu Corporation). As a result, the content of fatty acid methyl ester was 89.6% by mass. The conversion rate of the raw rice oil was 100%. In addition, fatty acid ester of glycerine carbonate was not detected.
  • Example 3 a fatty acid alkyl ester was produced using catalyst A.
  • 10.0 g (11.14 mmol) of rice oil and 10.0 g (111.0 mmol) of dimethyl carbonate (manufactured by Ube Industries, Ltd.) were weighed and added to a 50 ml reaction vessel.
  • the catalyst A separated and collected in Example 2 was added to this, and the rotor was rotated by a magnet stirrer under a nitrogen stream to carry out a reaction at a reaction temperature of 90 ° C. and atmospheric pressure for 2 hours. After cooling to room temperature, dimethyl carbonate was distilled off under reduced pressure.
  • the catalyst A accumulated in the lower layer was separated and removed to obtain 11.2 g of a mixture mainly composed of fatty acid methyl ester.
  • the obtained target substance was subjected to qualitative and quantitative analysis using gas chromatography (manufactured by Shimadzu Corporation). As a result, the content of fatty acid methyl ester was 89.1% by mass. The conversion rate of the raw rice oil was 100%. In addition, fatty acid ester of glycerine carbonate was not detected.
  • catalyst B The 1 H-NMR and 13 C-NMR analyzes of catalyst B were as shown in Table 8. It was street.
  • Example 4 a fatty acid alkyl ester was produced using catalyst B.
  • 10.0 g (11.14 mmol) of rice oil, 5.0 g (137.0 mmol) of methanol (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.38 g (1.17 mmol) of catalyst B were weighed and added to a 50 ml reaction vessel.
  • the rotor was rotated by a magnet stirrer under nitrogen flow, and reaction was performed at a reaction temperature of 60 ° C. and atmospheric pressure for 2 hours.
  • methanol was distilled off under reduced pressure.
  • the upper layer was washed with 5 ml of purified water. After the lower aqueous layer was separated and removed, the water was distilled off under reduced pressure at 70 ° C. to obtain 9.9 g of a fatty acid methyl ester as an object.
  • the obtained target substance was subjected to qualitative and quantitative analysis using gas chromatography (manufactured by Shimadzu Corporation) and TLC-FID method (Mitsubishi Chemical Yatron MK-5 type) using Chromatorod III. As a result, the content of fatty acid methyl ester was 96.9% by mass.
  • Example 5 a fatty acid alkyl ester was produced using catalyst B.
  • 10.0 g (11.14 mmol) of rice oil, 12.3 g (137.0 mmol) of dimethyl carbonate (manufactured by Ube Industries, Ltd.) and 0.38 g (1.17 mmol) of catalyst B are weighed and added to a 50 ml reaction vessel. The The rotor was rotated by a magnet stirrer under nitrogen flow, and reaction was performed at a reaction temperature of 90 ° C. and atmospheric pressure for 4 hours. After cooling to room temperature, catalyst B was removed by filtration and dimethyl carbonate was distilled off under reduced pressure. 10.9 g of a mixture containing fatty acid methyl ester as the main component was obtained.
  • the target product thus obtained was subjected to quantitative analysis using gas chromatography (manufactured by Shimadzu Corporation). As a result, the content of fatty acid methyl ester was 94.0% by mass. The conversion rate of the raw rice oil was 100%. In addition, fatty acid ester of glycerine carbonate was not detected.
  • the precipitated solid was filtered, washed with 10 ml of dimethyl carbonate, and dried to obtain 7.4 g of the target bis (1,1-dimethylpyrrolidinium) carbonate.
  • the pressure at this time was 0.3 MPaG.
  • catalyst C The 1 H-NMR and 13 C-NMR analyzes of the catalyst C are as shown in Table 9.
  • Example 6 a catalyst C was used to produce a fatty acid alkyl ester.
  • 10.0 g (11.14 mmol) of rice oil, 5.0 g (137.0 mmol) of methanol (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.30 g (1.17 mmol) of catalyst C were weighed and added to a 50 ml reaction vessel.
  • the rotor was rotated by a magnet stirrer under a nitrogen stream, and reaction was performed at a reaction temperature of 60 ° C. and atmospheric pressure for 3 hours. After cooling to room temperature, methanol was distilled off under reduced pressure.
  • the upper layer was washed with 5 ml of purified water. After the lower aqueous layer was separated and removed, the water was distilled off under reduced pressure at 70 ° C. to obtain 9.9 g of a fatty acid methyl ester as an object.
  • the obtained target substance was subjected to qualitative and quantitative analysis using gas chromatography (manufactured by Shimadzu Corporation) and TLC-FID method (Mitsubishi Chemical Yatron MK-5 type) using Chromatorod III. As a result, the content of fatty acid methyl ester was 98.2% by mass.
  • Example 7 a fatty acid alkyl ester was produced using catalyst C.
  • 10.0 g (11.14 mmol) of rice oil, 12.3 g (137.0 mmol) of dimethyl carbonate (manufactured by Ube Industries, Ltd.) and 0.30 g (1.17 mmol) of catalyst C are weighed and added to a 50 ml reaction vessel.
  • the rotor was rotated by a magnet stirrer under a nitrogen stream, and the reaction was carried out at a reaction temperature of 90 ° C. and atmospheric pressure for 6 hours.
  • catalyst C was removed by filtration and dimethyl carbonate was distilled off under reduced pressure.
  • the catalyst C accumulated in the lower layer was separated and removed to obtain 10.8 g of a mixture containing fatty acid methyl ester as a main component.
  • the target product thus obtained was subjected to quantitative analysis using gas chromatography (manufactured by Shimadzu Corporation). As a result, the content of fatty acid methyl ester was 94.8% by mass. The conversion rate of the raw rice oil was 100%. In addition, fatty acid ester of glycerine carbonate was not detected.
  • Example 8 a catalyst C was used to produce a fatty acid alkyl ester.
  • 10.0 g (11.14 mmol) of rice oil and 10.0 g (111.0 mmol) of dimethyl carbonate (manufactured by Ube Industries, Ltd.) were weighed and added to a 50 ml reaction vessel.
  • the catalyst C separated and recovered in Example 7 was added to this, and the rotor was rotated by a magnet stirrer under a nitrogen stream to carry out a reaction at a reaction temperature of 90 ° C. and atmospheric pressure for 12 hours.
  • catalyst C was removed by filtration and dimethyl carbonate was distilled off under reduced pressure.
  • the catalyst C accumulated in the lower layer was separated and removed to obtain 10.8 g of a mixture containing fatty acid methyl ester as a main component.
  • the obtained target substance was subjected to qualitative and quantitative analysis using gas chromatography (manufactured by Shimadzu Corporation). As a result, the content of fatty acid methyl ester was 93.2% by mass. The conversion rate of the raw rice oil was 100%. In addition, fatty acid ester of glycerine carbonate was not detected.
  • bis (4,4-dimethylmorpholinium) carbonate was produced as an example of the catalyst for fatty acid alkyl ester production according to the present invention.
  • a rotor is placed in a 50 ml sus autoclave (made by pressure resistant glass industry), and 20 g (0.22 mol) of dimethyl carbonate (made by Ube Industries, Ltd.) and N-methylmorpholine (5.0 g made by Wako Pure Chemical Industries, Ltd. 0.05 mol) was charged, and reacted for 8 hours at a reaction temperature of 130 ° C.
  • catalyst D The 1 H-NMR and 13 C-NMR analyzes of catalyst D were as shown in Table 10. Met.
  • Example 9 a fatty acid alkyl ester was produced using catalyst D.
  • 10.0 g (11.14 mmol) of rice oil, 5.0 g (137.0 mmol) of methanol (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.34 g (1.17 mmol) of catalyst D were weighed and added to a 50 ml reaction vessel.
  • the rotor was rotated by a magnet stirrer under nitrogen flow, and reaction was performed at a reaction temperature of 60 ° C. and atmospheric pressure for 2 hours. After cooling to room temperature, methanol was distilled off under reduced pressure.
  • the upper layer was washed with 5 ml of purified water. After the lower aqueous layer was separated and removed, the water was distilled off under reduced pressure at 70 ° C. to obtain 9.9 g of a fatty acid methyl ester as an object.
  • the obtained target substance was subjected to qualitative and quantitative analysis using gas chromatography (manufactured by Shimadzu Corporation) and TLC-FID method (Mitsubishi Chemical Yatron MK-5 type) using Chromatorod III. As a result, the content of fatty acid methyl ester was 97.7% by mass.
  • Example 10 fatty acid alkyl ester was produced using catalyst D.
  • 10.0 g (11.14 mmol) of rice oil in a 50 ml reaction vessel, dimethyl carbonate (Ube Industries G) (137.0 mmol) and catalyst D 0.34 g (1.17 mmol). was weighed out and added.
  • the rotor was rotated by a magnet stirrer under nitrogen flow, and reaction was performed at a reaction temperature of 90 ° C. and atmospheric pressure for 3 hours. After cooling to room temperature, dimethyl carbonate was distilled off under reduced pressure.
  • the catalyst D accumulated in the lower layer was separated and removed to obtain 10.8 g of a mixture mainly composed of fatty acid methyl ester.
  • the target product thus obtained was subjected to quantitative analysis using gas chromatography (manufactured by Shimadzu Corporation). As a result, the content of fatty acid methyl ester was 92.9% by mass. The conversion rate of the raw rice oil was 100%. In addition, fatty acid ester of glycerine carbonate was not detected.
  • catalyst E The 1 H-NMR and 13 C-NMR analyzes of the catalyst E were as shown in Table 11.
  • triethyl methyl ammonium monomethyl carbonate was manufactured as an example of the catalyst for fatty acid alkyl ester manufacture according to the present invention.
  • a 200 ml sus autoclave made by pressure resistant glass industry
  • 67.5 g (0.75 mol) of dimethyl carbonate made by Ube Industries, Ltd.
  • 75.0 g (0.74 mol) of triethylamine made by Wako Pure Chemical Industries, Ltd.
  • 48 g (1.5 mol) of methanol manufactured by Wako Pure Chemical Industries, Ltd.
  • catalyst F The pressure at this time was 2.0 MPa G. Excess dimethyl carbonate, triethylamine and methanol were depressurized. After distilling off the solvent, 98.5 g of the target triethylmethylammonium monomethyl carbonate was obtained, which is hereinafter referred to as catalyst F.
  • the 1 H-NMR and 13 C-NMR analyzes of the catalyst F are as shown in Table 12. there were.
  • Example 11 a fatty acid alkyl ester was produced using catalyst F.
  • 15.0 g (16.7 mmol) of soybean oil, 6.0 g (187.5 mmol) of methanol and 0.32 g (1.5 mmol) of catalyst F were weighed and added to a 50 ml reaction vessel. The reaction was performed at a reaction temperature of 60 ° C. for 3 hours under a nitrogen stream. After cooling to room temperature, methanol was distilled off under reduced pressure. After separating and removing the lower glycerin layer, the upper layer was washed with 5 ml of purified water. After the lower aqueous layer was separated and removed, the water content was distilled off at 70 ° C. under reduced pressure to obtain 14.9 g of a fatty acid methyl ester as a desired product.
  • Example 12 a fatty acid alkyl ester was produced using catalyst F.
  • 15.0 g (16.7 mmol) of soybean oil, 7.0 g (111.0 mmol) of dimethyl carbonate and 0.32 g (1.5 mmol) of catalyst F were weighed and added to a 50 ml reaction vessel. The reaction was carried out at a reaction temperature of 90 ° C. for 6 hours under a nitrogen stream. After cooling to room temperature, dimethyl carbonate was distilled off under reduced pressure. The brown layer containing the catalyst F accumulated in the lower layer was separated and removed to obtain 16.1 g of a mixture mainly composed of fatty acid methyl ester.
  • dimethyl carbonate Ube Industries, Ltd. 9.0 g (0.1 mol), 4- (N, N-dimethyl) aminopyridine (Wako Pure) as a raw material in a 200 ml sus autoclave (made by pressure glass industry) as a raw material 12.2 g (0.1 mol) of pharmaceuticals and 6.4 g (0.2 mol) of methanol (manufactured by Wako Pure Chemical Industries, Ltd.) were charged and reacted for 3 hours at a reaction temperature of 110 ° C. The pressure at this time was 2.1 MPaG.
  • catalyst G 1-methyl-4- (N) 17.0 g of, N-dimethylamino) pyridinium monomethyl carbonate was obtained, which is hereinafter referred to as catalyst G.
  • the 1 H-NMR and 13 C-NMR analyzes of the catalyst G are as shown in Table 13.
  • Example 13 a catalyst G was used to produce a fatty acid alkyl ester.
  • 15.0 g (16.7 mmol) of soybean oil, 6.0 g (187.5 mmol) of methanol and 0.32 g (1.5 mmol) of catalyst G were weighed and added to a 50 ml reaction vessel. The reaction was performed at a reaction temperature of 60 ° C. for 3 hours under a nitrogen stream. After cooling to room temperature, methanol was distilled off under reduced pressure. After separating and removing the lower glycerin layer, the upper layer was washed with 5 ml of purified water. After the lower aqueous layer was separated and removed, the water content was distilled off at 70 ° C. under reduced pressure to obtain 14.7 g of a fatty acid methyl ester as an object.
  • Example 14 fatty acid alkyl ester was produced using Catalyst G. First, 15.0 g (16.7 mmol) of soybean oil, 7.0 g (111.0 mmol) of dimethyl carbonate and 0.32 g (1.5 mmol) of catalyst G were weighed and added to a 50 ml reaction vessel. The reaction was carried out at a reaction temperature of 90 ° C. for 6 hours under a nitrogen stream. After cooling to room temperature, dimethyl carbonate was distilled off under reduced pressure. The brown layer containing the catalyst G accumulated in the lower layer was separated and removed to obtain 15.8 g of a mixture mainly composed of fatty acid methyl ester.
  • N, N-dimethylmorpholine monomethyl carbonate was produced as an example of the catalyst for fatty acid alkyl ester production according to the present invention.
  • dimethyl carbonate manufactured by Ube Industries, Ltd.
  • N-methylmorpholine manufactured by Wako Pure Chemical Industries, Ltd.
  • 15.4 g 0.48 mol
  • methanol manufactured by Wako Pure Chemical Industries, Ltd.
  • catalyst H The pressure at this time was 1.9 MPaG. Dimethyl and methanol are distilled off under reduced pressure, then acetone is added and the solid is filtered, washed with acetone and dried under reduced pressure to obtain 40.3 g of the target N, N-dimethylmorpholine monomethyl carbonate. Hereinafter, this is designated as catalyst H.
  • the 1 H-NMR and 13 C-NMR analyzes of the catalyst H are as shown in Table 14.
  • Example 15 fatty acid alkyl ester was produced using catalyst H.
  • 15.0 g (16.7 mmol) of soybean oil, 6.0 g (187.5 mmol) of methanol and 0.32 g (1.5 mmol) of catalyst H were weighed and added to a 50 ml reaction vessel. The reaction was carried out at a reaction temperature of 60 ° C. for 3 hours under a nitrogen stream. After cooling to room temperature, methanol was distilled off under reduced pressure. After separating and removing the lower glycerin layer, the upper layer was washed with 5 ml of purified water. After the lower aqueous layer was separated and removed, the water content was distilled off at 70 ° C. under reduced pressure to obtain 14.5 g of a fatty acid methyl ester as an object.
  • Example 16 fatty acid alkyl ester was produced using catalyst H.
  • 15.0 g (16.7 mmol) of soybean oil, 7.0 g (111.0 mmol) of dimethyl carbonate and 0.32 g (1.5 mmol) of catalyst H were weighed and added to a 50 ml reaction vessel. The reaction was carried out at a reaction temperature of 90 ° C. for 6 hours under a nitrogen stream. After cooling to room temperature, dimethyl carbonate was distilled off under reduced pressure. The brown layer containing the catalyst H accumulated in the lower layer was separated and removed to obtain 15.9 g of a mixture mainly composed of fatty acid methyl ester.
  • N, N-dimethylaminopiperidinium monomethyl carbonate was produced as an example of the catalyst for fatty acid alkyl ester production according to the present invention.
  • dimethyl carbonate manufactured by Ube Industries, Ltd.
  • N-methylpiperidine manufactured by Wako Pure Chemical Industries, Ltd.
  • Catalyst I 0.21 mol) and 14.1 g (0.44 mol) of methanol (manufactured by Wako Pure Chemical Industries, Ltd.) were charged and reacted at a reaction temperature of 120 ° C. for 3 hours. The pressure at this time was 1.9 MPaG. After excess dimethyl carbonate and methanol were distilled off under reduced pressure, acetone was added and the solid was filtered. After washing with acetone, it was dried under reduced pressure to obtain 40.3 g of the target N, N-dimethylaminopiperidinium monomethyl carbonate. Hereinafter, this is referred to as catalyst I.
  • the 1 H-NMR and 13 C-NMR analyzes of Catalyst I are as shown in Table 15.
  • Example 17 a fatty acid alkyl ester was produced using Catalyst I.
  • 15.0 g (16.7 mmol) of soybean oil, 6.0 g (187.5 mmol) of methanol and 0.32 g (1.5 mmol) of catalyst I were weighed and added to a 50 ml reaction vessel. The reaction was carried out at a reaction temperature of 60 ° C. for 3 hours under a nitrogen stream. After cooling to room temperature, methanol was distilled off under reduced pressure. After separating and removing the lower glycerin layer, the upper layer was washed with 5 ml of purified water. After the lower aqueous layer was separated and removed, the water content was distilled off at 70 ° C. under reduced pressure to obtain 14.8 g of a fatty acid methyl ester as a desired product.
  • Example 18 fatty acid alkyl ester was produced using Catalyst I.
  • 15.0 g (16.7 mmol) of soybean oil, 7.0 g (111.0 mmol) of dimethyl carbonate and 0.32 g (1.5 mmol) of catalyst I were weighed and added to a 50 ml reaction vessel. The reaction was carried out at a reaction temperature of 90 ° C. for 6 hours under a nitrogen stream. After cooling to room temperature, dimethyl carbonate was distilled off under reduced pressure. The brown layer containing catalyst I accumulated in the lower layer was separated and removed to obtain 15.4 g of a mixture mainly composed of fatty acid methyl ester.
  • tetramethylammonium monomethyl carbonate was produced as an example of the catalyst for fatty acid alkyl ester production according to the present invention.
  • 26.0 g (0.29 mol) of dimethyl carbonate (manufactured by Ube Industries, Ltd.) as a raw material and 200 g of a 11% solution of dimethylamine in methanol (manufactured by Wako Pure Chemical Industries, Ltd.) were used as a raw material in a 200 ml sus autoclave (manufactured by pressure glass industry). (0.16 mol) was charged and reacted at a reaction temperature of 120 ° C. for 3 hours.
  • Example 19 fatty acid alkyl ester was produced using catalyst J.
  • 15.0 g (16.7 mmol) of soybean oil, 6.0 g (187.5 mmol) of methanol and 0.32 g (1.5 mmol) of catalyst J were weighed and added to a 50 ml reaction vessel. The reaction was carried out at a reaction temperature of 60 ° C. for 3 hours under a nitrogen stream. After cooling to room temperature, methanol was distilled off under reduced pressure. After separating and removing the lower glycerin layer, the upper layer was washed with 5 ml of purified water. After the lower aqueous layer was separated and removed, the water was distilled off at 70 ° C. under reduced pressure to obtain 14.6 g of a fatty acid methyl ester as a target product.
  • diethyldimethylammonium monomethyl carbonate was produced as an example of the catalyst for fatty acid alkyl ester production according to the present invention.
  • a 200 ml sus autoclave made by pressure resistant glass industry
  • 15.8 g (0.17 mol) of dimethyl carbonate manufactured by Ube Industries, Ltd.
  • 12.6 g (0.17 mol) of diethylamine manufactured by Wako Pure Chemical Industries, Ltd.
  • methanol manufactured by Wako Pure Chemical Industries, Ltd.
  • catalyst K was diethyldimethylammonium monomethyl carbonate.
  • Example 20 catalyst K was used to produce fatty acid alkyl ester.
  • 15.0 g (16.7 mmol) of soybean oil, 6.0 g (187.5 mmol) of methanol and 0.32 g (1.5 mmol) of catalyst K were weighed and added to a 50 ml reaction vessel. The reaction was carried out at a reaction temperature of 60 ° C. for 3 hours under a nitrogen stream. After cooling to room temperature, methanol was distilled off under reduced pressure. After separating and removing the lower glycerin layer, the upper layer was washed with 5 ml of purified water. After the lower aqueous layer was separated and removed, the water content was distilled off at 70 ° C. under reduced pressure to obtain 14.8 g of a fatty acid methyl ester as a desired product.
  • trioctyl methyl ammonium monomethyl carbonate was manufactured as an example of the catalyst for fatty acid alkyl ester manufacture according to the present invention.
  • dimethyl carbonate (Ube Industries, Ltd.) 5.8 g (0.07 mol) and trioctylamine (Wako Pure Chemical Industries, Ltd.) 20.3 g (0 kg) were used as raw materials in a 200 ml sus autoclave (made by pressure glass industry).
  • 065 mol) and 4.0 g (0.014 mol) of methanol manufactured by Wako Pure Chemical Industries, Ltd.
  • Catalyst L was trioctylmethylammonium monomethyl carbonate.
  • Example 21 a catalyst L was used to produce a fatty acid alkyl ester.
  • 15.0 g (16.7 mmol) of rapeseed oil, 6.0 g (187.5 mmol) of methanol and 0.32 g (1.5 mmol) of catalyst L were weighed and added to a 50 ml reaction vessel. The reaction was carried out at a reaction temperature of 60 ° C. for 1 hour under a nitrogen stream. After cooling to room temperature, methanol was distilled off under reduced pressure. After standing for 3 hours, the lower glycerin layer was separated and removed to obtain 14.8 g of the target fatty acid methyl ester.
  • N- (2-hydroxyethyl) N, N, N-trimethylammonium monomethyl carbonate was produced as an example of the catalyst for fatty acid alkyl ester production according to the present invention.
  • dimethyl carbonate Ube Industries, Ltd. 25 g (0.28 mol
  • 2-dimethylaminoethanol Wako Pure Chemical Industries 22.6 g (0 g) were used as raw materials in a 200 ml sus autoclave (made by pressure glass industry).
  • Example 22 Next, as Example 22, a catalyst M was used to produce a fatty acid alkyl ester.
  • 15.0 g (16.7 mmol) of rapeseed oil, 6.0 g (187.5 mmol) of methanol and 0.32 g (1.5 mmol) of catalyst M were weighed and added to a 50 ml reaction vessel. The reaction was carried out at a reaction temperature of 60 ° C. for 1 hour under a nitrogen stream. After cooling to room temperature, methanol was distilled off under reduced pressure. After standing for 3 hours, the lower glycerin layer was separated and removed to obtain 14.9 g of a target fatty acid methyl ester.
  • tetramethylammonium monomethyl carbonate was produced as an example of the catalyst for fatty acid alkyl ester production according to the present invention.
  • 36.0 g (0.4 mol) of dimethyl carbonate (Ube Industries, Ltd.) and 80 g (0. 34 mol) was charged and reacted at a reaction temperature of 120 ° C. for 3 hours.
  • the pressure at this time was 0.7 MPaG.
  • 48.5 g of a solid was obtained. This was designated as catalyst N, and from the results of 1 H-NMR analysis shown in Table 20, catalyst N was tetramethylammonium monomethyl carbonate.
  • Example 23 fatty acid alkyl ester was produced using catalyst N.
  • 15.0 g (16.7 mmol) of rapeseed oil, 6.0 g (187.5 mmol) of methanol and 0.32 g (1.5 mmol) of catalyst N were weighed and added to a 50 ml reaction vessel. The reaction was carried out at a reaction temperature of 60 ° C. for 3 hours under a nitrogen stream. After cooling to room temperature, methanol was distilled off under reduced pressure. The lower glycerin layer was separated and removed, and then the upper layer was filtered with 2 g of activated clay S1 to obtain 14.1 g of a target fatty acid methyl ester.
  • Example 24 a fatty acid alkyl ester was produced using Catalyst A.
  • 15.0 g (11.14 mmol) of palm oil, 6.0 g (137.0 mmol) of methanol and 0.32 g (1.1 mmol) of catalyst A were weighed and added to a 50 ml reaction vessel.
  • the rotor was rotated by a magnet stirrer, and reaction was performed at a reaction temperature of 60 ° C. for 3 hours. After cooling to room temperature, methanol was distilled off under reduced pressure. After standing for 3 hours, the lower glycerin layer was separated and removed to obtain 14.9 g of a target fatty acid methyl ester.
  • Example 25 catalyst A was used to produce a fatty acid alkyl ester.
  • 15.0 g (11.14 mmol) of waste cooking oil, 6.0 g (137.0 mmol) of methanol and 0.32 g (1.1 mmol) of catalyst A were weighed and added to a 50 ml reaction vessel.
  • the rotor was rotated by a magnet stirrer, and reaction was performed at a reaction temperature of 60 ° C. for 3 hours. After cooling to room temperature, methanol was distilled off under reduced pressure. After standing for 3 hours, the lower glycerin layer was separated and removed to obtain 14.8 g of the target fatty acid methyl ester.

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Abstract

La présente invention a pour objet un procédé de production d’un ester alkylique d’acide gras qui permet sa production avec un rendement élevé à l’aide d’un catalyseur de métal alcalin. L’invention concerne également un catalyseur pour la production d’un ester alkylique d’acide gras. Le procédé de production d’un ester alkylique d’acide gras est caractérisé en ce qu’un ester alkylique d’acide gras est produit en faisant réagir un triglycéride avec un carbonate d’alkyle ou un alcool en présence d’une base organique carbonate. Le catalyseur pour la production d’un ester alkylique d’acide gras est caractérisé en ce qu’il est principalement composé d’une base organique carbonate.
PCT/JP2009/058268 2008-04-28 2009-04-27 Procédé de production d’ester alkylique d’acide gras et catalyseur pour la production de ce dernier WO2009133846A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012106982A (ja) * 2010-10-22 2012-06-07 Nagoya Univ エステル製造方法
WO2016186005A1 (fr) * 2015-05-21 2016-11-24 株式会社 東芝 Catalyseur réducteur et réacteur chimique
JP2021501808A (ja) * 2017-09-14 2021-01-21 ファーメンタ バイオテク リミテッドＦｅｒｍｅｎｔａ Ｂｉｏｔｅｃｈ Ｌｉｍｉｔｅｄ 魚油廃棄物残渣からのコレステロール抽出の改良された方法
CN114014775A (zh) * 2021-11-26 2022-02-08 华东理工大学 一种功能化表面活性离子液体及其制备方法和应用

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US20060058540A1 (en) * 2004-09-14 2006-03-16 Siegfried Peter Process for the transesterification of fats and oils of biological origin by means of alcoholysis using special carbonic acid salts
WO2007114441A1 (fr) * 2006-04-04 2007-10-11 Tohoku Techno Arch Co., Ltd. Procede et appareil de production d'ester d'acide gras et catalyseur
WO2008053825A1 (fr) * 2006-10-31 2008-05-08 Yamaguchi University Procédé de fabrication d'un ester alkylique d'acide gras

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060058540A1 (en) * 2004-09-14 2006-03-16 Siegfried Peter Process for the transesterification of fats and oils of biological origin by means of alcoholysis using special carbonic acid salts
WO2007114441A1 (fr) * 2006-04-04 2007-10-11 Tohoku Techno Arch Co., Ltd. Procede et appareil de production d'ester d'acide gras et catalyseur
WO2008053825A1 (fr) * 2006-10-31 2008-05-08 Yamaguchi University Procédé de fabrication d'un ester alkylique d'acide gras

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012106982A (ja) * 2010-10-22 2012-06-07 Nagoya Univ エステル製造方法
WO2016186005A1 (fr) * 2015-05-21 2016-11-24 株式会社 東芝 Catalyseur réducteur et réacteur chimique
US10308574B2 (en) 2015-05-21 2019-06-04 Kabushiki Kaisha Toshiba Reduction catalyst and chemical reactor
JP2021501808A (ja) * 2017-09-14 2021-01-21 ファーメンタ バイオテク リミテッドＦｅｒｍｅｎｔａ Ｂｉｏｔｅｃｈ Ｌｉｍｉｔｅｄ 魚油廃棄物残渣からのコレステロール抽出の改良された方法
JP7177081B2 (ja) 2017-09-14 2022-11-22 ファーメンタ バイオテク リミテッド 魚油廃棄物残渣からのコレステロール抽出の改良された方法
CN114014775A (zh) * 2021-11-26 2022-02-08 华东理工大学 一种功能化表面活性离子液体及其制备方法和应用

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