WO2007094468A1 - メタノール合成用触媒及び当該触媒の製造方法、並びにメタノールの製造方法 - Google Patents
メタノール合成用触媒及び当該触媒の製造方法、並びにメタノールの製造方法 Download PDFInfo
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- WO2007094468A1 WO2007094468A1 PCT/JP2007/052883 JP2007052883W WO2007094468A1 WO 2007094468 A1 WO2007094468 A1 WO 2007094468A1 JP 2007052883 W JP2007052883 W JP 2007052883W WO 2007094468 A1 WO2007094468 A1 WO 2007094468A1
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- Prior art keywords
- catalyst
- methanol
- formate
- alkali metal
- producing
- Prior art date
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 261
- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 32
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- -1 formic acid ester Chemical class 0.000 claims abstract description 52
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 44
- 239000007789 gas Substances 0.000 claims abstract description 34
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 22
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 17
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052802 copper Inorganic materials 0.000 claims abstract description 14
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 14
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 31
- 150000001340 alkali metals Chemical class 0.000 claims description 13
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 13
- 239000011949 solid catalyst Substances 0.000 claims description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 11
- 150000001298 alcohols Chemical class 0.000 claims description 9
- 230000002194 synthesizing effect Effects 0.000 claims description 9
- 238000000975 co-precipitation Methods 0.000 claims description 8
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical group [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 claims description 8
- 230000008859 change Effects 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 150000003138 primary alcohols Chemical class 0.000 claims description 4
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 3
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- SVWLIIFHXFGESG-UHFFFAOYSA-N formic acid;methanol Chemical compound OC.OC=O SVWLIIFHXFGESG-UHFFFAOYSA-N 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 16
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 abstract description 4
- 235000019253 formic acid Nutrition 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 24
- 235000019441 ethanol Nutrition 0.000 description 20
- 239000011734 sodium Substances 0.000 description 16
- 230000007423 decrease Effects 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000036962 time dependent Effects 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000004280 Sodium formate Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 2
- 235000019254 sodium formate Nutrition 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- QUWBSOKSBWAQER-UHFFFAOYSA-N [C].O=C=O Chemical compound [C].O=C=O QUWBSOKSBWAQER-UHFFFAOYSA-N 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- ATZQZZAXOPPAAQ-UHFFFAOYSA-M caesium formate Chemical compound [Cs+].[O-]C=O ATZQZZAXOPPAAQ-UHFFFAOYSA-M 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 238000006713 insertion reaction Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- ZIMBPNXOLRMVGV-UHFFFAOYSA-M rubidium(1+);formate Chemical compound [Rb+].[O-]C=O ZIMBPNXOLRMVGV-UHFFFAOYSA-M 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
Classifications
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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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- 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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
-
- 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
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/349—1,2- or 1,4-additions in combination with further or prior reactions by the same catalyst, i.e. tandem or domino reactions, e.g. hydrogenation or further addition reactions
-
- 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
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
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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
- 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
-
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Definitions
- Methanol synthesis catalyst method for producing the catalyst, and method for producing methanol
- the present invention relates to a catalyst for methanol synthesis, a method for producing the catalyst, and a method for producing methanol. More specifically, the present invention relates to a highly active catalyst and a method for obtaining a product with high efficiency when producing methanol from hydrogen from either carbon monoxide or carbon dioxide and hydrogen.
- the present inventors have so far used one or both of an alkali metal catalyst and an alkaline earth metal catalyst excluding alkali metal alkoxide as a catalyst with a small decrease in activity due to water and carbon dioxide.
- a system that is used in combination with a hydrocracking catalyst has been found (Patent Document 1).
- CuZMn, CuZRe, etc. are described as effective hydrocracking catalysts.
- Cu / MgO showed particularly high activity, but it was also found that there was degradation of activity over time.
- Patent Document 1 Japanese Patent Application Laid-Open No. 2001-862701
- Non-Patent Document 1 J. C. J. Bart et al, Catal. Today, 2, 1 (1987)
- Non-Patent Document 2 Satoshi Oyama, PETROTECH, 18 (1), 27 (1995)
- Non-Patent Document 3 S. Ohyama, Applied Catalysis A: General, 180, 217 (1999) Disclosure of Invention
- the present invention aims to solve the above problems, and even if a small amount of carbon dioxide, water, etc. are mixed in the methanol synthesis raw material gas, the degree of decrease in the activity of the catalyst is low.
- the present invention provides a catalyst capable of synthesizing formate ester and methanol at low temperature and low pressure, a method for producing the catalyst, and a method for synthesizing methanol in a liquid phase using the catalyst.
- a catalyst for synthesizing methanol via a formate ester that reacts in the presence of at least one of carbon monoxide and carbon diacid carbon and a source gas containing hydrogen and an alcohol as a solvent.
- alkali metal catalysts that can be converted to alkali metal formate
- the catalyst for methanol synthesis according to any one of to (4).
- a method for producing methanol by reacting a raw material gas containing at least one of carbon monoxide and carbon dioxide and hydrogen, and in addition to alkali metal formate, Cu, Mg, Na The reaction is carried out in the presence of the contained solid catalyst and alcohol to produce formate ester and methanol, and the produced formate ester is hydrogenated to produce methanol.
- the manufacturing method of methanol which manufactures.
- a source gas containing at least one of carbon monoxide, carbon dioxide, and hydrogen is added to an alkali metal formate in the presence of a solid catalyst containing Cu, Mg, Na, and alcohols.
- a method for producing methanol in which methanol is produced by separating a product obtained by reacting in a reaction system from a reaction system and then hydrogenating a formate ester in the product with a hydrocracking catalyst.
- FIG. 1 is a reaction apparatus for carrying out the low-temperature liquid phase methanol synthesis of the present invention.
- FIG. 2 is a time-dependent change in CO conversion rate in the reaction described in Example 1.
- FIG. 3 is a time-dependent change in CO conversion rate in the reaction described in Comparative Example 1.
- FIG. 4 is a time-dependent change in CO conversion rate in the reaction described in Comparative Example 2.
- the inventors of the present invention have added a catalyst containing Cu, Mg, and Na in addition to alkali metal formate in a semi-batch continuous reaction in which a catalyst and a solvent are charged into a reactor and a raw material gas is supplied.
- a catalyst and a solvent are charged into a reactor and a raw material gas is supplied.
- methanol can be continuously produced by the reaction process shown in FIG.
- semi-batch reactor 2 is charged with a solid catalyst containing Cu, Mg, and Na together with solvent alcohol, and syngas 1 is supplied.
- the product 3 at the outlet of the reactor (ester formate, methanol) and unreacted gas is cooled by cooler 4 and separated into unreacted gas 5 and liquid mixture 6 of formate ester and alcohol.
- the latter is separated into formate ester 8 and methanol 9 in distillation column 7 installed in the next stage.
- the conversion rate is low, it is possible to supply the unreacted gas 5 to the semi-batch reactor 2 again.
- the unreacted gas can be used as a heat source (fuel) Use as
- alkali metal formate examples include potassium formate, sodium formate, cesium formate, rubidium formate and the like.
- use of potassium formate is preferred because the catalytic activity is increased.
- an alkali metal catalyst that can take the form of formate during the reaction may be used without particular limitation.
- Examples of such an alkali metal catalyst include potassium carbonate and potassium methoxide. Can be mentioned. When potassium carbonate is used, it is presumed that it has changed to potassium formate by the reaction shown below. When charged in other forms, it is presumed to change to a stable formate.
- the solid catalyst coexisting with the alkali metal formate or alkali metal catalyst that can be converted to alkali metal formate is specifically CuZMgO ZNa (X is chemically acceptable.
- Cu / MgO ZHCOONa (where X is a chemically acceptable value).
- the Cu / MgO can be prepared by impregnation method, precipitation method, sol-gel method, coprecipitation method, ion exchange method, mixing method.
- the holding method is not particularly limited according to the above-mentioned ordinary method, but good results are easily obtained by the impregnation method or the evaporation to dryness method.
- the amount is not less than the minimum amount that exhibits the effect, and is not particularly limited, but is preferably in the range of 0.1 to 60 mass%, more preferably 1 to 40 mass%, and still more preferably 3 to 30 mass%. Further, sodium formate, sodium carbonate and the like are preferable as the Na salt to be supported. Although Cu / MgO, which does not support Na salt, has high activity,
- the above-mentioned solid catalyst containing Cu, Mg, Na is mainly used for the hydrogenation of the formate ester produced. It shows a catalytic action in the solution, but also shows a catalytic action in the CO insertion reaction into the solvent alcohol.
- the alcohol used in the reaction may be a chain or alicyclic hydrocarbon having a hydroxyl group, phenol and its substitute, and further a thiol and its substitute.
- These alcohols may be any of primary, secondary and tertiary alcohols, but from the viewpoint of reaction efficiency, primary alcohols are preferred, and lower alcohols such as methyl alcohol and ethyl alcohol are most common. It is.
- the reaction can employ a system capable of selecting mild conditions that can be carried out in either the liquid phase or the gas phase.
- the temperature is 70 to 250 ° C.
- the pressure is 3 to: LOO atmospheric pressure is a preferable condition, and more preferably, the temperature is 120 to 200 ° C. and the pressure is 15 to 80 atmospheric pressure.
- Alcohols only need to have such an amount that the reaction proceeds, but more than that can be used as a solvent.
- an organic solvent can be used as appropriate.
- the formic acid ester obtained can be used for the production of methanol as it is, as it can be purified by a conventional method such as distillation. That is, methanol can be produced by hydrogenolysis of formate.
- a hydrocracking catalyst is used for hydrocracking.
- a general hydrocracking catalyst such as Cu, Pt, Ni, Co, Ru, and Pd can be used, but the CuZMgO / Na of the present invention can be used.
- the product obtained in the reaction is distilled from the reaction system by distillation or the like. After separation, it is also possible to obtain methanol by hydrocracking the formate in the product in the presence of a hydrocracking catalyst and hydrogen.
- the activity is low.
- the lower the CO and HO concentrations contained in the raw material gas whose main component is CO as the carbon source the higher the yield. Even if each contains about 1% of methanol, the CO conversion rate and methanol yield are hardly affected. However, if the concentration is higher than that, CO conversion and methanol yield will decrease.
- the raw material for producing methanol is at least one of carbon monoxide and hydrogen, carbon dioxide and hydrogen, and alcohols can be recovered and reused. According to the method of the present invention, even if a small amount of water or carbon dioxide is present in the raw material gas, the decrease in the activity of the catalyst is small.
- CO conversion rate (%) [1 (number of moles of CO recovered after reaction) Z (number of moles of charged CO)] X 100
- Figure 3 shows the change over time.
- the CO conversion rate tended to decrease with time.
- CuZMgO has higher activity than CuZMnO.
- the present invention is for methanol synthesis via a formate ester that reacts in the presence of at least one of carbon monoxide and carbon dioxide carbon and hydrogen and a raw material gas containing alcohol as a solvent.
- the present invention relates to a catalyst for methanol synthesis characterized by containing Cu, Mg, Na in addition to alkali metal formate. According to the methanol synthesis catalyst of the present invention, it is possible to stably synthesize methanol with high efficiency in a continuous reaction at low temperature and low pressure. Further, even if a small amount of water, carbon dioxide, or the like is mixed in the synthesis raw material gas, the degree of decrease in the activity of the catalyst is low, so that methanol can be produced at low cost.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/224,001 US20100228059A1 (en) | 2006-02-17 | 2007-02-16 | Catalyst for Methanol Synthesis and Production Method Thereof, and Method for Producing Methanol |
CA002642387A CA2642387A1 (en) | 2006-02-17 | 2007-02-16 | Catalyst for methanol synthesis and production method thereof, adn method for producing methanol |
EP07714413A EP1987879A4 (en) | 2006-02-17 | 2007-02-16 | METHANOL SYNTHESIS CATALYST, PROCESS FOR PRODUCING SUCH CATALYST, AND PROCESS FOR PRODUCING METHANOL |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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JP2006-041575 | 2006-02-17 | ||
JP2006041575A JP5127145B2 (ja) | 2006-02-17 | 2006-02-17 | メタノール合成用触媒及び当該触媒の製造方法、並びにメタノールの製造方法 |
Publications (1)
Publication Number | Publication Date |
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WO2007094468A1 true WO2007094468A1 (ja) | 2007-08-23 |
Family
ID=38371644
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/JP2007/052883 WO2007094468A1 (ja) | 2006-02-17 | 2007-02-16 | メタノール合成用触媒及び当該触媒の製造方法、並びにメタノールの製造方法 |
Country Status (8)
Country | Link |
---|---|
US (1) | US20100228059A1 (ja) |
EP (1) | EP1987879A4 (ja) |
JP (1) | JP5127145B2 (ja) |
KR (1) | KR20080101918A (ja) |
CN (1) | CN101384362A (ja) |
CA (1) | CA2642387A1 (ja) |
RU (1) | RU2008134236A (ja) |
WO (1) | WO2007094468A1 (ja) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
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JP5626077B2 (ja) * | 2011-03-31 | 2014-11-19 | 新日鐵住金株式会社 | メタノールの製造方法およびメタノール製造用触媒 |
CA3096309C (en) * | 2018-04-06 | 2021-04-20 | Kare Chemical Technologies Inc. | Catalytic conversion of carbon dioxide to methanol |
CN109731596B (zh) * | 2019-01-18 | 2020-07-10 | 厦门大学 | 一种糠醛加氢制糠醇的改性铜基催化剂制备方法 |
CN109759105B (zh) * | 2019-03-08 | 2020-12-08 | 宁夏大学 | 一种甲醇合成催化剂 |
WO2021215408A1 (ja) * | 2020-04-24 | 2021-10-28 | 東京都公立大学法人 | 二酸化炭素還元触媒、及び二酸化炭素還元方法 |
Citations (10)
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JPS5585530A (en) * | 1978-12-19 | 1980-06-27 | Inst Francais Du Petrole | Manufacture of alcohols |
JPS5695137A (en) * | 1979-12-19 | 1981-08-01 | Union Carbide Corp | Manufacture of methanol from synthetic gas by use of palladiummcalcium catalyst |
JPS5998024A (ja) * | 1982-11-29 | 1984-06-06 | Res Assoc Petroleum Alternat Dev<Rapad> | 混合アルコ−ルの合成方法 |
JPS59116238A (ja) * | 1982-08-04 | 1984-07-05 | インペリアル・ケミカル・インダストリ−ズ・ピ−エルシ− | メタノール製造方法 |
JPH06319999A (ja) * | 1993-05-07 | 1994-11-22 | Exxon Res & Eng Co | 一酸化炭素及び水素からイソ−アルコールを合成するための触媒 |
JPH0987217A (ja) * | 1995-09-22 | 1997-03-31 | Tsushosangyosho Kiso Sangyokyokucho | エタノールの製造方法 |
JPH09509881A (ja) * | 1994-03-04 | 1997-10-07 | インペリアル・ケミカル・インダストリーズ・ピーエルシー | 銅触媒 |
WO2001062701A1 (fr) | 2000-02-25 | 2001-08-30 | Nippon Steel Corporation | Procede de preparation d'esters de formate ou de methanol et catalyseur destine a cet effet |
JP2005095872A (ja) * | 2003-08-19 | 2005-04-14 | Nippon Steel Corp | ギ酸エステル及びメタノール合成用触媒とギ酸エステル及びメタノールの製造方法 |
JP2005126427A (ja) * | 2003-09-30 | 2005-05-19 | Nippon Steel Corp | ギ酸エステル及びメタノールの製造方法 |
Family Cites Families (5)
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EP0117944B1 (en) * | 1982-12-13 | 1990-06-20 | Imperial Chemical Industries Plc | Methanol synthesis and catalyst therefor |
US5221652A (en) * | 1991-03-26 | 1993-06-22 | The University Of Pittsburgh | Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite for methanol synthesis |
JP3292989B2 (ja) * | 1991-05-10 | 2002-06-17 | ズードケミー触媒株式会社 | 蟻酸メチル製造用触媒 |
US5663458A (en) * | 1994-12-02 | 1997-09-02 | Sumitomo Chemical Company, Limited. | Process for producing α-phenylethyl alcohol |
CN100402149C (zh) * | 2006-07-07 | 2008-07-16 | 宁夏大学 | 一种浆态相低温合成甲醇的催化剂及其制备方法 |
-
2006
- 2006-02-17 JP JP2006041575A patent/JP5127145B2/ja not_active Expired - Fee Related
-
2007
- 2007-02-16 EP EP07714413A patent/EP1987879A4/en not_active Withdrawn
- 2007-02-16 CA CA002642387A patent/CA2642387A1/en not_active Abandoned
- 2007-02-16 US US12/224,001 patent/US20100228059A1/en not_active Abandoned
- 2007-02-16 WO PCT/JP2007/052883 patent/WO2007094468A1/ja active Application Filing
- 2007-02-16 RU RU2008134236/04A patent/RU2008134236A/ru not_active Application Discontinuation
- 2007-02-16 CN CNA2007800057169A patent/CN101384362A/zh active Pending
- 2007-02-16 KR KR1020087020064A patent/KR20080101918A/ko not_active Application Discontinuation
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS5585530A (en) * | 1978-12-19 | 1980-06-27 | Inst Francais Du Petrole | Manufacture of alcohols |
JPS5695137A (en) * | 1979-12-19 | 1981-08-01 | Union Carbide Corp | Manufacture of methanol from synthetic gas by use of palladiummcalcium catalyst |
JPS59116238A (ja) * | 1982-08-04 | 1984-07-05 | インペリアル・ケミカル・インダストリ−ズ・ピ−エルシ− | メタノール製造方法 |
JPS5998024A (ja) * | 1982-11-29 | 1984-06-06 | Res Assoc Petroleum Alternat Dev<Rapad> | 混合アルコ−ルの合成方法 |
JPH06319999A (ja) * | 1993-05-07 | 1994-11-22 | Exxon Res & Eng Co | 一酸化炭素及び水素からイソ−アルコールを合成するための触媒 |
JPH09509881A (ja) * | 1994-03-04 | 1997-10-07 | インペリアル・ケミカル・インダストリーズ・ピーエルシー | 銅触媒 |
JPH0987217A (ja) * | 1995-09-22 | 1997-03-31 | Tsushosangyosho Kiso Sangyokyokucho | エタノールの製造方法 |
WO2001062701A1 (fr) | 2000-02-25 | 2001-08-30 | Nippon Steel Corporation | Procede de preparation d'esters de formate ou de methanol et catalyseur destine a cet effet |
JP2005095872A (ja) * | 2003-08-19 | 2005-04-14 | Nippon Steel Corp | ギ酸エステル及びメタノール合成用触媒とギ酸エステル及びメタノールの製造方法 |
JP2005126427A (ja) * | 2003-09-30 | 2005-05-19 | Nippon Steel Corp | ギ酸エステル及びメタノールの製造方法 |
Non-Patent Citations (5)
Title |
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ARAKURA Y. ET AL.: "Formic acid esters o Keiyu suru Gosei Gas kara no Teion Methanol Gosei", DAI 85 KAI SHOKUBAI TORONKAI TORONKAI A YOKOSHU, 24 March 2000 (2000-03-24), pages 74, XP003016665 * |
J. C. J. BART ET AL., CATAL. TODAY, vol. 2, 1987, pages 1 |
S. OHYAMA, APPLIED CATALYSIS A: GENERAL, vol. 180, 1999, pages 217 |
See also references of EP1987879A4 |
SEIICHI OHYAMA, PETROTECH, vol. 18, no. 1, 1995, pages 27 |
Also Published As
Publication number | Publication date |
---|---|
EP1987879A4 (en) | 2009-07-29 |
EP1987879A1 (en) | 2008-11-05 |
JP2007216178A (ja) | 2007-08-30 |
KR20080101918A (ko) | 2008-11-21 |
RU2008134236A (ru) | 2010-02-27 |
CN101384362A (zh) | 2009-03-11 |
JP5127145B2 (ja) | 2013-01-23 |
US20100228059A1 (en) | 2010-09-09 |
CA2642387A1 (en) | 2007-08-23 |
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