WO1994005420A1 - Ru-Sn HETEROPOLYNUCLEAR COMPLEX AND PROCESS FOR PRODUCING ACETIC ACID OR METHYL ACETATE BY USING THE SAME - Google Patents
Ru-Sn HETEROPOLYNUCLEAR COMPLEX AND PROCESS FOR PRODUCING ACETIC ACID OR METHYL ACETATE BY USING THE SAME Download PDFInfo
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- WO1994005420A1 WO1994005420A1 PCT/JP1993/001282 JP9301282W WO9405420A1 WO 1994005420 A1 WO1994005420 A1 WO 1994005420A1 JP 9301282 W JP9301282 W JP 9301282W WO 9405420 A1 WO9405420 A1 WO 9405420A1
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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
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
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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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
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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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
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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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
- C07C53/08—Acetic acid
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- 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
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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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
Definitions
- the present invention provides a novel Ru—Sn heteronuclear polynuclear complex useful as a catalyst, and uses, as a starting material, methanol, methyl formate or formaldehyde as a starting material.
- the present invention relates to a method for producing acetic acid and methyl or methyl acetate.
- Acetic acid is industrially produced in large quantities by a methanol carbonylation method, a so-called monsant method.
- methanol and carbon monoxide are subjected to a liquid phase reaction in the presence of a catalyst system containing a rhodium catalyst and an iodide.
- the solubility of the cluster is as low as about 0.05 mM. Moreover, since the heteronuclear cluster is an anion complex, The solubility of the cluster is even lower not only in the acetic acid formed but also in normal organic solvents. Therefore, the catalyst concentration cannot be increased, and therefore the reaction rate cannot be increased. In addition, formaldehyde is generated by the dehydrogenation reaction of methanol, and the metal in the catalyst is reduced and precipitated by the formaldehyde, so that the catalyst is lost within a short time. It can be useful. In particular, when the reaction is performed at a high temperature, the catalyst is easily deactivated.
- an object of the present invention is to provide a novel catalyst having high catalytic activity and useful for obtaining acetic acid and / or methyl acetate from methanol.
- Another object of the present invention is to provide a method for producing acetic acid and Z or methyl acetate from methanol in a one-step reaction, in which the catalyst can be used at a high concentration and the catalytic activity is maintained during the reaction. It is to provide
- Still another object of the present invention is to provide a method for producing acetic acid and / or methyl or methyl acetate at a high reaction rate in the presence of a highly active catalyst.
- the present inventor has made intensive studies to achieve the above object. As a result, a novel Ru-Sn heteronuclear polynuclear complex is found, and the above object can be achieved by reacting methanol, methyl formate or formaldehyde using this catalyst. And were found. Then, based on these findings, the present invention has been completed.
- the present invention relates to a catalyst represented by the following general formula (10).
- Y represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkoxy group
- L represents a ligand.
- m is an integer of 1 to 6
- n is an integer of 0 to 5
- m + n is an integer of 1 to 6.
- n in the general formula (1) is 1 or 2
- n is an integer of 1 to 5
- m + n is 5 or 6, or in the general formula (1)
- Y in the formula is a halogen atom, and more preferably a fluorine atom.
- the catalyst represented by the general formula (10) may be a catalyst represented by the following general formula (1).
- Y represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkoxy group
- L represents a ligand.
- m is an integer of 1 to 6
- n is an integer of 0 to 5
- m + n is an integer of 1 to 6.
- the general formula (1) are, C p R u (S n C l 3) (L *) ⁇ wherein, C p is consequent Rope printer Jefferies sulfonyl group, L 'is PP h 3, A s P h 3 or 1 2 ⁇ 1,2-bis (diphenylphosphino) pulp bread (here, Ph represents a fluorine group). ⁇ Is not indicated. ]
- L in the general formula (10) is a ⁇ -gen atom, a hydrogen atom, a coordinating carbon-containing ligand, a coordinating nitrogen-containing ligand, a coordinating oxygen-containing coordination.
- One or more ligands selected from the group consisting of a ligand, a coordinating phosphorus-containing ligand, a coordinating sulfur-containing ligand and a coordinating arsenic-containing ligand, or a halogen atom, Hydrogen atom, coordination Carbon-containing ligands (excluding CO), coordinating nitrogen-containing ligands, coordinating oxygen-containing ligands (excluding CO), coordinating phosphorus-containing ligands, coordinating sulfur-containing ligands It is also preferable to use one or more ligands selected from the group consisting of ligands and coordinating arsenic-containing ligands.
- L is a halogen atom
- PR ⁇ 3 R 'is an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, or an aryl group
- P (OR ") a R b represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group
- 1/2 bis (shows a aryloxy group or an aryl alkoxy group)
- Those which are one or more ligands selected from the group consisting of diphenylphosphino) alkane) and a monovalent cyclic genenyl group are preferred.
- a catalyst represented by the following general formula (2) is preferable.
- X and Y ′ are the same or different and are a halogen atom
- R b represents an alkenyl group, a cycloalkyl group, an aryl group or an aryl group.
- c is 0 or 1
- m is 1 or 2
- c + m is 2
- d is 3 when c ′ is 0, and d is 4 when c ′ is S 1.
- a catalyst represented by the following general formula (30), (40) or (50) is preferable.
- Z is a monovalent cyclic genenyl group
- Y is a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkoxy group
- R "> is an alkyl group.
- ZR u (dppa) (S n Y 3) (4 0) [ wherein, Z is a monovalent cyclic Jeniru group, Y is a halogen atom, an alkyl group, consequent Russia alkyl group, ⁇ Re Ichirumoto, ⁇ La A rualkyl group or an alkoxy group, and dppa is a bis (diphenylphosphono) bisanolecane. ], One ZR u (PP h 3 ) 2 (S n Y 3 ) (50)
- Z represents a monovalent cyclic genenyl group
- Y represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkoxy group
- Ph represents a hydrogen atom. Represents a nyl group.
- a catalyst represented by the following general formula (30), (4) or (5) is preferable.
- Z is a monovalent cyclic genenyl group
- Y is a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkoxy group
- R b is an alkyl group.
- Z is a monovalent cyclic genenyl group
- Y is a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkoxy group
- dppa is a bis (diph Unil Phosphoino) Indicates an alkane.
- the general formula (4) is, C p R u (1, 2 - dppp) (S n C 1 3) ⁇ wherein, C p is consequent Ropenta Jeniru group, 1 2 dppp 1 2- bis (diphenyl Enylphosphino) Indicates propane. ⁇ Is not indicated. ],
- Z is a monovalent cyclic genenyl group
- Y is a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkoxy group
- Ph is phenyl.
- the general formula (5) is, C p R u (PP h 3) 2 (S n C 1 3) ⁇ wherein, C p is consequent Ropenta Jeniru group, P h denotes the full We group. ⁇ Is not indicated.
- the most preferred catalyst is one in which Z in the general formulas (30), (40), (50), (4), and (5) is a cyclopentenyl group.
- the present invention uses, as a starting material, at least one compound selected from the group consisting of methanol, methyl formate and formaldehyde as a starting material. And a method for producing acetic acid and z or methyl acetate.
- formaldehyde includes a polymer of formaldehyde such as paraformaldehyde equivalent thereto.
- the catalyst according to the present invention is a Ru—Sn heteronuclear polynuclear complex represented by the following general formula (10).
- Y represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkoxy group
- L represents a ligand.
- m is an integer of 1 to 6
- n is an integer of 0 to 5
- m + n is an integer of 1 to 6.
- n in the general formula (1) is 1 or 2
- II is an integer of 1 to 5
- m + n is 5 or 6
- the catalyst represented by the general formula (10) may be a catalyst represented by the following general formula (1).
- Y represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkoxy group
- L represents a ligand.
- m is an integer from 1 to 6
- n is an integer from 0 to 5
- m + ⁇ is an integer from 1 to 6.
- the general formula (1) are, C p R u (S n C l 3) (L ') 2 ⁇ wherein, C p is consequent Rope down evening Jeniru group, L' is PP h 3, A s P h 3 or 1/2 ⁇ 1,2—bis (diphenylphosphino) pulp bread (here, Ph represents a fluorine group).
- the halogen atom represented by Y includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- Preferred halogen atoms are chlorine atoms or fluorine atoms.
- Y may be an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkoxy group.
- the ligand represented by L includes a halogen atom, a hydrogen atom, a coordinating carbon-containing ligand, a coordinating nitrogen-containing ligand, and a coordinating oxygen.
- Ligands, coordinating phosphorus-containing ligands, coordinating sulfur-containing ligands and coordinating arsenic-containing ligands include a halogen atom, a hydrogen atom, a coordinating carbon-containing ligand, a coordinating nitrogen-containing ligand, and a coordinating oxygen.
- the ligand will be described more specifically.
- the halogen atom as a ligand is the same as the halogen atom represented by Y, but a preferred halogen atom is a chlorine atom.
- Examples of the coordinating oxygen-containing ligand according to the present invention include H 20 , alcohols such as aliphatic alcohols and aromatic alcohols, aliphatic ethers and aromatic ethers, and the like. Ethers, hydroxyion, and alkoxydion.
- R is an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkoxy group
- 1,2-bis (diphenylphosphino) ethane (1, 2-dppe)
- 1,3-bis (diphenylphosphino) propane (1,3-dppp)
- 1,4-bis (diphenylphosphino) butane (1, And bis (diphenylphosphino) alkanes such as 4-dppb), ie, bidentate phosphines.
- Examples of the coordinating ligand containing a ligand in the present invention include RSR and RSH (R is an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group) And the like.
- examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isopropyl group. And a pentyl group and a hexyl group.
- Cycloalkyl groups include cyclopentyl, cyclohexyl, cyclooctyl and the like.
- the aryl group includes a fuunyl group, a naphthyl group and the like.
- Examples of the aralkyl group include a benzyl group, a phenyl group, and a benzylhydryl group.
- the alkoxy group includes an alkoxy group corresponding to the alkyl group, for example, Examples include a toxic group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a pentyloxy group, and a hexyloxy group.
- X and Y ' are the same or different and each represents a halogen atom
- Rb represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
- c is 0 or 1
- m is 1 or 2
- c + m is 2
- d is 3 when c is 0, and d is 4 when c is 1.
- halogen atom, alkyl group, cycloalkyl group, aryl group, aralkyl group and the like in the above formula (2) are the same as those in the general formula (10).
- Preferred substituents R 6 include an alkyl group having 1 to 4 carbon atoms, particularly an alkyl group having 1 to 3 carbon atoms, particularly a methyl group.
- the compound represented by the general formula (2) that is, as a good Ri
- Specific examples of the complex for example, [R u C 1 (S n C 1 3) ⁇ P (0 CH 3) 3 ⁇ s [R u (S n C 1 3) 2 ⁇ P (0 CH 3) 3 ⁇ 3] , and the like.
- Examples of the solvent used for producing the complex represented by the general formula (2) include methanol and ethanol. ° Neusoft. 0 -nor, n-butanol, isobutanol, t-butanol, sec—alcohols such as butanol; hexane, heptane, octa Aliphatic hydrocarbons such as cyclohexene; aromatic hydrocarbons such as benzene, toluene and xylene; dichloromethane and tricyclone Halogenated hydrocarbons such as rometan, carbon tetrachloride, and ethylene chloride; nitro compounds such as nitromethane, nitroethane, and nitrobenzene; acetonitrile Trityl compounds such as tril, propionitrile and benzonitrile; ethers such as Jethyl ether, dimethoxetane, and tetrahydrofuran; acetone; Ketones such as
- the resulting Ru—Sn heteronuclear polynuclear complex represented by the general formula (2) can be purified by a conventional purification method such as a recrystallization method.
- catalysts according to the present invention a series of compounds represented by the following general formulas (30), (40), (50), (4) or (5), that is, Ru—Sn heteronuclear polynuclear. Complexes are also suitable.
- ZR u ⁇ P (OR b ) 3 ⁇ 2 (SnY 3 ) (30) wherein Z is a monovalent cyclic genenyl group, Y is a halogen atom, an alkyl group, a cycloalkyl group, R represents a reel group, an aralkyl group or an alkoxy group, and R represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. ], ZR u (dppa) (S n Y,) (4 0)
- Z is a monovalent cyclic genenyl group
- Y is a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkoxy group
- dppa is a bis ( Indicates diphenylphosphino) alkane.
- Z represents a monovalent cyclic diphenyl group
- Y represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkoxy group
- Ph represents a phenyl group.
- Z is a monovalent cyclic genenyl group
- Y is a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl.
- dppa represents a bis (diphenylphosphino) alkane.
- the general formula (4) is, C p R u (1, 2 - dppp) (S n C 1 s) ⁇ wherein, C p is consequent Ropenta Jeniru group, 1, 2 dppe is 1, 2-bis (Diphenylphosphino) Indicates propane. ⁇ Is not indicated. ],
- Z represents a monovalent cyclic genenyl group
- Y represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkoxy group
- Ph represents a phenyl group.
- the general formula (5) is, C p R u (PP h 3) 2 (S n C 1 3) ⁇ wherein, C p is consequent Ropenta Jeniru group, P h denotes a Tilia two Le group. ⁇ Is not indicated.
- the group, aranoalkyl group, 1,2-bis (diphenylphosphino) alkane and the like are the same as those in the general formula (10).
- Specific examples of the compound represented by the general formula (40) include CpRu (1,2-dppe) (SnF,), CpRu (1,2-dppe) ( S n C 1 s ) (wherein, C p represents cyclopentenyl group, and 1,2-dppe represents 1,2-bis (diphenylphosphino) ethane) And the like.
- This reaction is carried out in a suitable solvent, for example, at room temperature to reflux temperature with stirring.
- Examples of the solvent used in this reaction include the same solvents as used in the production of the compound represented by the general formula (2).
- the produced complex can be purified by a purification method such as recrystallization.
- the present invention uses, as a starting material, one or more compounds selected from the group consisting of methanol, methyl formate and formaldehyde as a starting material, and performs the reaction in the presence of the catalyst of the present invention.
- the present invention relates to a method for producing acetic acid and / or methyl acetate.
- a catalyst represented by the general formula (10) is used as the catalyst represented by the general formula (10), and the catalyst is reacted in the presence of the catalyst. It is better to respond.
- the catalyst represented by the general formula (10) used in the method for producing acetic acid and / or methyl acetate according to the present invention includes the general formulas (2), (30) and (40) ) And (50) are preferred, and the catalysts represented by the general formulas (2), (30), (4) and (5) are particularly preferred.
- the Ru—Sn heteronuclear polynuclear complex of the present invention can be suitably used as a catalyst for converting methanol, methyl formate, (para) formaldehyde and the like to acetic acid or methyl acetate. it can.
- the produced acetic acid further reacts with the starting material, methanol, to form methyl acetate. Therefore, by reducing the proportion of methanol in the reaction system, the production of methyl acetate can be suppressed, and acetic acid can be produced efficiently.
- methyl formate / methyl formate which is a compound useful as a precursor of acetic acid or methyl acetate, can be synthesized from methanol, methyl formate, (para) formaldehyde, and the like. Therefore, the method of the present invention can be used as a method for producing methyl formate and z or methylal by appropriately selecting reaction conditions.
- the reaction to produce methylal from methanol and formaldehyde is thought to proceed as follows.
- a feature of the production method of the present invention is that at least one component selected from methanol, methyl formate and formaldehyde is reacted with the Ru-Sn heteronuclear polynuclear complex as a catalyst. It is in the point to let.
- the heteronuclear polynuclear compound of Ru_Sn that is, the above-described Ru_Sn heteronuclear polynuclear complex may be directly used as a solid catalyst in the reaction. However, in order to further enhance the catalytic activity, it is supported on a carrier. It is preferable to use it.
- the carrier examples include activated carbon, silica, alumina, clay minerals such as silica-alumina and zeolite, copper oxide, bentonite, magnesia, silica, and the like.
- Inorganic carriers such as magnesium, titania and zirconia; and organic carriers such as ion exchange resins and chelating resins.
- inorganic carriers such as activated carbon, silica, alumina, zeolite, copper oxide, titania, and zirconia; and organic carriers such as ion-exchange resins and chelate resins
- Carriers containing at least one selected from the group are preferred.
- Preferred carriers include those that exhibit heat resistance up to temperatures higher than the reaction temperature.
- the catalyst supported on the carrier can be prepared by a conventional method such as a sedimentation method, an impregnation method, or an ion exchange method.
- the supported amount of the catalyst can be selected widely within a range that does not decrease the production efficiency of acetic acid and methyl acetate.
- 0.1 to 200 parts by weight, preferably 1 to 100 parts by weight of the carrier is used. 1100 parts by weight, more preferably 5 to 80 parts by weight.
- the shape of the solid catalyst may be any of powder, granule, pellet, rod, ellipse, and sphere.
- methyl formate is mainly isomerized to acetic acid in the presence of the catalyst.
- the produced acetic acid is ester-exchanged by a large amount of methyl formate, and is usually obtained as methyl acetate.
- formaldehyde is converted to acetic acid and methyl acetate in the presence of the catalyst.
- precursors of acetic acid such as methyl formate and methylal are by-produced depending on the reaction conditions.
- the formaldehyde includes, in addition to formaldehyde and paraformaldehyde, compounds that form formaldehyde under the reaction conditions, such as trioxane.
- reaction component that is, as a starting material, methanol, methyl formate, and formaldehyde may be used alone, or two or more of them may be used in combination.
- the selectivity of the reaction varies greatly depending on the type of catalyst and the reaction conditions such as the reaction temperature. Therefore, acetic acid or methyl acetate can be obtained with a high selectivity by appropriately selecting the reaction conditions.
- a by-product precursor of acetic acid such as methyl formate or methylal can be converted to acetic acid or methyl acetate as a target substance.
- the conversion can also increase the selectivity of acetic acid or methyl acetate.
- the reaction can be carried out by any of a liquid phase method and a gas phase method.
- the catalyst is characterized in that it is soluble in an organic solvent. Therefore, the catalyst is particularly useful for a liquid phase reaction as a homogeneous catalyst.
- a reaction component that is, a starting material itself or an intermediate product of the reaction may be used as a solvent, or a solvent inert to the reaction may be used.
- Solvents used in the liquid phase reaction include nitrometan, nitrone, and nitrovene.
- Nitrile compounds such as acetylene nitrile, propionitrile, benzonitrile, etc .; dimethyl compounds such as getyl ether, dimethoxetane, tetrahydro, etc.
- Ethers such as furan; ketones such as acetate, methylethyl ketone and cyclohexanone; carboxylic acids such as acetic acid; esters such as methyl acetate and dimethyl acetate; Protonic polar solvents such as dimethylformamide, dimethylacetamide, and dimethylsulfoxide; dichloromethane, trichloromethane, carbon tetrachloride, polyethylene chloride Halogenated hydrocarbons such as hexane; heptane, heptane, octane, etc .; aliphatic hydrocarbons; cycloaliphatic hydrocarbons such as mouth hexane; benzene, toluene, xylene Any aromatic hydrocarbon; and a mixed solvent thereof are exemplified.
- the concentration of the catalyst in the reaction solution i.e., the mixture of the raw materials and the solvent, can be appropriately selected depending on the solubility of the complex catalyst and the degree of catalytic activity, but is usually from 0.001 to 500 mM, preferably. Is about 0.01 to about 100 mM.
- the Ru—Sn heteronuclear polynuclear complex used in the production method of the present invention has high solubility in the reaction components, that is, the starting compound such as methanol and the organic compound such as acetic acid as the target compound. In the inventive method, the catalyst concentration can be increased, and therefore the reaction rate can be increased.
- the liquid phase reaction can be performed at a reaction temperature of, for example, about 0 to 300 ° C. (preferably, about 30 to 200 ° C.).
- the reaction is performed using nitrogen, helium, argon, or the like.
- the reaction can be carried out at normal pressure or under pressure in an atmosphere of an inert gas
- the reaction may be carried out batchwise or continuously, eg, methanol per mole of complex.
- the ratio of the raw material components can be appropriately selected within a range in which the production efficiency of acetic acid and methyl acetate does not decrease, and is, for example, about 0.1 to 100 mol, and preferably about 1 to 100 mol. .
- the dehydrogenation reaction of methanol in the gas phase is carried out, for example, at about 20 to 400 ° (:, preferably about 50 to 300. (: about.
- the reaction may be performed at normal pressure or under an atmosphere of an inert gas such as helium gas, argon gas, etc.
- the reaction may be performed batchwise or continuously.
- the ratio of methanol to complex is acetic acid and It may be appropriately selected as long as the production efficiency of methyl and methyl acetate does not decrease.
- the ratio of the raw material to 1 mol of the complex is, for example, about 0.1 to 10000 mol, preferably about 10 to 10000 mol.
- the supply amount of the raw material to 1 mol of the complex may be in a wide range where the production efficiency of acetic acid and methyl acetate is not reduced, for example, from 0.001 to 100 mol / mol. Minutes, preferably from about 0.01 to about 100 mol z.
- any of the conventional methods for example, a reaction method using a fixed bed or a fluidized bed, a reactive distillation method, and the like can be adopted.
- the catalyst comprising a Ru-Sn heteronuclear polynuclear complex used in the production method of the present invention has high solubility in an organic solvent, and is capable of converting methanol, methyl formate, and formaldehyde to acetic acid and acetic acid or acetic acid. It has catalytic ability to convert to methyl. Therefore, the catalyst is useful for producing acetic acid or methyl acetate in a one-stage reaction using methanol or the like as a starting material.
- the Ru_Sn heteronuclear polynuclear complex is used as a catalyst, the catalyst concentration in the reaction system can be increased, and high catalytic activity can be obtained for a long time. Since it can be maintained over a long period of time, it is possible to produce acetate or methyl acetate in a single-step reaction from methanol, methyl formate, and formaldehyde power.
- FIG. 1 is a graph showing the relationship between the reaction time and the catalyst turnover number in Examples 12 and 13.
- Example 1 Obtained in Example 1 0 [C p R u ( 1, 2-dppe) (S n C 1 3)] 3. except using 2 mg (4. 0 ⁇ mo 1 ), as in Example 1 2 The reaction was carried out. As a result, methyl acetate was produced with a catalyst turnover number of 11, a production rate of 0.053%, and a selectivity of 100%.
- Example 1 [C p R u ⁇ P (0 M e) 2 (S n C 1 3)] 2. except using 6 mg (4. 0 ⁇ mo 1), as in Example 1 2 The reaction was performed in the same manner. As a result, methyl acetate was produced with a catalyst turnover number of 7.5, a production rate of 0.036%, and a selectivity of 100%.
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EP93919636A EP0631814A4 (en) | 1992-09-10 | 1993-09-09 | HETEROPOLYNUCLEAR COMPLEX Ru-Sn AND METHOD USING THE SAME TO PRODUCE ACETIC ACID OR METHYL ACETATE. |
US08/211,050 US5414110A (en) | 1992-09-10 | 1993-09-09 | Ru-Sn hetero-polynuclear complex and process for producing acetic acid or methyl acetate by using the same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP26973792 | 1992-09-10 | ||
JP4/269737 | 1992-09-10 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1994005420A1 true WO1994005420A1 (en) | 1994-03-17 |
Family
ID=17476462
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1993/001282 WO1994005420A1 (en) | 1992-09-10 | 1993-09-09 | Ru-Sn HETEROPOLYNUCLEAR COMPLEX AND PROCESS FOR PRODUCING ACETIC ACID OR METHYL ACETATE BY USING THE SAME |
Country Status (3)
Country | Link |
---|---|
US (1) | US5414110A (ja) |
EP (1) | EP0631814A4 (ja) |
WO (1) | WO1994005420A1 (ja) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5441291A (en) * | 1977-09-09 | 1979-04-02 | Sagami Chem Res Center | Cluster fixed substance, production thereof and catalyst |
JPS5564533A (en) * | 1978-10-31 | 1980-05-15 | Rhone Poulenc Ind | Manufacture of acetic acid or mixture of acetic acid and methyl acetate |
JPH01294643A (ja) * | 1988-05-20 | 1989-11-28 | Daicel Chem Ind Ltd | 含酸素化合物の製造方法 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3975415A (en) * | 1975-05-05 | 1976-08-17 | E. I. Du Pont De Nemours And Company | Organotin complexes of platinum and palladium |
US4484002A (en) * | 1982-01-13 | 1984-11-20 | Texaco Inc. | Process for producing methyl acetate from methanol and carbon monoxide using a novel catalyst system |
JPS60162787A (ja) * | 1984-01-31 | 1985-08-24 | Tdk Corp | 電解用電極 |
EP0503618A1 (en) * | 1991-03-15 | 1992-09-16 | Ube Industries, Ltd. | Method of producing carbonic acid diester |
JPH0515786A (ja) * | 1991-07-11 | 1993-01-26 | Chiyoda Corp | 酢酸及び酢酸メチル合成用触媒 |
FR2682949B1 (fr) * | 1991-10-24 | 1993-12-17 | Rhone Poulenc Chimie | Procede de synthese d'aldehydes. |
-
1993
- 1993-09-09 US US08/211,050 patent/US5414110A/en not_active Expired - Fee Related
- 1993-09-09 WO PCT/JP1993/001282 patent/WO1994005420A1/ja not_active Application Discontinuation
- 1993-09-09 EP EP93919636A patent/EP0631814A4/en not_active Withdrawn
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5441291A (en) * | 1977-09-09 | 1979-04-02 | Sagami Chem Res Center | Cluster fixed substance, production thereof and catalyst |
JPS5564533A (en) * | 1978-10-31 | 1980-05-15 | Rhone Poulenc Ind | Manufacture of acetic acid or mixture of acetic acid and methyl acetate |
JPH01294643A (ja) * | 1988-05-20 | 1989-11-28 | Daicel Chem Ind Ltd | 含酸素化合物の製造方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP0631814A4 * |
Also Published As
Publication number | Publication date |
---|---|
EP0631814A4 (en) | 1995-04-19 |
US5414110A (en) | 1995-05-09 |
EP0631814A1 (en) | 1995-01-04 |
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