JPH0751575A - Catalyst for synthesis of acetic acid or methyl acetate and production of acetic acid or methyl acetate - Google Patents

Abstract

PURPOSE:To obtain an Ru-Sn catalyst with improved catalytic activity and with which acetic acid, etc., can be produced by using methanol as a single source by one step reaction by a method wherein the cation in a cation exchanger (e.g. zeolite) is cation-exchanged with a complex contg. a positive valent Ru and the cation exchanger is treated with a bi- or tetra-valent tin compd. CONSTITUTION:The catalyst for synthesis of acetic acid or methyl acetate is obtd. by using a cation exchanger (e.g. zeolite), an Ru complex contg. positive valent Ru carried on the cation exchanger by means of cation exchange (e.g. an Ru ammine complex) and a tin compd. with zero-, bi- or tetra-valence carried on the cation exchanger (e.g. tin (I) halide)). This catalyst exhibits high catalytic activity and acetic acid or methy acetate can be produced with this catalyst by using methanol as a single source by one step reaction. In addition, the high catalytic activity can be kept for a long period and acetic acid or methyl acetate can be prepd. therewith with a high selectivity.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst useful for producing acetic acid or methyl acetate from methanol in a one-step reaction, a process for producing this catalyst, and a process for producing acetic acid or methyl acetate using the above catalyst. .

[0002]

2. Description of the Related Art Acetic acid is a methanol carbonylation method,
It is industrially produced in large quantities by the so-called Monsanto method. In this method, methanol and carbon monoxide are caused to undergo a liquid phase reaction in the presence of a catalyst system containing a rhodium component and an iodide (see, for example, Japanese Patent Publication No. 47-3334).
60-54334, JP-A-60-239434, JP-B-3-38
No. 256).

However, these methods require very expensive rhodium. In addition, additional equipment is required to obtain high-purity carbon monoxide, which may limit the location conditions. Furthermore, the methyl iodide used as iodide corrodes the device. Furthermore, since the above-mentioned reaction is usually carried out in a liquid phase system containing water, a large amount of energy is required to recover the produced acetic acid.

On the other hand, as a catalyst for producing acetic acid and methyl acetate from methanol by a one-step liquid phase reaction, [Ru (S
A heteronuclear cluster (polynuclear compound) of Ru-Sn containing an anion consisting of nCl ₃ ) ₅ L] ^3- (L represents a ligand) has been proposed [J. Chem. Soc., Chem. Commun., 1511-1512 (1990)].

However, the solubility of the above-mentioned heteronuclear cluster in methanol is as small as about 0.05 mM. Moreover, since the heteronuclear cluster is an anion complex, the solubility of the heteronuclear cluster in not only the reaction raw material and acetic acid produced but also a normal organic solvent is further low. for that reason,
The catalyst concentration cannot be increased and the reaction rate becomes low. Further, since formaldehyde is produced by the reaction of methanol, the metal may be reduced and deposited, and the catalyst may be deactivated within a short time. Particularly when the reaction is carried out at a high temperature, the catalyst is easily deactivated.

Since the present inventor produces acetic acid and methyl acetate from methanol by a one-step reaction, Ru represented by [Ru (SnCl ₃ ) ₆ ] ⁴⁻ in a heterogeneous gas phase / solid phase reaction.
It was reported that the (II) -Sn (II) cluster complex is useful [Appl. Catal. 92A , .L1-L5 (1992)]. However, when this cluster complex reacts with methanol at high temperature,
The selectivity of acetic acid and methyl acetate is reduced.

[0007]

The object of the present invention is to further enhance the catalytic activity of the Ru-Sn catalyst described above, and a catalyst capable of producing acetic acid or methyl acetate in a single step reaction with methanol as a single source, and a catalyst thereof. It is to provide a manufacturing method.

Another object of the present invention is to provide a catalyst capable of producing acetic acid or methyl acetate with a high selectivity while maintaining a high catalytic activity for a long period of time, and a method for producing the same.

Still another object of the present invention is to provide a method capable of producing acetic acid or methyl acetate with high selectivity and reaction rate in the presence of a highly active catalyst.

[0010]

In order to achieve the above-mentioned object, the present inventor further studied the above Ru-Sn catalyst, and as a result, the cation of the cation exchanger and the Ru complex were cation-exchanged and Sn The present invention has been completed by finding that the solid catalyst supporting the components exhibits high catalytic activity.

That is, the present invention provides a cation exchanger, a ruthenium complex containing a positive valence ruthenium supported on the cation exchanger by cation exchange, and a zero-valent, divalent or The present invention relates to a catalyst for synthesizing acetic acid or methyl acetate composed of a tetravalent tin compound, and a method for producing acetic acid or methyl acetate by reacting methanol in the presence of the catalyst.

The catalyst of the present invention can be produced by cation exchange of the cation of the cation exchanger with a complex containing positive valence ruthenium and treatment of the cation exchanger with a divalent or tetravalent tin compound. .

The type of cation exchanger of the catalyst of the present invention is
There is no particular limitation as long as it has a cation exchange ability. Examples of the cation exchanger include natural or synthetic zeolites, carbonaceous exchangers such as sulfonated coal, zirconium phosphate heat-resistant ion exchangers, inorganic cation exchangers such as montmorillonite; polystyrene having a sulfone group and a sulfonylmethyl group. Examples thereof include strong acid cation exchange resins such as sulfonic acid type resins, and organic cation exchangers such as weak acid cation exchange resins having a carboxyl group, a phenolic hydroxyl group, a phosphon group and the like.

Preferred cation exchangers include inorganic cation exchangers and strongly acidic cation exchange resins, especially cation exchangers having a heat resistance higher than the reaction temperature (for example, a highly heat-resistant inorganic cation exchanger such as zeolite). included.

As the zeolite having the structure of condensed aluminosilicate, for example, A type zeolite, X type zeolite, Y type zeolite, ZSM-5 type zeolite, ZSM-
11 type zeolite, ZSM-34 type zeolite, T type zeolite, faujasite, mordenite, erionite,
Examples include chabazite and ferrierite. These zeolites can be used alone or in combination of two or more.

The Si / Al ratio in the zeolite can be appropriately selected. For example, Si / Al = 1 to 10,000, preferably 1 to 50.
It is a degree. The cation in the zeolite is not particularly limited, and examples thereof include Li ⁺ , K ⁺ , Na ⁺ , Cs ⁺ , Rb ⁺ , NH ₄ ⁺ , Ca ²⁺ . As the zeolite, zeolite containing Na ⁺ is often used, such as NaY type zeolite.

[0017] The specific surface area of the cation exchanger, such as an inorganic cation exchanger is not particularly limited, for example, a BET specific surface area of 20~3000m ² / g approximately, cation exchange about a specific surface area of 100-2000 m ² / g The body is heavily used.

The valence of Ru in the ruthenium complex (Ru complex) supported by cation exchange is preferably divalent or trivalent. The Ru complex cation has the general formula
The cation represented by (3) is included. [Ru (L) _m ] ^{q +} (3) (In the formula, L is a halogen atom, a hydrogen atom, a coordinating carbon-containing ligand, a coordinating nitrogen-containing ligand, a coordinating oxygen-containing ligand, Coordinating phosphorus-containing ligand, coordinating sulfur-containing ligand,
It represents a ligand selected from the group consisting of a coordinating arsenic-containing ligand and a coordinating atom contained in a cation exchanger, m is an integer of 0 to 6, and q is an integer of 1 to 3. When m is 2 or more, L may be the same or different. ) In the present invention, examples of the halogen atom represented by L 1 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Preferred halogen atoms are often chlorine and bromine atoms, especially chlorine atoms.

Examples of the coordinating carbon-containing ligand in the present invention include alkyl, cycloalkyl, aryl, aralkyl, optionally substituted cyclopentadienyl, optionally substituted olefin, CO, RNC (R = alkyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group) and the like can be mentioned.

The coordinating nitrogen-containing ligand referred to in the present invention includes, for example, NH ₃ , amines (eg, methylamine,
Amine such as ethylamine, dimethylamine, diethylamine, diamine such as ethylenediamine, nitrogen-containing heterocyclic compound such as imidazole, pyridine, pyrimidine, piperidine, piperazine, morpholine and phenanthroline, nitrogen-containing aromatic compound such as aniline, RCN
(R = alkyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group) and the like. Of these, NH ₃ is preferred.

Examples of the coordinating oxygen-containing ligand in the present invention include H ₂ O, alcohols such as aliphatic alcohols and aromatic alcohols, ethers such as aliphatic ethers and aromatic ethers, and hydroxy ions. , And alkoxide ions.

Examples of the coordinating phosphorus-containing ligand referred to in the present invention include PR ₃ or O═PR ₃ (R is an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkoxy group), 1 Examples thereof include bidentate phosphines such as 2,2-bis (diphenylphosphino) ethane.

Examples of the coordinating sulfur-containing ligand according to the present invention include RSR and RSH (R is an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkoxy group).

The coordinating arsenic-containing ligand referred to in the present invention is, for example, AsR ₃ or O═AsR ₃ (R is an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkoxy group), 1 Examples include bidentate arsines such as 2,2-bis (diphenylarsino) ethane.

In the present invention, examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl and hexyl groups. Examples of the cycloalkyl group include cyclopentyl, cyclohexyl and cyclooctyl groups. Examples of the aryl group include phenyl and naphthyl groups. Examples of the aralkyl group include benzyl, phenethyl and benzhydryl groups.
As the alkoxy group, for example, methoxy, ethoxy,
Examples include propoxy, isopropoxy, butoxy, isobutoxy, t-butoxy groups and the like.

The coordinating atom contained in the cation exchanger includes, for example, O ²⁻ which is lattice oxygen in zeolite.

Preferred Ru complexes include L = NH ₃ , Cl,
Br, CO, N ₂ or H ₂ O, complexes with m = 6 are mentioned.

The cation of the preferable Ru complex introduced into the cation exchanger is, for example, [Ru (NH ₃ ) ₆ ] ^{q +} , [Ru (NH
₃ ) ₅ Cl] ^{q +} , [Ru (NH ₃ ) ₅ (CO)] ^{q +} , [Ru (NH ₃ ) ₅ (N ₂ )] ^{q +} , [Ru
(NH ₃ ) ₅ H ₂ O] ^{q +} (wherein q = 1 to 3) and the like.

The amount of the Ru complex used is, in terms of Ru, for example, 0.1 to 25% by weight, preferably 0.5 to 25% by weight of the ion exchanger.
It is about 10% by weight.

A tin compound is further supported on the cation exchanger subjected to cation exchange as described above. The tin compound is preferably a divalent or tetravalent tin compound. Examples of the divalent tin compound include stannous halide (stannous fluoride, stannous chloride, stannous bromide, stannous iodide, etc.), tin alkoxide (for example, dimethoxytin, Diethoxytin, dipropoxytin, dibutoxytin, etc.). Examples of the tetravalent tin compound include stannic halides (stannic fluoride, stannic chloride, stannic bromide, etc.). Among these divalent or tetravalent tin compounds, stannous halide, particularly stannous chloride, is often used.
The amount of the tin compound supported is, for example, 1 to 5000 parts by weight, or preferably 5 to 1000 parts by weight with respect to 100 parts by weight of Ru of the Ru complex.
It is about part by weight. In the present invention, Ru has a positive valence such as monovalent to tetravalent. In addition, the following general formula
Sn in (1) and the general formula (4) has a zero-valent, divalent or tetravalent valence.

In the above general formula (3), when the Ru complex is a Ru complex containing divalent or trivalent Ru, the divalent Ru-containing complex reduces the complex containing trivalent Ru. The complex containing trivalent Ru can be produced by introducing a complex containing trivalent Ru by cation exchange or oxidizing the complex containing divalent Ru. Also, trivalent Ru (III) seems to be reduced to divalent Ru (II) during the reaction process.
The catalyst of the present invention also includes a catalyst containing a divalent Ru (II) complex formed in such a reaction process.

Furthermore, the supported state of the tin compound is as follows.
As an example, L of the general formula (3) (for example, NH ₃ etc.)
To Ru (II) or Ru (III) in which some or all of
SNZ ₃ enhances the catalytic activity ^- (Z represents a halogen atom or an alkoxy group) has been coordinated, and the Ru (II) -Sn (II) cluster catalyst and Ru (III) -Sn (II) cluster catalyst It seems to be mixed.

Such a complex can be obtained, for example, by the general formula (4)
Can be expressed as [Ru (L) _n (SnZ ₃ ) _r ] (4) (wherein L is a halogen atom, a hydrogen atom, a coordinating carbon-containing ligand, a coordinating nitrogen-containing ligand, a coordinating oxygen-containing Ligand, coordinating phosphorus-containing ligand, coordinating sulfur-containing ligand,
Represents a ligand selected from the group consisting of a coordinating arsenic-containing ligand and a coordinating atom contained in a cation exchanger, Z is a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkoxy group. Represents a group, L is Ru
And Ru and / or Ru and Sn may be crosslinked, n is an integer of 0 to 5, r is an integer of 1 to 6, and n +
r = 1 to 6. When n is 2 or more, L may be the same or different. ) SnZ ₃ ^-
The complex coordinated with may be a cation, nonion or anion. The halogen atom represented by Z includes fluorine, chlorine, bromine and iodine. Preferred halogen atoms are chlorine or bromine atoms, especially chlorine atoms. Examples of the alkoxy group represented by Z include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy and t-butoxy groups.

The catalyst of the present invention can be represented by, for example, the general formula (1). [Ru (L) _n (SnZ ₃ ) _r ] ・ I (1) (In the formula, L represents a halogen atom, a hydrogen atom, a coordinating carbon-containing ligand, a coordinating nitrogen-containing ligand, and a coordinating property. Oxygen-containing ligand, coordinating phosphorus-containing ligand, coordinating sulfur-containing ligand,
Represents a ligand selected from the group consisting of a coordinating arsenic-containing ligand and a coordinating atom contained in a cation exchanger, and Z is a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkoxy group. Represents a group, L is Ru
And Ru and / or Ru and Sn may be crosslinked. I represents a cation exchanger, n is an integer of 0 to 5, r
Represents an integer of 1 to 6, and n + r = 1 to 6. Note that n
When is 2 or more, L's may be the same or different. ) The catalyst may be in the form of powder, granules, pellets, rods, ellipses, spheres, or the like.

Since the Ru-Sn clusters are confined in the cage of the cation exchanger, the catalyst of the present invention is a catalyst supported on another carrier (for example, copper oxide, activated carbon, hydrotalcite, silica, etc.). Compared with, the catalyst has a feature that it has a very long catalyst life. This means that the catalyst component
It is presumed that it was confined in the cage of the ion exchanger and the deactivation due to aggregation was suppressed. Moreover, the cocatalyst effect of the Sn component is remarkably exhibited, and the catalytic activity is extremely high.

In order to obtain a catalyst in which an anion (or neutral or cation) and Ru—Sn complex having a large molecular size are confined in a cage of a cation exchanger, such as the catalyst of the present invention, Ru—Sn is used. It is easier to first cation-exchange the Ru complex, which is a cation, and then treat it with a tin compound, rather than once isolating and introducing the cluster.

As the Ru complex, a salt (complex salt) of a complex containing Ru among the compounds represented by the general formula (3) can be used. The Ru complex salt can be represented by, for example, the general formula (2). [Ru (L ') _m ] ^{q +} · A ^q- (2) (In the formula, L'is a halogen atom, a hydrogen atom, a coordinating carbon-containing ligand, a coordinating nitrogen-containing ligand, a coordinating property. Represents a ligand selected from the group consisting of an oxygen-containing ligand, a coordinating phosphorus-containing ligand, a coordinating sulfur-containing ligand and a coordinating arsenic-containing ligand, A represents an anion, m is an integer from 0 to 6, q
Is an integer of 1 to 3. When m is 2 or more, L ′ may be the same or different. ) Examples of the anion represented by A include halogen ions such as fluorine, chlorine, bromine and iodine, inorganic anions such as sulfate ion and phosphate ion; organic carboxylate anions such as acetate, trichloroacetate and trifluoroacetate, Organic anions such as sulfonate anions such as methane sulfonate, ethane sulfonate, benzene sulfonate and p-toluene sulfonate can be mentioned. Of these anions, inorganic anions, particularly halogen ions, such as chloride ions, are often used.

The ion exchange can be carried out by a conventional method, for example, by mixing the above-mentioned ion exchanger with the above-mentioned solution of the Ru complex. The solution of the Ru complex salt may be an aqueous solution, a hydrohalic acid corresponding to the halogen ion (for example, hydrochloric acid), an inorganic acid such as nitric acid, sulfuric acid, phosphoric acid, or an organic acid corresponding to the organic anion. An aqueous solution is often used. The pH of the Ru complex salt solution depends on the types of complex salt and ion exchanger, but is, for example, pH = 2 to
It is about 6.

The ion exchange can be carried out, for example, at about 10 to 40 ° C., and the stirring time is, for example, about 10 minutes to 96 hours, and the stirring is often carried out for about 1 to 48 hours.

After cation exchange, the ion exchanger is treated with the tin compounds exemplified above. The treatment with the tin compound was carried out using an ion exchanger in which the Ru complex was cation-exchanged,
It can be performed by dipping or mixing in a solution of a tin compound. The tin compound can be used as an aqueous solution, an aqueous solution of a hydrohalic acid (eg, hydrochloric acid), an inorganic acid such as nitric acid, sulfuric acid, phosphoric acid, an alcohol such as methanol or ethanol, or another organic solvent solution. If necessary, stannous halide may be sodium chloride,
It may be used as a solution containing a salt such as potassium chloride.

Immersion or mixing of the ion exchanger carrying the Ru complex by cation exchange is carried out at a suitable temperature, for example,
It can be performed at about 10 to 40 ° C., and the immersion or stirring time is not particularly limited, and is, for example, about 10 minutes to 96 hours, and often about 1 to 60 hours.

These operations can be carried out in air or in an inert atmosphere such as nitrogen, helium or argon under normal pressure, reduced pressure or increased pressure. After the tin compound is supported on the cation exchanger, the cation exchanger obtained by a method such as filtration is washed as needed and dried to obtain a catalyst. The catalyst may be granulated or molded by a conventional method using a binder if necessary.

The feature of the method of the present invention is that (a) acetic acid or methyl acetate can be produced by the stable and high activity of the above-mentioned catalyst, even though methanol is used as a single raw material, and (b) By adjusting the space velocity, acetic acid or methyl acetate can be produced with high selectivity while maintaining high catalytic activity.

The method of the present invention can be carried out by reacting methanol in the liquid phase in the presence of the above-mentioned solid catalyst, but utilizes a gas phase / solid phase reaction in which methanol is contacted with the catalyst in the gas phase to carry out the reaction. Is advantageous. When methanol is brought into contact with the solid catalyst and reacted, acetic acid or methyl acetate is produced in a one-step reaction. It is speculated that this reaction proceeds as follows. 2CH ₃ OH → 2HCHO + 2H ₂ 2HCHO → HCOOCH ₃ HCOOCH ₃ → CH ₃ COOH CH ₃ COOH + CH ₃ OH → CH ₃ COOCH ₃ + H ₂ O As is clear from the above reaction formula, the acetic acid produced is a raw material. Reacts with some methanol to produce methyl acetate.
Therefore, by reducing the proportion of methanol in the reaction system, it is possible to suppress the production of methyl acetate and efficiently produce acetic acid.

As is clear from the above reaction formula, in the method of the present invention, acetic acid or methyl acetate can be produced even when formaldehyde (or a formaldehyde source such as paraformaldehyde) or methyl formate is used as a reaction component. You can Therefore, acetic acid or methyl acetate can be produced by using at least one reaction component selected from methanol, formaldehyde, and methyl formate, but it is advantageous to use inexpensive methanol as a reaction component.

Depending on the reaction conditions, a relatively large amount of methyl formate useful as a precursor of acetic acid or methyl acetate may be produced as a by-product. Therefore, the method of the present invention can be used as a method for producing methyl formate by appropriately selecting the reaction conditions.

The reaction is carried out, for example, at 50 to 400 ° C., preferably
It can be performed at about 100 to 300 ° C. The reaction is preferably carried out under an inert atmosphere such as nitrogen, helium or argon,
It can be carried out under normal pressure or under pressure. The reaction may be carried out batchwise or continuously.

When the reaction is carried out in a batch system, the ratio of methanol to the solid catalyst can be appropriately selected within a range in which the efficiency of producing acetic acid or methyl acetate does not decrease. Ru complex and Sn component of solid catalyst (hereinafter referred to as catalyst component) 1
The ratio of methanol to the mole is, for example, 0.1 to 10,000.
It is about 10 to 1,000 mol, preferably about 10 to 1,000 mol.

A preferable method is a method in which gaseous methanol is continuously supplied to the solid catalyst. In the continuous method, the amount of methanol supplied can be appropriately selected, for example, in the range of about 0.001 to 1,000 mol / min with respect to 1 mol of the catalyst component of the solid catalyst.

In the continuous method, when the feed rate of methanol per unit weight of catalyst is expressed in mol / hr, the space velocity W / F
Can be selected in a wide range, for example W / F = 0.001 to 10,000
(g-cata.h mol ^-1 ), preferably 0.01 to 5,000 (g-cata.h
mol ^-1 ).

The catalyst of the present invention exhibits a peculiar behavior that the selectivity of acetic acid or methyl acetate is remarkably improved and the composition of the reaction product can be controlled by increasing the space velocity. That is, the space velocity is 50 to 300 (g-cata.h mol
^-1 ), methyl formate and acetic acid or methyl acetate are produced, and at a space velocity of 500 to 10,000 (g-cata.h mol ^-1 ), especially above 1,000 (g-cata.h mol ^-1 ), formate Almost no methyl is produced, and acetic acid or methyl acetate is produced with a high selectivity of approximately 100%. Therefore, acetic acid or methyl acetate can be industrially produced with high productivity using methanol as a single raw material.

In the continuous method, a conventional method, for example,
Any method such as a flow reaction method in which gaseous methanol is supplied to a packed bed filled with a solid catalyst, a method in which a solid catalyst is suspended in gaseous methanol to form a fluidized bed for reaction, and a reactive distillation method can be used. In the continuous reaction system, the flow reaction system is preferable. Acetic acid or methyl acetate can be produced by subjecting the reaction product to a purification step such as distillation, if necessary.

[0053]

INDUSTRIAL APPLICABILITY The catalyst of the present invention has a high catalytic activity and can produce acetic acid or methyl acetate in a single step reaction with methanol as a single source. In addition, high catalytic activity can be maintained for a long time, and acetic acid or methyl acetate can be produced with high selectivity. In the present invention, the catalyst having the above-mentioned excellent properties can be obtained by a simple operation of cation exchange and loading. Further, in the method of the present invention, it is possible to produce acetic acid or methyl acetate with a high selectivity and a high reaction rate in a single reaction using methanol as a single source. Moreover, by adjusting the space velocity, acetic acid or methyl acetate is almost 100%.
Can be manufactured with a high selectivity.

[0054]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

Example 1 (1) NaY type zeolite (manufactured by Tosoh Corporation, HSZ-320NA)
A, SiO ₂ / Al ₂ O ₃ = 5.5, specific surface area 700 m ² / g) 5.0 g, and [Ru (NH ₃ ) ₆ ] Cl ₃ 0.60 g (3% by weight based on the zeolite in terms of Ru) of hydrochloric acid The zeolite cation-exchanged with the Ru complex was prepared by adding it to 1500 ml of an aqueous solution (pH = 4.5) and stirring in air for 48 hours. (2) SnCl ₂ · in 500 ml of methanol under argon atmosphere
2.23 g of 2H ₂ O (Sn / Ru = 25) and 3.69 g of NaCl were dissolved. To the resulting solution was added 1.10 g of the above zeolite, the mixture was stirred at room temperature for 24 hours, filtered in air, and dried in vacuum to obtain a catalyst. (3) The atmospheric pressure fixed bed flow reactor was charged with 3.0 g of the above catalyst, and at a reaction temperature of 200 ° C., dry methanol was added with helium as a carrier gas at a space velocity of 1300 (g-
cata.h mol ^-1 ) for 240 hours. When the reaction product was quantified by gas chromatography, the results shown in FIG. 1 were obtained. As is clear from Fig. 1, the catalyst had a conversion rate of methyl acetate of about 9% after an induction period of about 40 hours.
The activity of Methyl acetate is produced with a selectivity of approximately 100%, and the by-product of methyl formate is extremely small. Even when the above reaction was carried out for 240 hours, the activity of the catalyst was only slightly decreased.

Example 2 1.00 g of the catalyst obtained in Example 1 was charged into a fixed pressure fixed bed flow type reactor and, together with helium as a carrier gas,
Space velocity of dried methanol was 1100 (g-cata.hmol ^-1 ).
When the reaction was carried out in the same manner as in Example 1 except that the solution was supplied in step 1, the results shown in FIG. 2 were obtained. As is clear from FIG.
After an induction period of about 70 hours, the catalyst converted to methyl acetate
In addition to showing 3.5% activity, methyl formate has a conversion rate of 0.3.
% Was a byproduct. Even if the reaction was carried out for 160 hours, the catalyst had a methyl acetate conversion rate of 3.5% and a methyl formate conversion rate.
It shows an activity of 0.3%, and the catalytic activity is almost unchanged.

Example 3 300 mg of the catalyst obtained in Example 1 was charged into an atmospheric fixed bed flow type reactor and, together with helium as a carrier gas,
Space velocity of dried methanol was 130 (g-cata.hmol ^-1 ).
When the reaction was carried out in the same manner as in Example 1 except that the solution was supplied in step 1, the results shown in FIG. 3 were obtained. As is clear from FIG.
After an induction period of about 20 hours, the catalyst converted to methyl acetate
It has 2.5% activity and methyl formate has a conversion rate of 2.3.
% Was a byproduct. Even if the reaction was carried out for 200 hours, the catalyst had a methyl acetate conversion of 2.2% and methyl formate conversion.
It shows an activity of 1.8%, and the catalytic activity is hardly reduced.

As is clear from Examples 1 to 3, the conversion rates of methyl acetate and methyl formate can be controlled by adjusting the amount of catalyst used and the space velocity.

Comparative Example In preparing the catalyst, SnCl 2 of step (2) of Example 1 was used.
_{In the same} manner as in Example 1 without performing the treatment according to ₂ ,
A zeolite cation exchanged with Ru complex was prepared. When methanol was continuously reacted for 90 hours in the same manner as in Example 2 except that the obtained catalyst was used, a trace amount of methyl formate was observed, but acetic acid or methyl acetate was not generated at all. There wasn't. .

[Brief description of drawings]

FIG. 1 is a graph showing the results of Example 1.

FIG. 2 is a graph showing the results of Example 2.

FIG. 3 is a graph showing the results of Example 3.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C07C 69/14 9279-4H // C07B 61/00 300

Claims (15)

[Claims] 1. A cation exchanger, a ruthenium complex containing positive valence ruthenium supported on the cation exchanger by cation exchange, and zero-valent, divalent or tetravalent tin supported on the cation exchanger. A catalyst for synthesizing acetic acid or methyl acetate composed of a compound. 2. A compound represented by the general formula (1) [Ru (L) _n (SnZ ₃ ) _r ] .I (1) (wherein L is a halogen atom, a hydrogen atom, a coordinating carbon-containing ligand, or a coordination atom). Nitrogen-containing ligand, coordinating oxygen-containing ligand, coordinating phosphorus-containing ligand, coordinating sulfur-containing ligand,
Represents a ligand selected from the group consisting of a coordinating arsenic-containing ligand and a coordinating atom contained in a cation exchanger, and Z is a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkoxy group. Represents a group, L is Ru
And Ru and / or Ru and Sn may be crosslinked. I represents a cation exchanger, n is an integer of 0 to 5, r
Represents an integer of 1 to 6, and n + r = 1 to 6. Note that n
When is 2 or more, L may be the same or different. ) The catalyst for synthesizing acetic acid or methyl acetate according to claim 1, represented by 3. The catalyst for synthesizing acetic acid or methyl acetate according to claim 1, wherein the cation exchanger is an inorganic cation exchanger. 4. The catalyst for synthesizing acetic acid or methyl acetate according to claim 1, wherein the cation exchanger is zeolite. 5. The catalyst for synthesizing acetic acid or methyl acetate according to claim 1, wherein the cation exchanger is NaY type zeolite. 6. The catalyst for synthesizing acetic acid or methyl acetate according to claim 1, wherein the ruthenium complex is a ruthenium ammine complex. 7. The catalyst for synthesizing acetic acid or methyl acetate according to claim 1, wherein the tin compound is stannous halide or an alkoxide of tin. 8. The catalyst for synthesizing acetic acid or methyl acetate according to claim 1, wherein the tin compound is stannous chloride. 9. A method for producing a catalyst, wherein the cation of the cation exchanger is cation-exchanged with a ruthenium complex salt containing ruthenium having a positive valence, and the cation exchanger is treated with a divalent or tetravalent tin compound. 10. The ruthenium complex salt has the general formula (2) [Ru (L ′) _m ] ^{q +} · A ^q− (2) (wherein, L ′ is a halogen atom, a hydrogen atom, and a coordinating carbon-containing coordination). Child, a coordinating nitrogen-containing ligand, a coordinating oxygen-containing ligand, a coordinating phosphorus-containing ligand, a coordinating sulfur-containing ligand and a coordinating arsenic-containing ligand Represents a selected ligand, A represents an anion, m is an integer of 0 to 6, and q
Is an integer of 1 to 3. When m is 2 or more, L ′ may be the same or different. 10. The method for producing a catalyst according to claim 9, which is a ruthenium complex salt represented by 11. The method for producing a catalyst according to claim 9, wherein the ruthenium complex salt is a ruthenium complex salt represented by the formula [Ru (NH ₃ ) ₆ ] Cl ₃ . 12. The method for producing a catalyst according to claim 11, wherein the cation exchanger is NaY type zeolite. 13. The method for producing a catalyst according to claim 12, wherein the tin compound is stannous chloride. 14. A process for producing acetic acid or methyl acetate, which comprises reacting methanol in the presence of the catalyst according to claim 1. 15. A method of reacting methanol in a gas phase.
14. The method for producing acetic acid or methyl acetate according to 14.