JPS6341372B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides ethylene glycol, methanol,
This invention relates to a method for directly producing oxygen-containing organic compounds such as ethanol from carbon monoxide and hydrogen. As a method for directly producing oxygen-containing organic compounds such as ethylene glycol, methanol, and ethanol from carbon monoxide and hydrogen, a catalyst system containing a group metal of the periodic table, such as a rhodium-based catalyst, is known. Among these conventionally known methods,
Methods using rhodium-based catalysts have considerably high catalytic activity, but in addition to the extremely high cost of rhodium-based catalysts, in both methods, the rhodium-based catalyst becomes inactive as rhodium metal after the reaction is completed. However, it has the disadvantage that it cannot be easily recovered and reused. Therefore, although the method using rhodium-based catalysts has a considerably high catalytic activity, it has become difficult to adopt it as a method for economically producing oxygen-containing organic compounds such as ethylene glycol on an industrial scale. In addition, other noble metal catalysts other than the above-mentioned rhodium catalysts include JP-A-55-115834 and USP No.
No. 4170605, J.Am.Chem.Soc., 102 , 6855
(1980), Erdol ko¨hle Erdgas Petrochem, 32 ,
313 (1979), Int. High Pressure Conf. (USA),
6th (1977), [1], 733-738 (1979), JP-A-1987-
Methods using ruthenium-based catalysts have been proposed in JP-A-82327 and JP-A-57-82328. In methods using these ruthenium-based catalysts, the catalyst itself is inexpensive and economically superior, but compared to rhodium-based catalysts, for example, the ethylene glycol production activity is inferior. Said USP 4170605 and Int.High Pressure Conf. (USA), 6th
(1977), [1], 733-738 (1979) proposes a method using a ruthenium complex catalyst formed from a specific ruthenium compound and a pyridine base ligand; No. 55-115834, JP-A-Sho
No. 57-82328 and others propose a method using a solubilized ruthenium carbonyl complex as a catalyst. Furthermore, these publications disclose the use of a Lewis base such as amines, pyridines, cyclic amines such as purine, pyrimidine, and piperazine as a promoter in addition to the ruthenium carbonyl complex. Further, JP-A-56-123925 discloses a method in which a compound of another group metal such as rhodium is used in combination with a ruthenium compound. This publication also discloses compounds of alkali metals and alkaline earth metals, such as halides, carboxylates, and nitrogen-containing cations, or bases, such as ammonium salts, iminium salts, and pyridines, as cocatalysts. has been done. However, no matter which of these ruthenium-based catalysts is used, the activity, especially under low pressure conditions, is not good, and oxygen-containing organic compounds such as ethylene glycol cannot be produced in high yield. The present invention relates to a method for significantly improving the activity of a ruthenium-based catalyst as described above. The present invention also relates to a method for producing oxygen-containing organic compounds such as ethylene glycol in high yield using a catalyst system comprising a benzimidazole compound in combination with a ruthenium compound. That is, the present invention provides a method for producing an oxygen-containing organic compound by reacting carbon monoxide and hydrogen in the presence of a catalyst and under heating and pressurizing conditions. The present invention relates to a method for producing an oxygen-containing organic compound, characterized in that the reaction is carried out using a catalyst in which the number of moles of (b) is 40 moles or more per gram atom of ruthenium metal in (a). The catalyst used in the method of the present invention is a ruthenium compound (a) and a benzimidazole compound.
It is a catalyst consisting of (b). Here, specific examples of the ruthenium compound include ruthenium halides, carboxylates, inorganic acid salts, oxides,
Examples include compounds having complex bonds with various organic ligands and compounds having complex bonds with various inorganic ligands. More specifically, ruthenium chloride,
Ruthenium bromide, ruthenium iodide, ruthenium formate, ruthenium acetate, ruthenium nitrate, ruthenium dioxide, ruthenium tetroxide, Ru(acac) ₃ ,
( _C5H5 )( _CH3 ) _Ru (CO) ₂ , ( _C5H5 ) _{2Ru , Ru3}
(CO) ₁₂ , Ru (CO) ₄ ^2- , Ru ₆ (CO) ₁₈ ^2- , H ₂ Ru ₄
Examples include (CO) ₁₃ , H ₆ Ru ₄ (CO) ₁₂ , [Ru(CO) ₃ Cl ₂ ] ₂ and the like. Further, finely powdered ruthenium metal can also be used because it forms a carbonyl complex in the reaction system and dissolves. The proportion of the ruthenium compound (a) to be used is not particularly limited, but the concentration of ruthenium atoms in the reaction system is usually 1 to 10 ^-6 gram atom/, particularly preferably 2 x 10 ^-1 to 10 ^-4 gram atom/range. The benzimidazole compound used in the present invention is a compound represented by the following general formula. (In the formula, R ¹ to R ⁶ are hydrogen or a group selected from arbitrary substituents. Among these, R ¹ and
Each set of R ² , R ² and R ³ , R ³ and R ⁴ , and R ⁴ and R ⁵ may be connected to each other to form a divalent hydrocarbon group or a polar group-substituted hydrocarbon group. . ) Examples of such benzimidazole compounds include the following. Benzimidazole, N-methylbenzimidazole, N-ethylbenzimidazole, N-n
-Propylbenzimidazole, N-iso-propylbenzimidazole, N-tert-butylbenzimidazole, N-n-butylbenzimidazole, N-phenylbenzimidazole, N-benzylbenzimidazole, N-cyclohexylbenzimidazole, N- Octylbenzimidazole, N-dodecylbenzimidazole, N-
Hexadodecylbenzimidazole, 4-methylbenzimidazole, 5,6-dimethylbenzimidazole, 4,5,6-trimethylbenzimidazole, N-methyl-5,6-dimethylbenzimidazole, N-ethyl-5,6-dimethyl Benzimidazole, N-iso-propyl-5,6
-dimethylbenzimidazole, 5,6-dimethoxybenzimidazole, 4,5-trimethylenebenzimidazole, naphtho[1,2-d]imidazole, naphtho[2,3-d]imidazole,
1-methyl-4-methoxybenzimidazole,
1-methyl-5-methoxybenzimidazole,
Examples include 1-methyl-4,5-dimethoxybenzimidazole. It should be added that 4-azabenzimidazole and 1-methyl-4-azabenzimidazole are also exemplified as other examples. The present invention is characterized in that a predetermined amount of one or more compounds selected from benzimidazole compounds (b) is used in combination with the ruthenium compound (a) in the reaction system. In the present invention, the benzimidazole compound (b) is used in an amount of 40 moles or more per gram atom of ruthenium in the reaction system. The usage amount is 40
Ethylene glycol if less than molar,
This is not preferable because the amount of oxygen-containing organic compounds such as methanol and ethanol produced decreases. In addition, if the amount used is too large, the effect of increasing the amount of oxygen-containing organic compounds produced will reach a plateau, so the amount of benzimidazole compound used is within the range of 40 to ¹⁰⁷ mol per 1 gram atom of ruthenium. used.
Furthermore, it is desirable to use the benzimidazole compound (b) in a concentration range of 10 ^-3 mol to 10 mol with respect to the reaction solution 1. In the present invention, other catalyst components can be used in combination with the ruthenium compound (a) and benzimidazole compound (b). Such compounds include compounds of at least one metal selected from metals in groups of the periodic table, groups other than ruthenium, and halides, carboxylates, and inorganic acid salts of these metals. , oxide,
Examples include various ligands, such as compounds complexly bound to carbon monoxide. Other catalyst components that can be used in combination include halogen compounds. Examples of halogen compounds include simple halogens such as iodine, bromine, and chlorine, hydrogen halides such as hydrogen iodide, hydrogen bromide, hydrogen chloride, and hydrogen fluoride, and halides such as alkali metals, alkaline earth metals, aluminum, and phosphorus. , quaternary ammonium halide, quaternary phosphonium halide, iminium halide, alkyl halide, aryl halide and the like. More specifically, these compounds include, for example, alkali metal halides such as lithium fluoride,
Lithium chloride, lithium bromide, lithium iodide, sodium fluoride, sodium chloride, sodium bromide, sodium iodide, potassium fluoride, potassium chloride, potassium bromide, potassium iodide, rubidium chloride, rubidium bromide, iodide These include rubidium, cesium fluoride, cesium chloride, cesium bromide, and cesium iodide, as well as aluminum trichloride, phosphorus trichloride, and phosphorus pentachloride. As quaternary ammonium halides, compounds produced by the reaction of various amines with alkyl halides, aryl halides, etc. can be used. Specifically, tetramethylammonium chloride, tetramethylammonium bromide, iodide Tetramethylammonium, tetramethylammonium fluoride, tetraethylammonium chloride, tetraethylammonium bromide, tetra n-propylammonium halide, tetra n-butylammonium halide, trimethylbenzylammonium halide, triethylbenzylammonium halide, triisopropylbenzylammonium halide, and more Pyridinium halides such as N-methylpyridinium halide, 1-methyl-2-hydroxypyridinium halide, and methyl-4-dimethylaminopyridinium halide; imidazolium such as methyl-1-methylimidazolium halide and ethyl-1-methylimidazolium halide; There are halides, etc.
Examples of the quaternary phosphonium halide include tetramethylphosphonium chloride, tetramethylphosphonium iodide, tetramethylphosphonium bromide, tetramethylphosphonium chloride, tetramethylphosphonium fluoride, tetraethylphosphonium iodide, tetraethylphosphonium bromide, tetraethylphosphonium chloride, Examples include tetraethylphosphonium fluoride, tetra n-propylphosphonium halide, tetra n-butylphosphonium halide, tetraphenylphosphonium halide, triphenylmethylphosphonium halide, and triphenylethylphosphonium halide. Iminium halides include bis(triphenylphosphine)iminium iodide, bis(triphenylphosphine)iminium bromide, and bis(triphenylphosphine) chloride.
There are also iminiums. Alkyl halides and aryl halides include halides of alkyl groups and aryl groups having about 1 to 20 carbon atoms, and specifically,
Alkyl halides such as methyl iodide, ethyl iodide, ethyl bromide, ethyl chloride, isopropyl iodide, isopropyl bromide, isopropyl chloride, n-butyl iodide, n-butyl bromide, n-butyl fluoride, iodide Examples include aryl halides such as phenyl, brominated phenyl, benzyl iodide, and benzyl bromide. The co-catalyst exemplified above is a ruthenium compound (a)
and a co-catalyst that may be further used in combination with the benzimidazole compound (b), and one type or two or more types may be used in combination as necessary. When using compounds of metals of Groups 1 and 3 of the Periodic Table and groups other than ruthenium, the proportion of combination is usually expressed as the ratio of the number of gram atoms of the compound of these metals to 1 gram atom of ruthenium in the reaction system. About 10 ^-2 to about 10 ² , especially about 10 ^-1 to about 10
is suitable. In addition, when a halogen compound is used in combination, the ratio of the number of moles of the halogen compound to the number of grams of ruthenium in the amount of ruthenium compound (a) used is approximately
10 ^-2 to 10 ³ , preferably about 10 ^-1 to 10 ² . To prepare the catalyst used in the method of the present invention, the ruthenium compound (a) and the benzimidazole compound (b), as well as other co-catalysts as necessary, are separately added to the reaction system. It is also possible to adopt a method in which catalytically active species are formed within the reaction system, or a complex or mixture formed from a ruthenium compound and a benzimidazole compound (b), as well as other co-catalysts as necessary, may be added to the reaction system. You can also. The ruthenium compound (a) may be premixed with an organic diluent before use. Furthermore, the benzimidazole compound (b) may be used as an organic diluent for other catalyst components. Furthermore, embodiments in which the benzimidazole compound (b) is formed within the reaction system are also exemplified, such as
Advances in Heterocyclic Chemistry 12,
The method disclosed in P.103-183 (1970) may also be adopted. The reaction of the present invention is usually carried out in the presence of a solvent. As the solvent, any organic solvent that is inert to the reaction can be used, and the above-mentioned organic diluents can also be used as they are. Specific examples of solvents include ethers such as tetrahydrofuran, dimethyl ether of diethylene glycol, dimethyl ether of tetraethylene glycol (tetraglyme), diethyl ether, diisopropyl ether, dioxane, 1,2-dimethoxybenzene, and 18-crown-6; methyl acetate. , ethyl acetate, butyl acetate, ethylene glycol diacetate, diethylene glycol diacetate, γ-butyrolactone, dimethyl-γ-butyrolactone,
Esters such as δ-valerolactone; Sulfones such as sulfolane and dimethylsulfone; Sulfoxides such as dimethylsulfoxide and diethylsulfoxide; N,N-dimethylformamide,
N,N-diethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, N-isopropylpyrrolidone,
Amides such as N-propylpyrrolidone, N-butylpyrrolidone, N-octylpyrrolidone, N-cyclohexylpyrrolidone, N-benzylpyridone, polyvinylpyrrolidone, N-methyl-2-pyridone; hexamethylphosphoric acid triamide, hexaethylphosphoric acid Phosphoracetic triamides such as triamide; N,N,N',N'-tetramethylurea,
Substituted ureas such as 1,3-dimethyl-2-imidazolidone; Alcohols such as methanol, ethanol, 2-methoxyethanol, ethylene glycol, diethylene glycol, and triethylene glycol; Carboxylic acids such as acetic acid, propionic acid, and benzoic acid; Phenols , phenols such as resorcin; amines such as trimethylamine and triethylamine; pyridines such as pyridine and 2-hydroxypyridine; nitriles such as acetonitrile and benzonitrile; ketones such as acetone and diphenyl ketone; hexane, heptane, hexene,
Hydrocarbons such as cyclohexane, naphtha, and kerosene;
Examples include aromatic hydrocarbons such as benzene, toluene, and xylene. Among these solvents, it is preferable to use aprotic dipolar solvents such as esters, polyethers, sulfones, and amides because they improve the reaction rate.
Furthermore, benzimidazole compounds can also be used as a solvent. In the method of the present invention, the ratio of carbon monoxide and hydrogen gas supplied to the reaction system is usually in the range of 20 to 0.05, preferably 5 to 0.2 as a molar ratio of carbon monoxide to hydrogen gas. In the method of the invention, the reaction is carried out under heated and pressurized conditions. The pressure during the reaction is usually 2000 to 1 Kg/cm ² -G, preferably 1000 to 50 Kg/cm ² -
It is in the range of G. Generally, the higher the pressure during the reaction, the better the reaction rate will be, and the method of the present invention is particularly characterized in that oxygen-containing organic compounds such as alkane polyols are produced even in a relatively low pressure region. Further, the temperature during production is usually in the range of 50 to 350°C, preferably 150 to 300°C. The time required for the reaction is usually
It ranges from 0.1 to 20 hours, preferably from 0.5 to 10 hours. Usually the reaction is carried out under stirring conditions. In the method of the present invention, the reaction mixture after completion of the reaction is treated by a conventional method such as distillation or extraction to contain methanol, ethanol, ethylene glycol, 1,2-propanediol, acetic acid, methyl acetate, methyl formate, etc. Oxygen organic compounds can be isolated. Next, the method of the present invention will be specifically explained using examples. Comparative Example 1 After replacing the inside of a Hastelloy C autoclave with a capacity of 60 ml with argon, 0.4 milligram atoms of Ru ₃ (CO) ₁₂ , 40 mmol of imidazole, and 10 ml of n-methylpyrrolidone (NMP) were placed in the autoclave, and the autoclave was placed in the autoclave. closed.
In this case, the ratio of the number of moles of imidazole to Ru1 gram atom is 100 moles. Next, a mixed gas with a carbon monoxide/hydrogen molar ratio of 1/1 was introduced into the autoclave from the gas introduction pipe into the reaction system, and the reaction was carried out at a pressure of 500 to 550 Kg/cm ² and a temperature of 240°C for 2 hours. . After the reaction was completed, the mixture was cooled to room temperature, excess gas was discharged, and the reaction mixture was taken out. Table 1 shows the results of quantifying this by gas chromatography. Comparative Examples 2 to 4 and Examples 1 to 38 The same procedures as in Comparative Example 1 were carried out except that the conditions shown in Table 1 were used. The results are shown in Table 1.

【table】

【table】

[Table] Examples 39 to 41 The same procedures as in Example 1 were carried out except that the compounds shown in Table 2 were used as the Ru compounds. The results are shown in Table 2.

[Table] Examples 42 to 43 Put Ru ₃ (CO) ₁₂ and imidazole compound in the amounts shown in Table 3 into an autoclave, and introduce a mixed gas with a carbon monoxide/hydrogen molar ratio of 1/1 into the reaction system. The reaction was carried out under the conditions shown in Table 3. The results are shown in Table 3.

[Table] Examples 44 to 48 Ru ₃ (CO) ₁₂ , imidazole compound, additives and solvent (100 ml) were placed in an autoclave as shown in Table 4, and the molar ratio of carbon monoxide/hydrogen was 1/1.
A mixed gas of was introduced into the reaction system, and the reaction was carried out under the conditions shown in Table 4. The results are shown in Table 4.

[Table] Comparative Examples 5 to 7 and Examples 49 to 50 After replacing the inside of a stainless steel autoclave with a capacity of 60 ml with argon, Ru ₃ (CO) ₁₂ , 1-methylbenzimidazole, and the solvent tetraglyme were added to the autoclave. (TGM) was added in the amount shown in Table 5, and the autoclave was closed. Table 5 shows the ratio of the number of moles of 1-methylbenzimidazole to Ru1 gram atom in this case. Next, a mixed gas with a carbon monoxide/hydrogen molar ratio of 1/1 was pressurized into the autoclave from the gas inlet pipe until the pressure inside the reaction system reached 200 kg/ ^cm2 , and then the temperature was increased to 240°C.
heated to. The pressure in the reaction system reached approximately 550 Kg/cm ² . This was heated to 240°C for 2 hours to react. After the reaction was completed, the mixture was cooled to room temperature, excess gas was discharged, and the reaction mixture was taken out. Table 5 shows the results of quantifying this by gas chromatography. Further, FIG. 1 shows the relationship between the ratio of the number of moles of 1-methylbenzimidazole to Ru1 gram atom of the catalyst and the amount of ethylene glycol (EG) and methanol produced in this case.

【table】 [Brief explanation of the drawing]

Figure 1 shows the ratio of moles of 1-methylbenzimidazole to Ru1 gram atom in the catalyst and the reaction product ethylene glycol (EG).
It is a graph showing the relationship between the amount of methanol produced and the amount of methanol produced.

Claims (1)

[Scope of Claims] 1. A method for producing an oxygen-containing organic compound by reacting carbon monoxide and hydrogen in the presence of a catalyst and under heating and pressurizing conditions, wherein a ruthenium compound (a) and a benzimidazole compound ( b)
A method for producing an oxygen-containing organic compound, characterized in that the reaction is carried out using a catalyst in which the number of moles of (b) is 40 moles or more per gram atom of ruthenium metal in (a). 2. Claim 1, wherein the oxygen-containing organic compound is one or more compounds selected from methanol, ethanol, ethylene glycol, 1,2-propanediol, acetic acid, methyl acetate, and methyl formate. The manufacturing method described in. 3. The manufacturing method according to claim 1 or 2, wherein the oxygen-containing organic compound is ethylene glycol.