JPS6114129B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing oxygen-containing organic compounds such as ethylene glycol and methanol. Conventionally, it has been known to use a ruthenium-based catalyst as a method for producing ethylene glycol by reacting carbon monoxide and hydrogen;
No., J.Am.Chem.Soc., 102, 6855 (1980),
Erdol Kohle Ergas Petrochem., 32 , 313
(1979), Int.High Pressure Conf. (USA),
6th, [1] 733-738 (1979) and J.Catl. 61 ,
359 (1980), etc. These methods using ruthenium-based catalysts are cheaper than rhodium-based catalysts and are economically superior, but their catalytic activity is low, especially under low reaction pressure conditions. For example, JP-A-55-115834 discloses that cyclic amines such as amines, pyridines, purines, pyrimidine, piperazine, etc., bis(triphenylphosphine) and solubilized ruthenium carbonyl complexes are used as cocatalysts. It is disclosed that minium halides, alkali metal halides, alkaline earth metal halides, cobalt iodide, iron iodide, etc. can be used. Also, the aforementioned U.S. Pat. No. 4,170,605 and Int.
High Pressure Conf. (USA), 6th [1] 733~
738 (1979) proposes a method using a ruthenium complex catalyst formed from a specific ruthenium compound and a pyridine base ligand. Furthermore, JP-A-56-123925 proposes a method of using a catalyst consisting of a ruthenium compound, a compound of a group metal other than ruthenium, and a co-catalyst component, and the co-catalyst component is an alkali metal halide compound, It is proposed to use alkaline earth metal halide compounds, quaternary ammonium halide compounds, quaternary iminium halide compounds, pyridine or substituted pyridine compounds. JP-A-56-100728 discloses an embodiment in which phosphonium halide and ammonium halide are used together with a ruthenium compound. Furthermore, JP-A No. 55-9088 describes a method for simultaneously producing alkanol esters and glycol esters by carrying out a reaction in the presence of a carboxylic acid such as acetic acid, trifluoroacetic acid, or monofluoroacetic acid, in which a phosphonium halide is used together with a ruthenium compound as a catalyst. , or an embodiment in which ammonium halide is used in combination. However, even when these conventionally proposed cocatalysts are used in combination with a ruthenium compound, the catalytic activity is not sufficient, and oxygen-containing organic compounds such as alkane polyols cannot be produced in high yield. In contrast, the present inventors have already found that the production activity of oxygen-containing organic compounds such as ethylene glycol is dramatically improved by using an imidazole compound as a cocatalyst together with a ruthenium compound. The inventors have discovered that the production activity of oxygen-containing organic compounds can be further improved by further using at least one metal hydride selected from hafnium, lanthanum, and niobium in the combined catalyst system, and have arrived at the present invention. That is, the present invention provides a method for producing an oxygen-containing organic compound by reacting carbon monoxide and hydrogen under heat and pressure in the presence of a catalyst. The present invention relates to a method for producing an oxygen-containing organic compound, which uses a catalyst comprising a metal hydride (c). Among the catalysts used in the method of the present invention, specific examples of the ruthenium compound (a) include ruthenium halides, carboxylates, inorganic acid salts, oxides, compounds complexed with various organic ligands, Examples include compounds that have 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 ,}
( _C2H5 ) _2Ru , _Ru3 (CO) ₁₂ , Ru( _CO ) ^2-4 _{, Ru6}
(CO) ^2-18 , H ₂ Ru ₄ (CO) ₁₃ , H ₆ Ru ₄ (CO) ₁₂ , [ _Ru
(CO) ₃ Cl ₂ ] ₂ etc. can be exemplified. It is also possible to supply ruthenium metal in the form of fine powder to the reaction system and form a soluble carbonyl complex there. The proportion of ruthenium compound (a) used is not particularly limited, but the concentration of ruthenium atoms in the reaction system is usually 1 to 10 ^-6 gram atoms/
, particularly preferably in the range of 2×10 ⁻¹ to 10 ⁻⁴ gram atoms/atom. On the other hand, imidazoles (b) include imidazole and imidazole derivatives having arbitrary substituents. Preferred compounds as imidazoles (b) are:
It is represented by the general formula below.

[Formula] (In the formula, R ¹ , R ² , R ³ and R ⁴ are hydrogen and arbitrary substituents. Among these, R ¹ and R ² , R ³ and
Each set of R ⁴ , R ¹ and R ⁴ may be linked to each other to form a divalent hydrocarbon group or a polar group-substituted hydrocarbon group. ) Here, the following are specifically exemplified as the polar group and other substituents. Halogens such as chlorine, bromine, and iodine, hydroxyl groups, carboxyl groups,
formyl group, acyl group such as acetyl, butyroyl, benzoyl, toluoyl, amino group, substituted amino group such as dimethylamino, diethylamino, alkoxy group such as methoxy, ethoxy, cyano group,
Alkyl-substituted silyl groups such as isocyano group, nitro group, silyl group, trimethylsilyl, as well as methyl, ethyl, n-propyl, iso-propyl, n
-butyl, iso-butyl, tert-butyl, octyl, dodecyl, hexadecyl, cyclohexyl,
There are hydrocarbon groups such as phenyl and benzyl, and hydrocarbon groups substituted with the above polar groups. Among these imidazoles (b), preferably used imidazoles (b) include imidazole, hydrocarbon group-substituted imidazole, hydroxyalkyl group-substituted imidazole, carboxyalkyl group-substituted imidazole, aminoalkyl group-substituted imidazole, polyvinylimidazole, etc. imidazole substituted with a polar group-substituted hydrocarbon group,
Specifically, imidazole, N-methylimidazole, N-ethylimidazole, N-propylimidazole, N-isopropylimidazole, N
-Butylimidazole, n-methylimidazole, 2-ethylimidazole, 2-propylimidazole, 2-isopropylimidazole, 4-
Methylimidazole, 4-ethylimidazole,
4-propylimidazole, 4-isopropylimidazole, 4-butylimidazole, 4,5-
Dimethylimidazole, 4,5-diethylimidazole, N-methyl-2-ethylimidazole,
N-methyl-4-ethylimidazole, 1-phenylimidazole, 4-phenylimidazole benzimidazole, 1,2-trimethyleneimidazole, 1,5-trimethyleneimidazole,
4,5-trimethyleneimidazole, 4,5.
Hydrocarbon group-substituted imidazole such as 6,7-tetrahydrobenzimidazole, 1-hydroxymethylimidazole, 2-hydroxymethylimidazole, 4-hydroxymethylimidazole, 1
-(2-hydroxyethyl)imidazole, 2-
(2-hydroxyethyl)imidazole, 4-(2-hydroxyethyl)imidazole,
1-carboxymethylimidazole, 2-carboxymethylimidazole, 4-carboxymethylimidazole, 1-(2-carboxyethyl)imidazole, 4-(2-carboxyethyl)imidazole, 4-(2-carboxy-2-hydroxyethyl) Imidazole, 1-aminomethylimidazole, 4-aminomethylimidazole, 1-(2-aminoethyl)imidazole, 4-(2-aminoethyl)imidazole, 1-(3-aminopropyl)imidazole, 4
-(3-aminopropyl)imidazole, 2-(2
Imidazole substituted with a polar group-substituted hydrocarbon group such as -imidazolyl)imidazole, 4-(2-pyridine)imidazole, and 2-beizoylimidazole can be mentioned. Most preferred imidazoles (b) in the present invention
is a benzimidazole compound represented by the general formula below.

[Formula] (In the formula, R ¹ to R ⁶ are hydrogen or a group selected from arbitrary substituents. Among these, R ¹ and R ² , R ²
and each set of R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ is
They 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, 1,2-dimethylbenzimidazole, 5,6-dimethylbenzimidazole, 4,5,6-trimethylbenzimidazole, N-methyl-5,6-dimethylbenzimidazole, N -ethyl-5,6-dimethylbenzimidazole, 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, 1-methyl-4,5-dimethoxybenzimidazole,
Examples include 1-methyl-4-dimethylaminobenzimidazole, 1-methyl-4-aminobenzimidazole, and 1-methyl-4-trimethylsilylbenzimidazole. Other examples include 4-azabenzimidazole and 1-methyl-4-azabenzimidazole. Although the concentration of the imidazole (b) is not particularly limited, it is preferable to use it in a larger amount than the ruthenium compound (a). For example, imidazoles (b) are used in an amount exceeding 10 mol per gram atom of ruthenium in the reaction system,
It is desirable to use it within a range of ¹⁰⁷ mol or less.
Also, for reaction solution 1, imidazole (b)
It is preferable to use it in a concentration range of 10 ^-3 mol to 10 mol. Among the catalysts used in the present invention, hafnium,
Specific examples of the metal hydride (c) selected from lanthanum and niobium include H _f H ₂ , LaH ₃ and NbH, and at least one of these hydrides can be used in the present invention. The ratio of the metal hydride (c) used is not particularly limited, but it is usually the concentration of metal atoms in the metal hydride (c) relative to the concentration of ruthenium atoms in the ruthenium compound (a) in the reaction system. as a ratio of about 10 ^-2
It is preferably from about 10 ³ to about 10 ³ , particularly from about 10 -1 to about 10 ² . Another catalyst component that can be used in combination in the present invention is a halogen compound. 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. The halogen compounds exemplified above are ruthenium compounds (a), imidazoles (b), and metal hydrides selected from hafnium, lanthanum, and niobium (c).
In addition, it is a co-catalyst that may be used in combination, and one type or two or more types may be used in combination as necessary. When a halogen compound is used in combination, the ratio of the number of moles of the halogen compound to the gram atoms of ruthenium in the amount of ruthenium compound (a) used is about 10 ^-2 to 10 ³ , particularly about 10 ^-1 to 10 ² . desirable. The method for preparing the catalyst used in the method of the present invention includes ruthenium compounds (a) imidazoles;
(b), metal hydride (c), and other co-catalysts as necessary may be added separately to the reaction system to form catalytically active species within the reaction system, or ruthenium A complex or mixture formed from the compound (a) imidazoles (b) metal hydride (c) and other co-catalysts if necessary can also be added to the reaction system. The ruthenium compound (a) may be premixed with an organic diluent before use. The imidazoles (b) may also be used as organic diluents for other catalyst components. Furthermore, the imidazoles (b) do not necessarily need to be supplied as such to the reaction system, and may be formed within the reaction system. For example, in Advances in Heterocyclic
The method disclosed in Chemistry 12, P. 103-183 (1970) may be employed. 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 the solvent include tetrahydrofuran, dimethyl ether of diethylene glycol, dimethyl ether of tetraethylene glycol (tetraglyme), diethyl ether, diisopropyl ether, dioxane, 1,2-dimethoxybenzene, 1,2,3-
Ethers such as trimethoxybenzene and 18-crown-6; esters such as methyl acetate, ethyl acetate, butyl acetate, ethylene glycol diacetate, diethylene glycol diacetate, γ-butyrolactone, dimethyl-γ-butyrolactone, and δ-valerolactone. ; Sulfones such as sulfolane and dimethylsulfolane; Sulfoxides such as dimethyl sulfoxide and diethyl sulfoxide; N/N-dimethylformamide, N/N-
Diethylformamide, N/N-dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, N-isopropylpyrrolidone, N-propylpyrrolidone, N-butylpyrrolidone, N-octylpyrrolidone, N-cyclohexylpyrrolidone, N-benzylpyrrolidone, Amides such as polyvinylpyrrolidone and N-methyl-2-pyrrolidone; phosphoric triamides such as hexamethyl phosphoric triamide and hexaethyl phosphoric triamide;
N・N・N′・N′-tetramethylurea, 1.3-
Substituted ureas such as dimethyl-2-imidazolidonne; methanol, ethanol, butanol, t-
Alcohols such as butanol, dodecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, 2-methoxyethanol, ethylene glycol, diethylene glycol, and triethylene glycol; Carboxylic acids such as acetic acid, propionic acid, and benzoic acid; Phenols such as phenol and soresorcin ; Trimethylamine, triethylamine, N-methylmorpholine, aniline, N・N-
Dimethylaniline, N·N-dimethyl-o-toluidine, N·N-dimethyl-m-toluidine,
Amines such as N/N-dimethyl-p-toluidine, naphthylamine, N/N-dimethylnaphthylamine, 4-chloro-1-naphthylamine, 4-chloro-2-naphthylamine, 3-chloro-1-naphthylamine; pyridine, 2 -Hydroxypyridine, pyrrole, N-methylpyrrole, indole, pyrazole, 3,5-dimethylpyrazole,
Nitrogen-containing heterocyclic compounds such as imidazole, triazole, oxazole, isoxazole, benzoxazole, benzisoxazole, and benztriazine; Nitriles such as acetonitrile and benzonitrile; Ketones such as acetone and diphenyl ketone; Hexane, heptane, hexene, and cyclohexane Hydrocarbons such as , naphtha, and kerosene; Aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, dodecylbenzene, tetradecylbenzene, and hexadecylbenzene; Silicon compounds such as silicone oil; Chlorobenzene, fluorobenzene, and trifluoro Examples include halogen compounds such as methylbenzine and chloroform; carbonates such as ethylene carbonate and propylene carbonate. Among these, it is preferable to use a solvent selected from ethers, hydrocarbons, alcohols, and aromatic amines because the reaction rate is improved. Among these, it is preferable to use polyethers because they improve the selectivity of ethylene glycol production. As a solvent, a solvent having a boiling point higher than that of the reaction product of the invention, for example ethylene glycol, is preferred for separating the product by distillation. For example, if the purpose is to produce ethylene glycol, 760mm
It is preferable that Hg has a boiling point of 200°C or higher. In the method of the present invention, the ratio of carbon monoxide and hydrogen gas supplied to the reaction system is usually 20 to 20 molar ratio of carbon monoxide to hydrogen gas.
0.05, preferably in the range 5 to 0.2. 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 1Kg/cm ² -G, preferably 1000 to 50Kg/cm ² -G.
is within the range of Generally, the higher the pressure during the reaction, the better the reaction rate is, so the method of the present invention is characterized in that oxygen-containing organic compounds such as alkane polyols are produced even in a relatively low pressure region. Furthermore, the temperature during the reaction is usually 50 to 350°C, preferably 150 to 350°C.
It is in the range of 300℃. The time required for the reaction is usually 0.1
It ranges from 0.5 to 20 hours, preferably from 0.5 to 10 hours. The reaction is usually carried out under stirring conditions. According to the present invention, oxygen-containing organic compounds such as ethylene glycol and methanol are efficiently produced, and the excellent effect of suppressing the by-product of carbon dioxide can be obtained. In the method of the present invention, methanol, ethanol, ethylene glycol, 1,2-propanediol, glycerin,
Oxygenated organic compounds such as acetic acid, methyl acetate, methyl formate, glycerin, etc. can be isolated. Next, the method of the present invention will be specifically explained using examples. Example 1 After replacing the inside of a Hastelloy C autoclave with a capacity of 60 ml with argon, 0.1 milligram atoms of Ru ₃ (CO) ₁₂ , 10 mmol of N-methylbenzimidazole, 0.3 mmol of niobium hydride, and 10 ml of tetraglyme were added to the autoclave. and closed the autoclave. 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 260°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. Examples 2 to 5 The same procedures as in Example 1 were carried out except that the conditions shown in Table 1 were used. The results are shown in Table 1. Comparative Examples 1 and 2 The same procedure as in Example 1 was carried out except that niobium hydride was not added and the conditions shown in Table 1 were used. The results are shown in Table 1.

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Claims (1)

[Claims] 1. A method for producing an oxygen-containing organic compound by reacting carbon monoxide and hydrogen under heat and pressure in the presence of a catalyst, comprising a ruthenium compound (a), an imidazole (b), hafnium, and lanthanum. A method for producing an oxygen-containing organic compound, which comprises using a catalyst comprising (c) a hydride of a metal selected from