JPS6054331A - Production of oxygen-containing organic compound - Google Patents

Abstract

PURPOSE:To obtain an oxygen-containing organic compound advantageously from carbon monoxide and hydrogen in high yield, by reacting the carbon monoxide with hydrogen in the presence of a ruthenium compound, an imidazole and metallic compound selected from hafnium, lanthanum and niobium together under heating and pressure conditions. CONSTITUTION:Carbon monoxide is reacted with hydrogen in the presence of a catalyst under heating and pressure conditions to produce an oxygen-containing organic compound, e.g. ethylene glycol or methanol. In the process, a catalyst consisting of (A) a ruthenium compound, (B) an imidazole, preferably benzimidazole based compound, and (C) a compound of a metal selected from hafnium, lanthanum and niobium is used to suppress the formation of carbon dioxide as a by-product and give the aimed compound in high yield. The concentration of the component (B) is 10-10<7>mol based on the gram atom ruthenium in the reaction system, and the concentration of the component (C) is about 10<-2>-10<3>, preferably 10<-1>-10<2> expressed in terms of the ratio between the concentration of the metallic atoms in the component (C) and the concentration of the ruthenium atoms.

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 oxide and hydrogen, for example, as disclosed in JP-A-55-1.
No. 15834, U.S. Pat. No. 4.1'70,605, J
,A+n,Chem,Soc,+1026855 (1
980), Erdol Kohle ErgasPe
trochem, +32+313 (1979),
Int, formerly ghPressure Conf, (US
A), 6th, (1) 733-738 (1979)
and J. Catl., 61, 359 (1980). 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, in JP-A-55-115834, amines, pyridines, cyclic amines such as purine, pyrimidine, and piperazine, and bis(triphenylphosphine)iminium are used as cocatalysts in addition to solubilized ruthenium carbonyl complexes. It is disclosed that halides, alkali metal halides, alkaline earth metal halides, cobalt iodide, iron iodide, etc. can be used.

Also, the above-mentioned U.S. Pat. No. 4,170,605 and In
t,llgh Pressure Conf, (U
SA), 6 th (1) 733-73B (19
79) proposes a method using a ruthenium complex catalyst formed from a specific ruthenium compound and a pyridine base group 41'.

Furthermore, JP-A-56-123925 proposes a method in which a catalyst consisting of a ruthenium compound, a compound of a group 1 metal other than ruthenium, and a co-catalyst component is used in 1, and an alkali metal is used as a co-catalyst component. It is proposed to use halide compounds, alkaline earth metal halide compounds, quaternary ammonium halide compounds, quaternary iminium halide compounds, pyridine, or substituted pyridine compounds.

JP-A-56-100728 discloses ruthenium compounds, bosphonium halide, ammonium halide 1
An embodiment in which `` is used in combination is shown.

Furthermore, JP-A No. 55-9088 describes a method for simultaneously producing alkanol esters and glycol esters by carrying out the reaction in the coexistence of a carboxylic acid such as acetic acid, trifluoroacetic acid, monofluoroacetic acid, etc., in which a ruthenium compound is used as a catalyst. An embodiment is shown in which a phosphonium halide or an 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 compound selected from hafnium, lanthanum, and niobium in the combined catalyst system, and have thus arrived at the present invention.

That is, the present invention provides a method for producing an oxygen-containing organic compound by reacting -carbon oxide 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, characterized by using a catalyst consisting of the compound (C1).

Among the catalysts used in the method of the present invention, specific examples of the ruthenium compound + al include ruthenium halides, carboxylates, inorganic acid salts, oxides, compounds complexed with various organic ligands, and various ruthenium compounds. Examples include compounds that have complex bonds with inorganic ligands. More specifically, ruthenium chloride, ruthenium bromide, ruthenium iodide, ruthenium formate, ruthenium acetate, ruthenium nitrate, ruthenium dioxide, ruthenium tetroxide, Ru (ac
ac), (C1l) (CIl) Ru (Co), (
C1l) Ru, Ru (Co), Ru (Co), R11 (Co), HRu (Co
), II Ru(CO), (Ru(Co)Cj), etc.Also, ruthenium metal in the form of fine powder is supplied to the reaction system, where a soluble carbonyl complex is formed and used. You can also do that.

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-' gram atom/β, particularly preferably 2X10-' to 10'# Durham atoms/l range.

On the other hand, imidazoles (bl) include imidazole and imidazole derivatives having arbitrary substituents.

Preferred imidazoles (bl) are represented by the following general formula.

1 (in the formula, R', ``R'' and R41, hydrogen, and optional substituents. Among these, R1 and ♂, ♂ and RtR
1 and R'+7) 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 groups, acyl groups such as cetyl, butyroyl, benzoyl, and toluoyl, amino groups, substituted amino groups such as dimethylamino and diethylamino, methoxy, and ethoxy. Alkoxy groups such as cyano groups, isocyano groups, 21-mouth groups, silyl groups, "r-alkyl-substituted silyl groups such as trimethylsilyl, and methyl,
Hydrocarbon groups such as ethyl, n-p1:1 pyl, 1so-propyl, n-butyl, 1so-butyl, tar L-butyl, octyl, dodecyl, hexadecyl, cyclohexyl, phenyl, benzyl, etc., dipolar groups There are substituted hydrocarbon groups.

Among these imidazoles (bl), imidazole Ii (b) which is preferably used includes imidazole, hydrocarbon Iff-converted imidazole, and hydroxyalkyl group i￥
lj! ! imidazole, imidazole substituted with a carboxyalkyl group, imidazole substituted with an aminoalkyl group, imidazole substituted with a polar group-substituted hydrocarbon group such as polyvinylimidazole, and specifically, imidazole, N-methylimidazole, N-ethylimidazole, N-propylimidazole, N-isopropylimidazole, N-butylimidazole, 2-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, 1.2-1-rimethyleneimidazole, 1.5-trimethyleneimidazole, 4.5-1
-Hydrocarbon-substituted imidazole such as rimethylene imidazole, 4.5,6.7-titrahydrobenzimidazole, 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-carboxyethyl)imidazole -2-hydroxyethyl)imidazole, I-aminomethylimidazole, 4-aminomethylimidazole, 1-(2-aminoethyl)imidazole, 4-(2-aminoethyl)
Imidazole, 1-(3-aminopropyl)imidazole, 4-(3-aminopropyl)imidazole, 2-(
Imidazole substituted with a polar group-substituted hydrocarbon group such as 2-imidazolyl)imidazole, 4-(2-pyridine)imidazole, and 2-benzoylimidazole can be mentioned.

The most preferred imidazoles (bl are benzimidazole compounds represented by the following general formula) in the present invention.

(In the formula, R1 to R6 are hydrogen or a group selected from arbitrary substituents. Among these, each set of R1 and R2, ♂ and R3, ♂ and R4, R4 and R5 are connected to each other, and the divalent or a hydrocarbon group substituted with a polar group.) Examples of such benzimidazole compounds include the following.

Benzimidazole, N-methylbenzimidazole,
N-ethylbenzimidazole, N-n-propylbenzimidazole, N-1so-7'robilbenzimidazole, N-tert-butylbenzimidazole,
N-n-butylbenzimidazole, N-phenylbenzimitazole, N-ben0 Zylbenzimidazole, N-cyclohexylbenzimidazole, N-octylbenzimidazole, N-1
Decylbenzimidazole, N-hexylbenzimidazole, 4-methylbenzimidazole, 1
．． 2-dimethylbenzimidazole, 5. -dimethylbenzimidazole, 4,5,6-dimethylbenzimidazole, N-methyl-5,6-dimethylbenzimidazole, N
-ethyl-5,6-dimethylbenzimidazole, N-
1so-p11pyru-5,6-dimethylbenzimidazole, 5.6-dimethoxybenzimidazole, 4.5
-I rimethylene benzimidazole, naphtho (1,2
-d] imidazole, nut (2,3-d) imidazole, l-methyl-4-methoxybenzimidazole, 1
-Methyl-5-methoxybenzimidazole, 1-methyl-4,5-dimethoxybenzimidazole, l-methyl-4-dimethylaminobenzimidazole, 1-methyl-4-aminobenzimidazole, 1-methyl-4-
Examples include trimethylsilylbenzimidazole.

Others include 4-azabenzimidazole, 1
-Methyl-4-azabenzimidazole and the like can also be exemplified.

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 +8).

For example, imidazoles (bl) are preferably used in a range of more than 10 moles and less than 109 moles per 1 gram atom of ruthenium in the reaction system.
1, imidazoles (bl) are preferably used in a concentration range of lo-3 mol to 10 mol.

Among the catalysts used in the present invention, the metal compound (C) is
It is at least one metal compound selected from hafnium, lanthanum, and niobium.

Such metal compounds include, for example, metal halides selected from hafnium, lanthanum and niobium;
Examples include carboxylic acid salts, inorganic acid salts, oxides, hydrides, and compounds complexed with various ligands. More specifically, halides such as hafnium chloride, hafnium odoride, lanthanum chloride, lanthanum bromide, niobium chloride, and niobium bromide, alkoxide compounds such as niobium ethoxy], ranknium propoxide, ranknium acetate, etc. Examples include carboxylic acid compounds, oxides such as hafnium oxide, lanthanum oxide, and niobium oxide, among which 1lfl12.1. al13
．． Hydrides such as Nb1l are preferred.

The proportion of metal compound (C1 used is not particularly limited, but is usually ruthenium compound + al in the reaction system)
The ratio of the atomic concentration of the metal compound (C1) to the concentration of ruthenium atoms in the metal compound (C1) is preferably about 10@-2 to about 10@-2 to about 10@-2 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 soot; halides such as alkali metals, alkaline earth metals, aluminum, and phosphorous; , quaternary ammonium halide, quaternary phosphonium halide, iminium halide, alkyl halide, aryl halide, and the like.

The halogen compounds exemplified above include ruthenium compounds (
a) Imidazole [It is a co-catalyst that may be used in combination with (b) and a metal compound IC1 selected from hafnium, lanthanum and niobium, and if necessary, one type or two or more types may be used in combination. Ru.

When using halogen compounds together, use ruthenium compounds (
The ratio of the number of moles of the halogen compound to the gram atom of ruthenium in the amount of al used is about 1 to 103. and (is preferably about 10-' to 102).

The method for preparing the catalyst used in the method of the present invention is to separately add a ruthenium compound, Tal imidazole (BL), a metal compound (C1, and other cocatalysts as necessary) to the reaction system. It is also possible to adopt a method of forming catalytically active species, or to add a complex or mixture formed from a ruthenium compound ta + imidazole 1 + b + metal 4 compound (C1 and other co-catalysts depending on the requirements) into the reaction system. It can also be added.

The ruthenium compound +al may be premixed with an organic diluent before use. Also, imidazole I, n
(1+l may be used as an organic diluent for other catalyst components.

Furthermore, imidazoles (bl) do not necessarily need to be supplied as such to the reaction system, and may be formed within the reaction system, for example,
cyclic(:l+emistry 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 can be used as long as it is inert to the reaction, and the organic diluent described in "1" can also be used as is. Specifically, the solvent includes tetrahydrofuran,
Dimethyl ether of diethylene glycol, dimethyl ether of tetraethylene glycol (tetraglyme)
, diethylconythiron, 1.2-dimethoxybenzene, 1.2.3-trimethoxybenzene, 18-crown-6 and other ethers; methyl acetate, ethyl acetate, butyl acetate, ethylene glycol diacetate, diethylene glycol diacetate, Esters such as T-butyrolactone, dimethyl-γ-butyrolactone, and δ-valerolactone; Sulfones such as sulfolane and dimethylsulfolane; Sulfoxides such as dimethylsulfoxide and diethylsulfoxide; N, ? l-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, N-isopropylpyrrolidone, N-propylpyrrolidone, N-butylpyrrolidone, N-octylpyrrolidone, N -Amides such as cyclohexylpyrrolidone, N-benzylpyrrolidone, polyvinylpyrrolidone, and N-methyl-2-pyrrolidone; Phosphoric acid triamides such as hexamethylphosphoric triamide and hexaethylphosphoric triamide iN, N, N:
Substitution of N'-tetramethylurea, 1,3-dimethyl-2-imidazolidon, etc. Alcohols such as glycol, diethylene glycol and triethylene glycol; Acid-resistant, carboxylic acids such as propionic acid and benzoic acid; Phenols such as phenol and tresorcin; Trimethylamine, triethylamine, N-methylmorpholine, aniline, N,N-
Dimethylaniline, N,N-dimethyl-〇toluidine, N,N-dimethyl-m-1-luidine, N,N-dimethyl-p-toluidine, naphthylamine, N. N-dimethylnaphthylamine, 4-chloro-1-naphthylamine, 4-chloroL1-2-naphthylamine, 3-chloro11-
Amines such as 1-naphthylamine; pyridine, 2-H
゛roxypyridine, pyrrole, N-methylpyrrole, indole, pyrazole, 3,5-dimethylpyrazole,
Indazole, triazole, oxazole, isoxazole, benzoxazole, benzisoxazole, benzdoor 6 Nitriles such as riazine and benzonitrile; ketones such as acetone and diphenylketone; carbonization of hexane, heptane, hexene, cyclohexane, naphtha, and kerosene Water i; Aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, dodecylbenzene, tetradecylbenzene, hexadecylbenzene; Silicon compounds such as silicone oil; Chlorobenzene, fluorobenzene, trifluoromethylbenzene, chloroform, etc. Halogen compounds; carbonates such as ethylene carbonate and propylene carbonate can be exemplified. 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, polyethers are preferably used 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.

8 For example, if the purpose is to produce ethylene glycol,
It is preferable to have a boiling point of 200° C. or higher at 760 mm and 11 g.

In the method of the present invention, the ratio of carbon monoxide and hydrogen gas supplied to the reaction system is usually 20 to 0.05, preferably 5 to 0.2 as a molar ratio of carbon monoxide to hydrogen gas. range.

In the method of the present invention, the reaction is carried out under heating and pressure conditions.
be done. The pressure during the reaction is usually 2000 to 1 kg.
/cIa-G, preferably 1000 to 50k
g/CJJ-G range. Generally, the higher the pressure during the reaction, the better the reaction rate (G111), but 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. Further, the temperature during the reaction is usually 50 to 350°C, preferably 150 to 300°C.
℃ range. The time required for the reaction is usually in the range of 0.1 to 20 hours, preferably 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, the reaction mixture after the completion of the reaction is treated by a conventional method such as distillation or extraction to produce methanol, ethanol, ethylene glycol, 1,2-propanediol, glycerin, acetic acid, methyl acetate, methyl formate, glycerin. It is possible to isolate oxygen-containing organic compounds such as

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 an internal capacity of 60 ml with argon, Ru was added to the autoclave.
3 (CO)20+, 1 mg atoms, 10 mmol of imidazole, 0.3 mmol of niobium hydride and 10 ml of tetraglyme were added and the autoclave was closed. Next, a mixed gas with a carbon monoxide/hydrogen molar ratio of 1/l was introduced into the reaction system from the gas inlet pipe into the autoclave, and the pressure was increased to 500 to 550 k.
g/cIil, and the reaction was carried out at 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 Same as Example I except that niobium hydride was not added and the conditions shown in Table 1 were used. , Kazuo Wakasugi, Commissioner of the Japanese Patent Office.Indication of the case.Showa SG year patent application No. ISQθ3S.Name of the invention.Process for producing oxygen-containing organic compounds 3.Amendment person.Relationship with the case.Patent applicant S.Increase due to the amendment. Number of inventions: 0 Column for detailed description of the invention in the specification to be amended Contents of the amendment The descriptions in page S/left line to line 9 of the specification are amended as follows.

Claims (1)

[Claims] (1) In a method for producing an oxygen-containing organic compound by reacting -carbon oxide and hydrogen under heat and pressure in the presence of a catalyst, a ruthenium compound (al, imidazole (bl) and a metal selected from hafnium, lanthanum and niobium) is used. A method for producing an oxygen-containing organic compound, characterized in that a catalyst consisting of a compound (C1) is used.