JPS58225031A - Production of oxygen-containing organic compound - Google Patents

Abstract

PURPOSE:The reaction of carbon monoxide and hydrogen is carried out in the presence of a catalyst consisting of ruthenium and an imidazole under heating and pressure to achieve high-yield of a product of oxygen-containing organic compound such as ethylene glycol, methanol or others. CONSTITUTION:The reaction between carbon monoxide and hydrogen is carried out in the presence of (A) a Ru compound and (B) an imidazole, at 1,000-50kg/ cm<2> and 150-300 deg.C for 0.5-10hr to produce oxygen-containing organic compounds including ethylene glycol. As component A, is cited ruthenium chloride, ruthenium acetate or its complex in a concentration of 2X10<-11>-10<-4>g.atom/l as Ru element and, as component B, is optimal benzimidazole of the formula in a concentration of 10<-3>-10mol per liter of the reaction mixture. Further it is preferred that the ratio of component B to 1g.atom of metallic Ru is 10- 10<7>mol.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for directly producing oxygen-containing organic compounds such as ethylene glycol, methanol, and ethanol from -carbon oxide and hydrogen.

As a method for directly producing ix-containing organic compounds such as ethylene glycol, methanol, and ethanol from carbon monoxide and hydrogen, a catalyst system containing a metal of group 1 of the periodic table, such as a rhodium-based catalyst, is known. Among these conventionally known methods, the method using a rhodium catalyst is
Although the catalytic activity is quite high, in addition to the fact that the price of the rhodium-based catalyst is extremely high, in any method, the rhodium-based catalyst becomes inactive as rhodium metal after the reaction is completed, and cannot be easily recovered and reused. There is a drawback.

Therefore, the method using a rhodium-based catalyst is difficult to adopt as a method for economically producing oxygen-containing organic compounds such as ethylene glycol on an industrial scale, although the catalytic activity is quite high.

In addition, examples of noble metal catalysts other than the rhodium catalysts include JP-A-55-115834 and USP No. 4.17.
No. 0,605, J, Am, Ohem, 5ac-+
102.6855 (1980), Erdol Koh
le Erdgae Petrocham+ 32+3
13 (1979), Int, HJ (h Pressu
re 0onf, (USA).

6th (1977), (1), 733-738 (197
9), JP-A-57-82327, JP-A-57-823
No. 28, etc., proposes a method using a ruthenium-based catalyst. 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 41170,6
05 and nt, H14h PressureQo
nf, (USA), 6th (1977) + (1) 73
3-738 (1979) proposes a method using a ruthenium complex catalyst formed from a specific ruthenium compound and a pyridine base ligand;
No. 5-115834, JP-A No. 57-82328, etc. propose a method of using a solubilized ruthenium carbonyl complex as a catalyst. Further, in these publications, in addition to the ruthenium carbonyl complex, Lewis bases such as amines, pyridines, -::-shaped amines such as purine, pyrimidine, piperazine, etc.

Its use as a cocatalyst is disclosed.

Further, JP-A No. 56-123925 G discloses a method of using moss, a ruthenium compound, and a compound of another Group I metal such as rhodium. This publication also describes the use of alkali metal or alkaline earth metal compounds such as decogenides, carboxylic acid salts, nitrogen-containing cations, or bases such as ammonium salts, iminium salts, pyridines, etc. as cocatalysts. is disclosed.

However, no matter which of these ruthenium-based catalysts is used, the activity, especially under low pressure conditions, cannot be said to be good.
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 by using a catalyst system comprising a ruthenium compound and an imidazole.

That is, the present invention provides a method for producing an oxygen-containing organic compound by reacting -carbon oxide 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 in the presence of a catalyst.

The catalyst used in the method of the invention is a catalyst consisting of a ruthenium compound (a) and an imidazole (b). Here, specific examples of the ruthenium compound include, for example, ruthenium genides, 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(00)2 , (05H5)
2Ru, Ru5(co)12, Ru(co)2-1R
u6(00)? H2Ru4ca 0)13, Hb R
ua (OO)12, (Ru(Co)5 J2,1
2 etc. can be exemplified. 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 1 tl-'' Durham atom/l.

Particularly preferred is a range of 2.times.10''-' to 10@-4 gram atoms/l.

On the other hand, imidazoles (1) include imidazole and imidazole derivatives having arbitrary substituents.

Preferred compounds as the imidazoles (b) are represented by the following general formula.

1 (wherein R1, R2, R6 and R4 are hydrogen and arbitrary substituents. Among these, R1 and R2, R3 and R
Each set of 4, R1 and R4 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 acetyl, butyroyl, benzoyl, toluoyl,
Amine groups, substituted amine groups such as dimethylamino and diethylamino, alkoxy groups such as methoxy and ethoxy, alkyl-substituted silyl groups such as cyanide groups, isocyano groups, nitro groups, silyl groups and trimethylsilyl, as well as methyl, ethyl, n-propyl, 18o-propyl, n-butyl, 1s
o-butyl, tert-butyl, octyl, dodecyl,
There are hydrocarbon groups such as hexadecyl, cyclohexyl, 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, and folivinyl. Imidazole substituted with a polar group-substituted hydrocarbon group such as imidazole, 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, kJ
-Methyl-4-ethylimidazole, 1-phenylimidazole, 4-phenylimidazole, benzimidazole, 1,2. ) rimethylene imidazole, 1.5
-) rimethyleneimidazole, 4.5-) rimethyleneimidazole, hydrocarbon group-substituted imidazole such as 4,5,6.7-titrahydrobenzimidazole, 1-hydroxymethylimidazole, 2-hydroxymethylimidazole, 4-hydroxy Methylimidazole, 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 substituted with a polar group-substituted hydrocarbon group such as imidazole, 4-(2-aminoethyl)imidazo-imidazole, and 2-benzoylimidazole can be mentioned.

The most preferred imidazoles (1,) in the present invention are:
Benzimidazole threading represented by the following general formula (wherein R1 to R6 are hydrogenated groups selected from arbitrary substituents. Among these, R and R2, R2 and R5
, R5 and R4, ' Each set of R4 and R5 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-1so-propylbenzimidazole, N-1ert-butylbenzimidazole, N-
n-Butylbenzimidazole, N-phenylbenzimidazole, N-penzylbenzimitazole, 4-methylbenzimidazole, 5.6-dimethylbenzimidazole, 4,5.6-)limethylbenzimidazole, N- Methyl-5,6-dimethylbenzimidazole,
N-ethyl-5,6-dimethylbenzimidazole, N
-1so-propyl-5,6-dimethylbenzimidazole, 5,6-simethoxybenzimidazole, 4.5
-) Rimethylenebenzimidazole, 1-methyl-4-dimethylaminobenzimidazole, 1-methyl-4-aminobenzimidazole, 1-methyl-4
-Trimethylsilylbenz In the present invention, one or more compounds selected from imidazoles (b) are used in the reaction system,
It is characterized in that it is used in combination with the ruthenium compound (a). , l The concentration of the imidazole (a) is not particularly limited, but the concentration of the ruthenilated locus (a) is not particularly limited.
) (It is preferable to use a larger amount than this).

The imidazoes (a) are preferably used in an amount of more than 10 moles and less than 10 moles per gram atom of ruthenium in the reaction system. Reaction liquid 11 again! In contrast, the imidazole (1) is 10-3 mol to 10
It is desirable to use a molar concentration range.

In the present invention, other catalyst components can be used in combination with the ruthenium compound (a) and imidazole (b). Such compounds include Group W) of the periodic table.
There is a compound of at least one metal selected from the metals of Group 1 and Group 1 other than ruthenium, and halides, carboxylates, inorganic acid salts, oxides, and various ligands of these metals, such as -oxidized Examples include compounds having complex bonds with carbon.

Other catalyst components that can be used in combination include halogen compounds.

Halogen compounds include iodine, bromine, chlorine, etc.
- Elemental halogen, hydrogen halides such as hydrogen iodide, hydrogen bromide, hydrogen chloride, hydrogen fluoride, halides such as alkali metals, alkaline earth metals, aluminum, phosphorus, etc.
Examples include class ammonium halides, quaternary phosphonium halides, iminium halides, alkyl halides, and aryl halides.

More specifically, these compounds include, for example, alkali metal halides such as lithium fluoride, lithium chloride,
Lithium bromide, lithium iodide, sodium fluoride, Fium chloride, sodium bromide, sodium iodide, potassium fluoride, potassium chloride, potassium bromide, potassium iodide, rubidium chloride, rubidium bromide, rubidium iodide , cesium fluoride, ruhalide, etc. can be used, specifically, tetramethylammonium chloride, tetramethylammonium bromide, 8
, tetramethylammonium iodide, tetramethylammonium fluoride, tetraethylammonium chloride, tetraethylammonium bromide, tetra n-propylammonium halide, tetra n-butylammonium halide,
Pyridinium halides such as trimethylbenzylammonium halide, triethylbenzylammonium halide, triisopropylbenzylammonium halide, ZaraN-methylpyridinium halide, 1-methyl-2-hydroxypyridinium halide, methyl-4-dimethylaminopyridinium halide, methyl-1 -Imidazolium halides such as methylimidazolium halide and ethyl-1-methylimidazolium halide. Examples of quaternary phosphonium halides include tetramethylphosphonium chloride, tetramethylphosphonium iodide, tetramethylphosphonium bromide, tetramethylphosphonium chloride, tetramethylphosphonium fluoride, tetium halide iodide, tetraphenylphosphonium halide, and triphenylmethylphosphonium halide. , triphenylethylphosphonium halide, etc. Iminium halide includes bis(triphenylphosphine) iodide.
These include iminium, bis(triphenylphosphine)iminium bromide, and his(triphenylphosphine)iminium chloride. Alkyl halides and aryl halides include halides of alkyl groups and aryl groups having about 1 to 20 carbon atoms, and specifically, methyl iodide, ethyl iodide,
Ethyl bromide, ethyl chloride, isopropyl iodide, isopropyl bromide, isopropyl chloride, iodide. -butyl, bromide n
Examples include alkyl halides such as -butyl and n-butyl fluoride, and aryl halides such as phenyl iodide, phenyl bromide, benzyl iodide, and benzyl bromide.

The co-catalysts exemplified above are co-catalysts that may be further used in combination with the ruthenium compound (a) and the imidazoles (b), and one type or two or more types may be used in combination as necessary.

When using compounds of metals from Groups ■, Group ■, and Group ■ of the periodic table other than ruthenium, the combined ratio is expressed as the ratio of the number of Durham atoms in the compounds of these metals to 1 gram atom of ruthenium in the reaction system. , usually about 10-2 to about 10
2, particularly from about 10@-1 to about 10.

When a halogen compound is used in combination, the ratio of the number of moles of the halogen compound to the number of Durham atoms of ruthenium in the amount of ruthenium compound (a) used is about 10-2 to 1.
03, particularly about 10-1 to 102.

The method for preparing the catalyst used in the method of the present invention includes a ruthenium compound (1) and an imidazole (b).
Furthermore, if necessary, it is also possible to adopt a method in which other co-catalysts are separately added to the reaction system to form catalytically active species within the system. Complexes or mixtures formed from other co-catalysts can also be added to the reaction system depending on the requirements.

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, embodiments in which the imidazoles (b) are formed within the reaction system are also exemplified, for example, Advances 1nHe
Terocyclic Chemistry 12y
P, 103 to 183 can be used, and the above 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, r-butyrolactone, dimethyl-r-butyrolactone, δ-valerolactone, and other esters; sulfolane, dimethylsulfone, and other sulfones; dimethylsulfoxide, diethylsulfoxide, etc. sulfoxides of
N,N-dimethylformamide, N,N-diethylformamide, NlN-dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, N-isopropylpyrrolidone, N-propylpyrrolidone, N-butylpyrrolidone, N-octylpyrrolidone, glycol , alcohols such as triethylene glycol sodium; carboxylic acids such as acetic acid, propionic acid, and benzoic acid; phenols such as phenol and resorcinol; pyridines such as trimethylamine and triethylamine; nitriles such as acetonitrile and benzonitrile; acetone and diphenyl ketone Examples include ketones such as hexane, heptane, hexene, cyclohexane, naphtha, and kerosene; 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.

Moreover, imidazoles can also be used as a solvent.

In the method of the present invention, the reaction is carried out in the first step supplied to the reaction system. The pressure during the reaction is usually 2000 to 1
kg/cm2-0, preferably 1000 to 5o
kg/a;'-a range. Generally, a higher pressure during the reaction is preferable because it improves the reaction rate, 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. The temperature during the reaction is usually 50 to 650°C, preferably 150 to 30°C.
It is in the range of 0°C. 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.

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 obtain methanol, ethanol, ethylene glycol, 1,2-propanediol, 1% "acid, lf[methyl, methyl formate]. It is possible to isolate oxygen-containing organic compounds such as

Next, the method of the present invention will be specifically explained using examples.

Decoration Example 1 After replacing the inside of a Hastelloy C autoclave with an internal capacity of 60 me with argon, Ru3 was added to the autoclave.
(00) 120.4 milligram atoms, imidazole 40
mmol, and N-methylpyrrolidone (NMP) 10m
The autoclave was closed.

Next, carbon monoxide/
A mixed gas having a hydrogen molar ratio of 1/1 was introduced into the reaction system, and the reaction was carried out at a pressure of 500 to 550 kg10n2 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.

Examples 2 to 55 Example 56 using the conditions shown in Table 1 in Example 1
~58 The same procedure as in Example 16 was carried out except that the compound shown in Table 2 was used as the l'(u compound. The results are shown in Table 2.

/ Examples 59 to 61 Put Ru (CO), 2 and imidazole compound in the amounts shown in Table 3 into an autoclave, and introduce a mixed gas with a carbon oxide/hydrogen molar ratio of 1/1 into the reaction system. The reaction was carried out under the conditions shown in Table 5. The results are shown in Table 6.

/ / Examples 62 to 69 Ru (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 oxide/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.

Example 70 The same procedure as in Example 1 was carried out except that the amount of imidazole used was 2 mmol and the reaction time was 1 hour. The results are shown in Table 5.

Example 71 In Example 3, the amount of 1-methylimidazole used was 0.
．． The same procedure was carried out except that 5 mm IJ mol was used. The results are shown in Table 5.

Procedural amendment dated July 4, 1976 Kazuo Wakasugi, Commissioner of the Patent Office1, Indication of the case, Patent Application No. 108339, filed in 19832, Name of the invention, Process for producing oxygen-containing organic compounds, 3 Person making the amendment, 5 Amendment In Column 6 of Detailed Description of the Invention in the Subject Specification, Table 1 (Continued) on page 26 of the Specification of Contents of Amendment, the numerical values in the "Product" section of Examples 38 and 69 are amended as follows. do.

Claims (1)

[Scope of Claims] (1) A method for producing an oxygen-containing organic compound by reacting -carbon oxide and hydrogen in the presence of a catalyst and under heating and pressurizing conditions, comprising: a ruthenium compound (a) and an imidazole ( A method for producing an oxygen-containing organic compound, characterized in that the reaction is carried out in the presence of a catalyst consisting of b). (2) A method for producing an oxygen-containing organic compound by reacting -carbon oxide and hydrogen in the presence of a catalyst and under heating and pressurizing conditions, consisting of a ruthenium compound (-) and an imidazole (b), (a ) The method for producing an oxygen-containing organic compound according to claim (1), characterized in that a catalyst is used in which the number of moles of (→ is 10 to 107 moles per gram atom of ruthenium metal in ). (6) The oxygen-containing organic compound is methanol, ethane,
Claims (1) or (2), characterized in that the compound is one or more compounds selected from ethylene glycol, 1,2-propanediol, acetic acid, methyl acetate, and methyl formate. Production method. (4) The imidazole (b) is a benzimidazole compound.
The method for producing an oxygen-containing organic compound according to item 1) or item (2). (5) The manufacturing method according to claim (1), (2) or (4), wherein the oxygen-containing organic compound is ethylene glycol.