JPS5829728A - Preparation of alkane polyol - Google Patents

Abstract

PURPOSE:In preparing the titled compound by reacting carbon monoxide with hydrogen, to improve the yield in a low-pressure range, by carrying out the reaction in the presence of a catalyst comprising a ruthenium compound and a quaternary phosphonium halide in an aprotic polar solvent. CONSTITUTION:In the presence of a catalyst comprising a ruthenium compound and a quaternary phosphonium halide in an aprotic polar solvent such as a sulfone, e.g., sulfolane, a lactone, e.g., gamma-butyrolactone, etc., preferably an aprotic polar solvent having a dielectric constant[epsilon]of >=20, carbon monoxide is reacted with hydrogen usually at 2,000-1kg/cm<2>-G, preferably 1,000-50kg/cm<2>-G at 300-50 deg.C, preferably at 250-150 deg.C, to give the titled compound. The amount of the catalyst used is selected arbitrarily, and usually the concentration of ruthenium atom in the reaction system is preferably 10<-1>-10<-4> gram atom/l, and the concentration of the quaternary phosphonium halide is preferably 1- 10<-4>mol/l.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for producing alkane polyols, in particular ethylene glyfur, by reacting -carbon oxide and hydrogen in the presence of a catalyst. For more details,
The object of the present invention is to provide a method that has higher activity than conventional catalysts, yet can produce alkane polyols in high yields even in reactions under relatively low pressure conditions.

Conventionally, many methods using rhodium-based catalysts have been proposed as methods for producing alkane polyols by reacting -carbon oxide and hydrogen.

These methods using rhodium-based catalysts have fairly high catalytic activity, but in addition to the fact that rhodium-based catalysts are extremely expensive, in both methods, rhodium-based catalysts are released as rhodium metal inside the reactor after the reaction is completed. Otherwise, it has the disadvantage that it must be recovered and activated by some method before being reused because it is deposited in other places and inactivated. Therefore, although the method using a rhodium-based catalyst has a considerably high catalytic activity, it is difficult to adopt it as a method for economically producing an alkane polyol on an industrial scale.

In addition, other noble metal catalysts have been proposed to avoid the drawbacks of the rhodium catalysts. For example, as a noble metal catalyst other than rhodium catalyst, JP-A-55-1158
! No. 14, U.S. Pat. No. 4,170,605, 1. Am, C! hem, Soc,, 10
2.

6855 (1980), F, rd61 KO) 111
3 Ergas Petrochem,.

52.313 (1979), Eng. nt, Hlgh P.
Ressure 0onf.

(USA), 6th (1977), (1)-78-73
8 (1979) and T, 0ata1.61,359
(1980) and others propose a method using a ruthenium-based catalyst.

Methods using these ruthenium-based catalysts are economical because the catalyst itself is inexpensive, but
It is inferior to rhodium-based catalysts in activity, especially under low reaction pressure conditions. For example, the aforementioned U.S. Pat. No. 4,170,605 and et al.
H1gh Pressure 0onf.

(USA), 6th (1977) t(1), 735-7
3B (1979) proposes a method using a ruthenium complex catalyst formed from a specific ruthenium compound and a pyridine base ligand;
No. 58!14 proposes a method of using a solubilized ruthenium carbonyl complex as a catalyst, and the publication also discloses that cyclic amines, pyridines, purines, pyrimidine, piperazine, etc. are used as co-catalysts together with the ruthenium carbonyl complex. It is disclosed that amines, bis(triphenylphosphine) iminium oxides, alkali metal halides, alkaline earth metal halides, cobalt iodide, iron iodide, and the like can be used. However, there is no description in the publication that suggests that the reaction is carried out using a catalyst consisting of two components, a ruthenium compound and a quaternary phosphonium halide. Any of the ruthenium-based catalysts described in these prior art documents have no activity or
In particular, the activity is low under relatively low reaction pressure conditions,
Alkane polyols cannot be produced in high yields.

The present inventors conducted studies aimed at improving the above-mentioned drawbacks of ruthenium catalysts, and as a result, they found that the yield of ol was improved and arrived at the present invention.

That is, the present invention provides a method for producing an alkane polyol by reacting -carbon oxide and hydrogen in the presence of a catalyst and under heating and pressurizing conditions. )
This is a method for producing an alkane polyol, characterized in that the reaction is carried out in the presence of a catalyst consisting of:

The catalyst used in the process of the invention is a catalyst consisting of a ruthenium compound (IL) and a phosphonium halide (b). Here, specific examples of ruthenium compounds include ruthenium halides, carboxylates, inorganic acid salts, oxides, compounds complexed with various organic ligands, complex bonded with various inorganic ligands, etc. Examples include compounds such as More specifically, ruthenium chloride, ruthenium bromide, ruthenium iodide, ruthenium formate, ruthenium acetate, ruthenium nitrate, ruthenium dioxide,
! ! Ruthenium 11 oxide, Ru (FLCae) 5
It is useful because it forms an N carbonyl complex.
be able to. Among these ruthenium compounds (a), ruthenium compounds soluble in the reaction system are preferred.
Specifically, tetramethylphosphonium fluoride, tetramethylphosphonium chloride, tetramethylphosphonium bromide are used as a ruthenium compound complexed with carbon monoxide under the reaction conditions, or as at least one of hydrogen and organic ligands together with carbon monoxide. Methylphosphonium, tetramethylphosphonium iodide, tetraethylphosphonium fluoride, tetraethylphosphonium chloride, tetraethylphosphonium bromide, tetraethylphosphonium iodide, as well as nitetrabrobylphosphonium halide, tetrabutylphosphonium halide, tetrapentylphosphonium halide, tetrahexylphosphonium halide , tephenylphosphonium halide, triphenylmethylphosphonium halide, heptyltriphenylphosphonium halide, n-
Examples include hexadecyltriphenylphosphonium halide. Alternatively, as the quaternary phosphonium halide (b), a tertiary phosphine and an alkyl halide may be supplied to the reaction system to form the quaternary phosphonium halide within the reaction system.

In the process of the invention, the reaction of -carbon oxide and hydrogen is carried out in the presence of an aprotic polar solvent. Specific examples of the aprotic polar solvent include amides such as sulfolane, dimethylsulfone, and tetramethylsulpyrrolidone, substituted ureas such as N,N,N',N'-tetramethylurea, hexamethylphosphoric triamide, Examples include phosphoric acid triamides such as hexaethyl phosphate triamide, polyethers containing 4 or more oxygen atoms such as tetraglyme and 18-crown-6, and lactones such as γ-butyrolactone and dimethyl-γ-butyrolactone. can do. Among these aprotic polar solvents, it is preferable to use an aprotic polar solvent having a dielectric constant [ε] of 20 or more. In particular, it is preferable to use an aprotic polar solvent consisting of sulfones, lactones, ethers or amides because the reaction rate is improved.

atoms/l, preferably in the range 10-1 to 10-4 gram atoms/l. Furthermore, the ratio of the quaternary phosphonium halide (b) to the ruthenium compound (IL) in the quaternary phosphonium hala reaction system is usually 1 as the quaternary phosphonium halide to 1 gram atom of ruthenium.
It ranges from 0 to 10 mol, preferably from 50 to 1 mol. The method for preparing the catalyst used in the method of the present invention is to add a ruthenium compound and a quaternary phosphonium compound to the reaction system separately, and add them to the reaction system as an illusion of catalytic activity within the system. A method of forming catalytically active species can also be adopted.

0.05, preferably in the range of 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 1 kg/
14-G, preferably 1000 to 50 kg/-
The range is J-G. Generally, it is preferable to increase the pressure during the reaction because the reaction rate improves, but the method of the present invention is characterized in that alkanboliol is produced even in a relatively low pressure region.

Further, the temperature during the reaction is usually in the range of 500 to 50°C, preferably 250 to 150°C. The time required for the reaction is usually 20 to 0.1 hours, preferably 1 hour.
It ranges from 0 to 0.1 hours. The reaction is usually carried out under stirring conditions.

In the method of the present invention, the alkane polyol can be isolated by treating the reaction mixture after completion of the reaction by a conventional method such as distillation or extraction. The alkane polyol obtained by the method of the present invention contains ethylene glycol as a main component, a small amount of propylene glycol, a very small amount of glycerin, etc. In addition, Example 1 obtained by the method of the present invention After purging the inside of a stainless steel autoclave with an internal volume of 38 ml with argon, the molar ratio of this autoclave was 1.
/1 after pressurizing the mixed gas to 200 kq/-20
The mixture was heated to 0°C and reacted for 4 hours.

After the reaction was completed, the reaction mixture was cooled to room temperature and excess gas was discharged, and then the reaction mixture was taken out and analyzed by gas chromatography. The result was 3.10 mmo/ylJ)/-/
l/, Q, 77 mmo4 ethanol, 0.57 myn
ol ethylene glycol was produced. Further, as a result of gas chromatography analysis of the gas discharged after the reaction, it was found that 1 mmo/mop of methane and 5.85 mmop of carbon dioxide gas were produced.

Comparative Example 1 The reaction was carried out in the same manner as in Example 1, except that tetraphenylphosphonium chloride was replaced with cesium chloride. The result was 1.16 mmo1! of methanol N O, 06 mmo4 (Dx ta/-/l/, 0
．． 09mmo7 ethylene glycol, 0.23mmo
(lt:D Carbon dioxide gas was generated.

Comparative Examples 2 to 4 Example 1 except that tetraphenylphosphonium chloride in Example 1 was replaced with an alkali metal halide.
The reaction was carried out in the same manner. The results are shown in Table 1. Examples 2 to 4 The reaction was carried out in the same manner as in Example 1, except that triphenylmethylphosphonium iodide was used as the phosphonium salt and the amount added or the solvent was changed.

The results are shown in Table 2.

Examples 5 to 7 The reaction was carried out in the same manner as in Example 1, except that tetraphenylphosphonium iodide and tetraethylphosphonium iodide were used as the phosphonium salts. The results are shown in Table 2. Examples 8 to 10 The reaction was carried out in the same manner as in Example 1 except that the solvent and reaction time were changed. The results are shown in Table 5.

Comparative Example 5 The reaction was carried out in the same manner as in Example 1 except that the solvent was changed to acetic acid. The results are shown in Table 6.

Claims (1)

[Claims] (1) A method for producing an alkane polyol by reacting -carbon oxide and hydrogen in the presence of a catalyst and under heating and pressurizing conditions, comprising: a ruthenium compound (IL);
) and a quaternary phosphonium halide (b), and the reaction is carried out in an aprotic polar solvent. (2) The method according to claim (1), wherein the concentration of the ruthenium compound (a) in the reaction system is in the range of 10-1 to 10-4 gram atoms/l as ruthenium atoms. C5) The method according to claim (1), wherein the concentration of the quaternary phosphonium halide (1)) in the reaction system is in the range of 1 to 10-4 mol/e. (4) The usage ratio of quaternary phosphonium halide (b) is
(5) The quaternary phosphonium halide (b) is a quaternary phosphonium halide chloride, Claim H (method according to claim 1) which is quaternary phosphonium bromide or quaternary phosphonium iodide. (6) The non-protic polar solvent has a dielectric constant [ε
] is an aprotic polar solvent of 20 or more, the method according to claim (1).