JPS609733B2 - Production method of alkanpolyol - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for producing alkane polyols, particularly ethylene glycol, by reacting carbon monoxide and hydrogen in the presence of a catalyst.

More specifically, the present invention provides a method that has higher activity than conventional catalysts and 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 monoxide and hydrogen.

Although the catalytic activity of these methods using rhodium-based catalysts is quite high, "In addition to the fact that the cost of rhodium-based catalysts is extremely high, in both methods, rhodium-based catalysts are released as rhodium metal inside the reactor after the reaction is completed." Alternatively, it has the disadvantage that it must be collected and reactivated in some way to be deactivated by placing it in another location.Therefore, methods using rhodium-based catalysts have a considerably high catalytic activity. Nevertheless, it is difficult to adopt this method as an economical method for producing alkane polyols on an industrial scale.Furthermore, 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,
Tsubaki Seki Publication No. 55-115834, U.S. Patent No. 41
No. 70605, J. Am. Chem. Soc. ,
102, 6855 (1980), Erd0, I Ko
hleErscales Petrochem. , 32, 313
(1979), lnt. High Pressure
Conf. (USA), 6m (1977), [1], 7
33-738 (1979) and J. Catal. 61
, 359 (1980), etc., propose a method using a ruthenium-based catalyst. Methods using these ruthenium-based catalysts are economical because the catalysts themselves are inexpensive, but they are inferior in activity, particularly under low reaction pressure conditions, compared to rhodium-based catalysts. For example, the US Pat. No. 4,170,605
No. specification and lnt. High PressureC
onf. (USA), 6m (1977), [1], 73
3-738 (1979) proposes a method using a ruthenium chain catalyst formed from a specific ruthenium compound and a pyridine base ligand;
Japanese Patent No. 1115834 proposes a method using a solubilized ruthenium carbonyl complex as a catalyst. It is disclosed that cyclic amines, bis(triphenylphosphine) iminium halides, alkali metal halides, alkali metal halides, cobalt iodide, iron iodide, and the like can be used. However, there is no description in the publication that suggests carrying out the reaction using a catalyst consisting of two components, a ruthenium compound and a quaternary phosphonium halide. Even if any of the ruthenium-based catalysts described in these prior art documents are used, the activity, particularly under relatively low reaction pressure conditions, is low, and alkane polyols cannot be produced in high yields. The present inventors conducted research with the aim of improving the drawbacks of ruthenium catalysts as described above, and as a result, using a catalyst consisting of a ruthenium carbonyl body and a quaternary phosphonium halide, the present inventors conducted research in an aprotic polar solvent. The inventors have discovered that when the reaction is carried out, the activity is improved and the yield of the alkane polyol is improved, and the present invention has been achieved.

That is, the present invention provides a method for producing an alkane polyol by reacting carbon monoxide 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 (1) and (2).

The catalyst used in the method of the present invention is a catalyst consisting of a ruthenium carbonyl body 'a} and a phosphonium halide 'a}.

Here, specifically as a ruthenium carbonyl rust body,
For example, (C5 public) (CH3) Ru(CO)2, Ru3
(CO), 2, Ru (CO) reed: Ru6 (CO) Kamahi 2
RL(CO),8, ratio Ru4(CO),2, [Ru(C
Examples include ruthenium compounds having at least one CO as a ligand such as O)3CI2]2. The catalyst used in the method of the present invention is a ruthenium carbonyl complex formed in a reaction system in the presence of carbon monoxide and hydrogen under heated and pressurized conditions. is formed, it is not necessarily necessary to initially charge the ruthenium compound in the form of a ruthenium complex to the reactor before starting the reaction. That is, with regard to the ruthenium-power luponyl complex constituting the catalyst of the present invention, as long as the ruthenium-power luponyl complex is formed in the reaction system, the method of the present invention can be used to form any of the following ruthenium carbonyl anchors. The use of ruthenium compounds is also encompassed by the method of the invention. Examples of ruthenium compounds that can be converted into ruthenium carbonyl keys in such a reaction system include, for example, ruthenium halogen compounds, carboxylates, inorganic acid salts, oxides,
Examples include compounds that have complex bonds with various organic ligands and compounds that have key bonds with various inorganic ligands other than CO. Specifically, examples include ruthenium chloride, ruthenium bromide, ruthenium iodide, Examples include ruthenium formate, ruthenium acetate, ruthenium nitrate, ruthenium dioxide, ruthenium tetroxide, Ru(acac)3 and (C5)2Ru, and finely powdered ruthenium metal also forms carbonyl bodies in the reaction system. It can be used as it melts. Additionally, quaternary phosphonium halide {
Specifically, as b), tetramethylphosphonium fluoride "tetramethylphosphonium chloride, tetramethylphosphonium bromide, tetramethylphosphonium iodide, tetraethylphosphonium fluoride, tetraethylphosphonium chloride, tetraethylphosphonium bromide, tetraethylphosphonium iodide, Similarly, tetrapropylphosphonium halide, tetrabutylphosphonium halide, tetrabentylphosphonium halide, tetrahexylphosphonium halide, tetraphenylphosphonium halide, triphenylmethylphosphonium halide, heptyltriphenylphosphonium halide, n-hexadecyltriphenylphosphonium halide For example,

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 method of the invention, the reaction of carbon monoxide and hydrogen is carried out in the presence of an aprotic polar solvent.

Specifically, the aprotic polar solvents include sulfolane,
Sulfones such as dimethyl sulfone, sulfoxides such as dimethyl sulfoxide and jetyl sulfoxide,
Substituted ureas such as N・N-dimethylformamide, N・N-diethylformamide, N・N-dimethylacetamide, amides, N・N・N′・N′-tetramethylurea, hexamethylphosphoric acid triamide, hexaethylphosphate Phosphate triamides such as acid triamides, polyethers containing 4 or more oxygen atoms such as tetraglyme, 18-crown-6, N-methylpyrrolidone, y
Examples include lactones such as -butyrolactone and dimethyl-y-butyrolactone. Among these aprotic polar solvents, it is preferable to use an aprotic polar solvent having a yield factor 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. The proportion of catalyst used in the method of the present invention is arbitrary, but is generally as follows.

The proportion of ruthenium carbonyl atom used is usually 1 to 10-6 as the concentration of ruthenium atoms in the reaction system.
gram atom/unit, preferably in the range of 10-1 to 10-4 gram atom/unit. In addition, the usage ratio of the quaternary phosphonium halide [b} is usually 5 to 10-6 mol/unit, preferably 1 to 10-4 mol/unit, as the concentration of the quaternary phosphonium halide in the reaction system. It is a model.
The ratio of quaternary phosphonium halide to ruthenium carbonyl in the reaction system is usually 1 to 10-2 moles, preferably 50 to 2 moles of quaternary phosphonium halide to 1 gram atom of ruthenium. It is in the range of 1 mole. As a method for preparing the catalyst used in the method of the present invention, a ruthenium compound and a quaternary phosphonium compound are each added separately into the reaction system,
It is also possible to adopt a method in which catalytically active species are formed within the system, or by adding a ruthenium compound formed from both the ruthenium compound and the quaternary phosphonium halide to the reaction system as a body. A method of forming catalytically active species can also be adopted. 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 or less, as a molar ratio of carbon monoxide to hydrogen gas.
It is in the range of 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, lk9'
Uniform G, preferably without 1000, and 50k9/c
It is within the range of ○. Generally, the higher the pressure during the reaction, the better the reaction rate will be, and the method of the present invention is characterized in that an alkane polyol is produced even in a relatively low pressure region. Further, the temperature during the reaction is usually 300 to 5000, preferably 250 to 1
The range is from 50:00 to 0:00. The time required for the reaction is usually in the range of 20 to 0.1 hours, preferably 10 to 0.1 hours. Usually the reaction is carried out under condensing conditions. In the method of the present invention, the reaction mixture after completion of the reaction is distilled,
The alkane polyol can be isolated by processing by conventional methods such as 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 to the above-mentioned alkane polyols, the products obtained in the method of the present invention include methanol and ethanol. Next, the method of the present invention will be specifically explained using examples.

Example 1 After replacing the inside of a stainless steel autoclave with an internal volume of 38' with argon, the autoclave was charged with an R ratio of CO. 2
0.3 mg-atm as Ru atoms, 1.80 mmol of tetraphenylphosphonium chloride, and 7.5' of sulfolane were charged.

Next, a mixed gas with a carbon monoxide/hydrogen molar ratio of 1/1 was pressurized to 200 k9/m in this autoclave.
000 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. As a result, 3.10 mmoi of methanol, 0
．． 77 skin moles of ethanol and 0.57 skin moles of ethylene glycol were produced.

In addition, the gas discharged after the reaction was analyzed using gas chromatography, and the results showed that 0.1 mol of methane and 3.85 mm
ol carbon dioxide gas was being produced. Comparative Example 1 The reaction was carried out in the same manner as in Example 1, except that cesium chloride was used instead of tetraphenylphosphonium chloride.

As a result, 1.16 mmol of methanol, 0.06 skin m
1 of ethanol, 0.09 mmol of ethylene glycol, and 0.23 mmol of carbon dioxide gas were 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. 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. [Ru3(00),2 0.3m
g-atm, 300K, 200°C] 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 3. 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 3. Comparative Example 6 The reaction was carried out in the same manner as in Example 1 except that sulfolane was not used as a solvent.

The results are shown in Table 3. Table 3

Claims (1)

[Scope of Claims] 1. A method for producing an alkane polyol by reacting carbon monoxide and hydrogen in the presence of a catalyst and under heating and pressurizing conditions, comprising a ruthenium carbonyl complex (a) and a quaternary phosphonium halide (b). ) A method for producing an alkane polyol, characterized in that the reaction is carried out in the presence of a catalyst consisting of: and in an aprotic polar solvent. 2. The concentration of ruthenium carbonyl complex (a) in the reaction system is 10^-^1 to 10 as ruthenium atoms.
2. A method according to claim 1, in the range ^-^4 gram atoms/l. 3. The method according to claim 1, wherein the concentration of the quaternary phosphonium halide (b) in the reaction system is in the range of 1 to 10^-^4 mol/l. 4 The proportion of quaternary phosphonium halide (b) used is 50 to 1 per gram atom of ruthenium in the reaction system.
2. The method of claim 1 in the molar range. 5. The method according to claim 1, wherein the quaternary phosphonium halide (b) is quaternary phosphonium chloride, quaternary phosphonium bromide or quaternary phosphonium iodide. 6
2. The method according to claim 1, wherein the aprotic polar solvent has a dielectric constant [ε] of 20 or more.