JPS6114133B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing oxygen-containing compounds such as methanol, ethanol, and ethylene glycol from synthesis gas, that is, a mixed gas of carbon monoxide and hydrogen. Methanol, ethanol, ethylene glycol, and other chlorine-containing compounds are a group of important basic chemicals with a wide range of applications, and industrially inexpensive production methods are always expected. Conventionally, as a method for directly producing oxygen-containing compounds such as methanol, ethanol, and ethylene glycol in one step using carbon monoxide and hydrogen as raw materials,
Many methods using rhodium-based catalysts have been proposed. However, these methods, as exemplified in Japanese Patent Publication No. 53-31122, use expensive rhodium, and there are difficulties in putting them into practical use on an industrial scale, such as recovering and reusing the rhodium catalyst. In addition, the catalytic performance is not necessarily sufficient, so the actual situation is that it has not been completed as a practical process. On the other hand, as a way to avoid the drawbacks of these rhodium catalysts, several methods have been proposed in which a ruthenium catalyst, which is cheaper than rhodium, is used. For example, US Patent No. 4170605
The specification describes a method for producing ethylene glycol using a catalyst consisting of ruthenium and pyridine ligands. In this case, the amount of pyridine ligand used is 10 moles or less per mole of ruthenium complex, and the reaction pressure is 10,000 psi (705.2 Kg/cm ² ).
It is stated that it is carried out within the range of 50000psi (3526.1Kg/cm ² ). More specifically, in the example, 5.74 moles of 2-hydroxypyridine was used per 1 g atom of ruthenium, and the pressure was 15000 psi (1057.8 Kg/
cm ² ) is shown. In addition, other pyridine ligands include 2-aminopyridine, 2-
An example of (dimethylamino)pyridine is also mentioned, but there is no example of it actually being used, and there is no description of what kind of effect it can achieve. Further, JP-A-55-115834 proposes a method in which a Lewis base is used as an unspecified promoter together with ruthenium. However, in this case, various amines, iminium salts, alkali metal halides, alkaline earth halides, and the like are clearly specified as examples of Lewis bases. However, the Lewis bases described in the examples are iminium salts, alkali metal halides, and alkaline earth metal halides, and it is unclear specifically what kind of structure exhibits an excellent effect, especially for organic N bases. There are no examples. In addition, JP-A-56-100728 discloses a system in which a ruthenium compound is dispersed in a low-melting point phosphonium salt, an ammonium base, or an ammonium salt, while JP-A-56-123925 discloses a system in which ruthenium is dispersed in an acetic acid solvent system. A composite metal system of rhodium has been proposed. The activity of the ruthenium catalyst shown in the above-mentioned prior art cannot be said to be at a high level in any case, and in many cases, there are many examples of reactions under high pressure of around 1000 atmospheres, making it difficult to efficiently produce oxygen-containing compounds. The standard has not been reached. The present inventors have arrived at the present invention as a result of extensive studies to increase the activity of ruthenium catalysts. That is, the present invention provides a method for producing an oxygen-containing compound by reacting carbon monoxide and hydrogen in the presence of a catalyst, wherein the catalyst contains (a) a ruthenium compound and (b) diaminopyridines as catalyst components. The present invention provides a method for producing an oxygen-containing compound characterized by the following. The ruthenium compounds used in the method of the invention include, for example, ruthenium halides, carboxylates, inorganic acid salts, oxides, various organic and/or
Alternatively, there are compounds with complex bonds with inorganic ligands, metal ruthenium, etc. Specifically, ruthenium chloride,
Ruthenium bromide, Ruthenium iodide, Ruthenium formate, Ruthenium acetate _, Ruthenium nitrate, Ruthenium oxide (), Ruthenium oxide (), Ruthenium acetylacetonate (), ( _C5H5 )( _CH3 )Ru
(CO) ₂ , (C ₅ H ₅ ) ₂ Ru, Ru ₃ (CO) ₁₂ , Ru ₆ C
(CO) ₁₇ , HRu (CO) ₄ ^- , Ru ₆ (CO) ₁₈ ² , HRu ₄
(CO) ⁻ ₁₃ , H ₂ Ru ₄ (CO) ₁₃ , H ₆ Ru ₄ (CO) ₁₂ , HRu ₃
(CO) ₁₁ , Ru ₆ C(CO) ^2- ₁₆ , [Ru(CO) ₃ Cl ₂ ] ₂ and the like can be exemplified. The amount of ruthenium used is 1 x 10 ^-6 to 100 gram atoms of ruthenium per 1 liter of reaction solution, preferably 1
×10 ^-5 to 10 gram atoms. Diaminopyridines, which are reaction accelerators used in the method of the present invention, have two amino groups or substituted amino groups at the 2nd and 3rd positions or the 3rd and 4th positions of the pyridine ring, and the general formula is as follows: It is as follows.

[Formula] In the above general formula (), R ₁ , R ₂ , R ₃ and R ₄
may be the same and represent hydrogen, an alkyl group, etc. As the alkyl group, a lower alkyl group having 1 to 10 carbon atoms is generally used. R ₁ and R ₂ and R ₃ and
R ₄ may be bonded to each other to form a saturated or unsaturated ring, or may be bonded via a heteroatom, such as 3 to 8,
Preferably it is a 5- to 7-membered ring, and examples of the hetero atom include oxygen, nitrogen, and sulfur. Among the diaminopyridines used in the present invention, pyridines having amino groups at the 3rd and 4th positions seem to give preferable results. Specific examples of such preferable compounds include:
3,4-diaminopyridine, N・N・N′・N′-
Tetramethyl-3,4-diaminopyridine, N.
N'-dimethyl-3,4-diaminopyridine,
N・N'-di(n-butyl)-3,4-diaminopyridine, 3,4-di(1-piperidinyl)pyridine, 3,4-di(1-pyrrolidinyl)pyridine,
2-methyl-3,4-diaminopyridine, 2,3
-diaminopyridine, N・N・N′・N′-tetramethyl-2,3-diaminopyridine, N・N′-
Examples include dimethyl-2,3-diaminopyridine. The various diaminopyridines mentioned above can be used alone or in combination. The amount of diaminopyridines used is ruthenium 1
The number of moles of diaminopyridine per gram atom is from 1 to 5,000, preferably from 2 to 2,000. However, this does not apply when diaminopyridines are used as a solvent. As the reaction solvent, those described below can be used. For example, ethers such as diethyl ether, tetrahydrofuran, dioxane, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether,
Ketones such as acetone, diethyl ketone and acetophenone; alcohols such as methanol, ethanol, n-butanol and ethylene glycol; carboxylic acids such as formic acid, acetic acid and propionic acid; phenols such as phenol and methoxyphenol; methyl acetate and acetic acid Esters such as ethyl, ethylene glycol diacetate and γ-butyrolactone, sulfones such as sulfolane and dimethylsulfone, sulfoxides such as dimethylsulfoxide and diethylsulfoxide, N/N-dimethylformamide, N/N-dimethylacetamide, N-
Amides such as methylpyrrolidinone, N-isopropylpyrrolidinone, N-methyl-2-pyridone,
N・N・N′・N′-tetramethylurea, N・N′-
Substituted ureas such as dimethylimidazolidinone, phosphoric acid triamides such as hexamethyl phosphoric acid triamide and tripiperidinophosphine oxide, aromatic hydrocarbons such as benzene, toluene, xylene, and tetralin, n-hexane, n- Aliphatic or alicyclic hydrocarbons such as octane, cyclohexane and decalin, nitro compounds such as nitromethane and nitrobenzene, triethylamine, tri-n-butylamine, pyridine, N-methyl-piperidine, N-methylmorpholine, α-picoline, 2・
These include tertiary amines such as 6-lutidine and 1-methylimidazole, nitriles such as acetonitrile and benzonitrile, and carbonic acid esters such as dimethyl carbonate and ethylene carbonate. In the method of the present invention, the reaction is carried out under heated and pressurized conditions. The reaction pressure is usually 1 to 2000
Kg/ ^cm2G , preferably in the range of 30-1000Kg/ ^cm2G . At this time, the ratio of carbon monoxide and hydrogen supplied to the reaction system as raw material gas for ethylene glycol production is usually in the range of 0.05 to 20, preferably 0.1 to 10 as a molar ratio of carbon monoxide to hydrogen gas. . In addition, the reaction temperature is usually 50 to 350℃,
Preferably it is in the range of 100 to 300°C. Furthermore, the reaction time is usually 0.1 to 20 hours, preferably 0.3 to 10 hours.
A time range is used. The process can be carried out batchwise, semi-continuously or continuously. The present invention will be explained in detail with reference to Examples below.
The present invention is not limited to the following examples. Example 1 Triruthenium dodecacarbonyl (10.6 mg,
0.05 mg atom), 3,4-diaminopyridine (1.09 g, 10 mmol), N·N'- as solvent
Add 4.0 ml of dimethylimidazolidinone to a magnetically induced stirring autoclave (30 ml internal volume, Hastelloy C).
Made in Japan). After sealing this autoclave,
After purging three times with a 1:1 molar ratio of CO:H ₂ synthesis gas, 340 Kg/cm ² of synthesis gas was injected at room temperature. The autoclave was heated to 230° C. in 30 minutes with stirring and then maintained at this temperature for 2 hours.
During this time, the reaction pressure reached a maximum of 500Kg/cm ² . After cooling the autoclave to room temperature, the liquid phase components were analyzed by gas chromatography, and the concentrations of ethylene glycol, ethanol, and methanol were 6.3, 0.2, and 0.2, respectively, per gram atom of ruthenium.
It was confirmed that it was being produced at a production rate of 58.1 mol/hour. Examples 2-7 Triruthenium dodecacarbonyl (10.6 mg,
0.05 mg atom), 3,4-diaminopyridine (545 mg, 5 mmol), and 4.0 ml of N・N'-dimethylimidazolidinone or tetraglyme shown in Table 1 as the solvent, and the reaction temperature was adjusted for each. The activity was examined by the same reaction procedure as in Example 1 except that the temperature was changed to 230, 250 and 270°C. In addition to methanol and ethylene glycol, some methyl formate, ethanol, and ethylene glycol monoformate were confirmed as reaction products. The production rates of methanol and ethylene glycol are shown in the table for each solvent and each reaction temperature.
The results are shown in 1.

[Table] Example 8 The reaction was carried out under the same conditions as in Example 1 except that 2,3-diaminopyridine (0.545 g, 5 mmol) was used. The production rate of ethylene glycol and methanol per gram atom of ruthenium was were 0.8 and 40.3 mol/h, respectively. Comparative Example 1 Triruthenium dodecacarbonyl (21.3 mg,
When the reaction was carried out under the same conditions as in Example 1 using 7.5 ml of N・N'-dimethylimidazolidinone as a solvent, no formation of ethylene glycol was observed, and methanol was
It was produced at a rate of 1.7 moles per gram atom/hour. Comparative Example 2 The same reaction as in Comparative Example 1 was carried out except that 7.5 ml of tetraglyme was used as the solvent, but substantially no ethylene glycol or methanol was produced. Comparative Examples 3 to 6 The same procedure as in Example 1 was conducted except that 5 mmol of each of the amines shown in Table 2 was used in place of 3,4-diaminopyridine, and the results were shown in Table 2.

【table】

Claims (1)

[Claims] 1. A method for producing an oxygen-containing compound by reacting carbon monoxide and hydrogen in the presence of a catalyst, characterized in that the catalyst contains (a) a ruthenium compound and (b) diaminopyridines as catalyst components. A method for producing an oxygen-containing compound.