JPS617221A - Preparation of oxygen-containing compound - Google Patents

Abstract

PURPOSE:To obtain efficiently the aimed oxygen-containing compound, by reacting CO with H2 in the presence of a ruthenium compound as a catalyst in a general-purpose inexpensive solvent using an organic halide as a reaction promoter. CONSTITUTION:An oxygene-containing compound is obtained by reacting CO with H2 in the presence of a ruthenium compound catalyst, wherein the reaction is carried out in an aprotic solvent (example; THF, DMF, Xylene) in the coexistence of an organic halide (example; methyl iodide, benzotrichloride) expressed by the formula RXn (R represents mono- - traivalent hydrocarbon; X is halogen atom; n is 1, 2 or 3) as the reaction promotor. The organic halide is added in an amount necessary to set the ratio of the total halogen atom to the total ruthenium (Ru) atom (X/Ru) present in the reaction system within 1-20 range. EFFECT:The organic halide is capable of promoting the reaction without requiring any special solvent such as phosphine oxide.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing oxygen-containing compounds by reacting synthesis gas in the presence of a Ru compound catalyst.

More specifically, the present invention relates to an efficient method for producing an oxygen-containing compound, characterized in that the reaction is carried out in the presence of an organic halide as a reaction promoter.

The so-called C1 chemical technology, which produces ethanol and ethylene glycol from synthesis gas that can be produced from a variety of raw materials such as heavy oil and coal, is a promising technology for the future of chemistry, rather than the conventional petrochemical technology that uses ethylene, propylene, etc. as raw materials. It is expected that it will play a role in industry, and catalyst development for this purpose is being raced. Various methods have been proposed for producing oxygen-containing compounds from synthesis gas using ruthenium catalysts, and it is also known that organic halides are effective additives. That is, JP-A-57-82327 discloses a method for producing ethanol and methanol using methyl triprobylphosphuride and butyl iodide.

However, the coexistence of expensive phosphine oxide is essential, and it is difficult to say that this method is advantageous from an industrial standpoint. -1 is an effective additive in commonly used solvents other than phosphine oxide, and an alkali metal halide,
A number of compounds including phosphonium salts and iminium rings have been proposed, but their effects are not yet sufficiently high or they are too expensive to be considered as industrially advantageous additives.

In view of this situation, the present inventors conducted intensive research into additives for producing oxygen-containing compounds from synthesis gas using Ru catalysts that are inexpensive and have a large activity-improving effect. However, they discovered the novel and useful fact that reactions often require special solvents such as phosphine-oquinde, and based on this knowledge, they completed the present invention. That is, according to the present invention, when reacting a wide range of synthesis gases to those skilled in the art, the general formula RXn
An advantageous method for producing an oxygen-containing compound is provided, which is characterized in that the reaction is carried out in the presence of an organic compound represented by (R1, X, and n are the same as above).

As the T compound used as a catalyst in the method of the present invention, a ruthenium carbonyl derivative or any compound that can form a ruthenium carbonyl derivative under the reaction conditions of pressurizing synthesis gas can be used. Such ruthenium compounds include various ruthenium complexes, ruthenium inorganic or organic salts, oxides, and the like.

Ru3(Co) as a suitable ruthenium compound.
, )(, u (Co)5. Ru (Co)3(PP
h,)2. n, u(co)3c12. Ru (Co)3
Brz Jtu (co)3■2゜C3(R,u(CO
)3C13], PPN(I]R11J, (CO)11]
, PPNCl■R1λ(Co)4) , (1, 3, 5
-cyclooctatriene)(1°5-cyclooctadiene)ruthenium, f(, uC12(CO)2 (P
Ph5)2, (Ru(Co)3C12'). ,R
yuC13, RuBr3゜Ru I 3. Ru (O
A C)a, Ru (aCaC)a,”u(NO
a) 3°RuO2, rt, uo4, etc. can be exemplified. Powdered or colloidal ruthenium metal can also be used. The amount of ruthenium catalyst used is 10 to 1 g atoms per ruthenium metal, preferably 10 to 10
selected from a range of g atoms.

The organic halogenide used in the reaction method of the present invention is not particularly limited as long as it has the structure of the general formulas R and Xn. R represents a valent, divalent, or trivalent hydrocarbon group, including monovalent hydrocarbon groups such as methyl, ethyl, butyl, allyl, crotyl, cyclohexyl, phenyl, benzyl, methylene, ethylene, Divalent hydrocarbon groups such as ethylidene, benzylidene, xylylene, 2-butene T1,4-diyl, 1. , ] , ]-methynyl, α
, α, α-phenylmethynyl and the like are included. Also, the rogen atom represented by X is chlorine, bromine, or iodine. Examples of such organic compounds include methyl iodide, butyl iodide, iodohensen, allyl chloride, benzyl bromide, benzyl iodide, arylidene dibromide, benzal chloride, and the reaction of System: If the total amount of 7.logen in the reaction system is less than 1 equivalent relative to the total number of T(,u my -atoms in the system), the activity improvement effect will be insufficient,
Compared to the number of m9-atoms (~), when the number of However, in general, the ratio of the total number of mg-atoms of 2 and rogens in the system to the number of total R,u-atoms is
It is preferable to set the amount necessary for R and u to be in the range of 1≦X/R and +1≦20.

This does not exclude the addition of a co-catalyst metal component or a second additive component, but depending on the reaction conditions and solvent, the co-catalyst component and/or may be added to further improve the selectivity of a specific oxygen-containing compound. Alternatively, the reaction according to the method of the invention may advantageously be carried out in the presence of a second additive component.
It is carried out at a temperature of 0° to 350°C, preferably 150 to 300°C. The pressure of the synthesis gas is 50 to 2000 atm or more, preferably 100 to 1000 atm, and the gas composition is such that when the partial pressure of H2 is high, the reaction activity increases, but by-products such as methane are also produced. Since CO tends to increase, it should be determined by taking into account activity and selectivity, but it is usually set between /H2-5 and 1/1o, with a preferred range of 2 to 115.

Various solvents can be suitably used in the present invention, including solvents conventionally used in the synthesis of oxygen-containing compounds from synthesis gas.

Examples of these include tetrahydrofuran, diglyme,
Ethers such as tetraglyme, esters such as ethyl acetate and γ-butylactone, dimethylformamide,
N-methylpyrrolidone, N-isopropylpyrrolidone,
Amides or ureas such as tetramethylurea and dimethyl imigzolidinone, aromatic carbonization such as benzene, toluene, xylene, etc. The oxygen-containing compounds obtained by the present invention include:
These include methanol, ethanol, furopanol, ethylene glycol, etc., and these can be easily separated by commonly used methods such as distillation or extraction of the reaction solution.

The embodiments of the present invention will be explained in more detail with reference to Examples.

Example 1 Ru3 was placed in a Hastelloy C micro cylinder with an internal volume of 40 m1.
(CO)+2 as l(, Q per u atom, i ~-ato
m, benzyl chloride @ 9.5 mm01, N-isopropylpyrrolidone] Oml preparation, room temperature T300
atm (7) synthetic scum (CO/H2-1) is press-fitted,
The reaction was carried out at 30° for 3 hours. Pour the reaction solution into Chromosolve 101
The reaction results of the method were obtained as a result of analysis by gas chromatography using as a packing material.

Methanol production amount 8.09 m mol
Ethanol production amount Q, 59 m mol
Ethylene glycol-generated IJ, 0.5 mm
Amount of ol acetic acid + methyl acetate produced Q, 33 m m
Example 2゜The reaction was carried out in the same manner as in Example 1, using 0.3 mmol of benzyl chloride, and the following reaction results were obtained.

Methanol production amount 5.52 mmol Ethanol production amount Q, 55 mmol Ethylene glycol production amount 0.29 mmol acetic acid + methyl acetate production amount Q, l 9 mmol Example 3゜Te((CsHs) )3P)2
The reaction was carried out in the same manner as in Example 1 except that 1'L (HRu3(Co)n) was used, and the following reaction product was obtained.

Methanol production amount: 9.78 m mol Ethanol production amount: Q, 75 m mol Ethylene glycol production amount: 0.75 m mol Acetic acid + Methyl acetate production amount: 0.4: 4-fn m
ol Example 4,5゜Methanol production amount (mmol) 6,31
5.19 Ethanol production amount (mmol)
1.58 1.27 Example 6 The same reaction as in Example 1 was carried out using 0.5 mmol of the second additive.
In addition, the results shown in the table below were obtained.

t-1h Po Feast 00 ■ When conducted in the presence of , the following results were obtained.

Claims (2)

[Claims] (1) When producing an oxygen-containing compound by reacting carbon monoxide and hydrogen using a Ru compound as a catalyst, the general formula RXn
(R represents a monovalent, divalent, or trivalent hydrocarbon group, X represents a halogen atom, or n represents a positive integer of 1≦n≦3). A method for producing an oxygen-containing compound characterized by (2) The ratio of all halogen atoms to all Ru atoms present in the reaction system, that is, X/Ru, is 1≦X/
(3) The organic halide is an organic bromide or an organic iodide, and the organic halide is an organic bromide or an organic iodide, and the organic halide is added in an amount necessary for Ru≦20 to react. The method according to claim 1 (4 ) The method according to claims 1 to 3, in which the reaction is carried out using an aprotic compound as a solvent.