JPS58157733A - Production of oxygen-containing compound - Google Patents

Abstract

PURPOSE:The liquid-phase reaction between carbon monoxide and hydrogen is carried out in the presence of a catalyst consisting of ruthenium or its compound and a salt of phosphine oxide or a phosphine oxide having a halogen-phosphorus linkage to produce an oxygen-containing compound in high yield. CONSTITUTION:In the production of an oxygen-containing compound such as methanol, ethanol or ethylene glycol by the liquid-phase reaction between carbon monoxide and hydrogen, a catalyst is used, consisting of ruthenium and/ or its compound and a salt of phosphine oxide such as a compound of formulaI(R<1>-R<3> are alkyl, aryl; Me is alkali metal; X is halogen) and/or a phosphine oxide having a halogen-phosphorus linkage such as a compound of formula II (R<4>, R<5> are alkyl, aryl, alkoxy, amino; X is halogen). The amount of ruthenium is 0.001-10moles, as ruthenium atom, per liter of the reaction mixture.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is a method for producing oxygenated compounds such as methanol, ethanol, and ethylene glycol from synthesis gas, that is, a mixture of carbon monoxide and hydrogen. It is one of the basic chemicals. Ethanol has become increasingly important in recent years as a hydrocarbon fuel and chemical raw material. Additionally, ethylene glycol is a synthetic intermediate useful as a raw material for polyester fibers and antifreeze.

- Many examples of using rhodium catalysts have been proposed as a method for producing oxygen-containing compounds such as methanol, ethanol, and ethylene glycol by reacting carbon oxide and hydrogen. However, it has drawbacks such as difficulty in adopting it.

As one measure to avoid these drawbacks of rhodium catalysts, a method of using a ruthenium-based catalyst, which is cheaper than rhodium, has been proposed. For example, US Pat. No. 70.60.5 describes an example of using a catalyst consisting of ruthenium and a pyridine base cocatalyst. Also, JP-A-55-//3. g
Publication No. 3 proposes a method in which a Lewis base is used as an unspecified promoter together with ruthenium. Examples of Lewis bases in this case include cyclic amines, iminium salts, alkali metal halogenides, alkaline earth metal halogenides, etc. A method has been proposed for producing oxygen-containing compounds using a catalyst in which ruthenium is dispersed in a medium consisting of a grade phosphonium salt or a grade ammonium salt shown in the following. However, the activity of the ruthenium catalysts shown in the above-mentioned prior arts cannot be said to be of a high level in any case, and the target oxygen-containing compound cannot be efficiently produced.

The present invention was achieved by discovering that oxygen-containing compounds such as ethylene glycol and ethylene glycol can be synthesized.

The present invention will be explained in more detail below.

The raw material gases used in the present invention, that is, carbon monoxide and hydrogen sources, are not particularly limited, and include a small amount of nitrogen gas,
It may also contain an inert gas such as carbon dioxide. The volume ratio of hydrogen and carbon monoxide is usually in the range of light to curvature, and a composition in the range of 2 to 2% is particularly preferred.

31 In the present invention, examples of the catalyst for the reaction between carbon monoxide and hydrogen include ruthenium, ruthenium acid radicals, and complex compounds.

Specifically, examples include ruthenium dioxide, ruthenium tetroxide, engineered ruthenium hydroxide, ruthenium chloride, hirthenium odor, ruthenium iodide, ruthenium nitrate, ruthenium acetate, tris(acetylacetone)ruthenium, sodium hexachlororuthenate, and tetracarbonylruthenium. dipotassium acid, pentacarbonylruthenifine) tricarbonylruthenium, dodecacarbonyltriruthenium, tetrahydridodecanocarbonyltetraruthenium, dicesium octadecacarbonylhexarthenate, tetraphenylphosphonium undecacarbonylhydridotriruthenate, etc.

Even when ruthenium compounds other than carbonyl compounds are used among these ruthenium compounds, they are considered to be converted into carbonyl compounds in the reaction system. However, it is preferable to add it as a carbonyl compound from the early stage of the reaction.

The concentration of ruthenium in the reaction solution is determined by using oxide.

The following compounds are preferable as salts of phosphine oxyto. That is, Eq.

0 R2-P-R’・・・・・・(1)■ 3 It is a salt of a compound represented by

In the above formula, R1, R2, and R3 represent an alkyl group or an aryl group, and the alkyl group is preferably a lower alkali metal or alkaline earth metal chloride. −
As an example, a salt of an alkali metal halide and a phosphine oxide has the following structure.

, -In the above formula, Me represents an alkali metal, and X is 1In the above formula, R', R5 is an alkyl group,
It represents an alkoxy group, an aryloxy group, an amino group, or a substituted amino group, and represents an x ys '/logen atom. As an alkyl group or alkoxy group, a lower alkyl group or a lower alkoxy group (preferable).Also, as a substituted amine group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group or a piperidino group or a 7-morpholino group It may also contain a cyclic amino group such as

Specific compounds include the following.

Examples include diethylchlorophosphine phosphine oxide, jetoxychlorophosphine oxide, dibutoxychlorophosphine oxide, bis(ethylamine)bromophosphine oxide, and the like.

The various phosphorus compounds mentioned above may be used alone or in combination.

The amount of the phosphorus compound to be used is 0.07 to 1000 mmol as phosphorus atoms per mole of ruthenium, preferably 0.07 to 1000 mmol as phosphorus atoms. /-, 100 mmol.

As the reaction solvent, the following can be used. For example, ethers such as diethyl ether, anisole, tetrahydrofuran, ethylene glycol dimethyl ether, dioxane, ketones such as acetone, methyl ethyl ketone, acetophenone, alcohols such as methanol, ethanol, n-butanol, benzyl alcohol, ethylene glycol, diethylene glycol, etc. phenols such as phenol and substituted phenols; carboxylic acids such as formic acid, acetic acid, propionic acid, and toluyl; esters such as methyl acetate, n-butyl acetate, and benzyl benzoate; benzene, toluene, ethylbenzene, and tetralin; Aromatic hydrocarbons, aliphatic alothylamines such as n-hexane, -n-ioctane, and cyclohexane, tertiary amines such as benzyldimethylamine, pyridine, α-picoline, and euhydroxyhyricine, N,N-dimethylformamide, N , N-dimethylacetamide, hexamethylphosphoric triamide, N-methylpyrrolidone, N,
N'-dimethylimidazolitone, N, N, N'
, amides such as N'-tetramethylurea, sulfones such as dimethyl sulfone and tetramethylene sulfone, sulfoxides such as dimethyl sulfoxide and diphenyl sulfoxide, lactones such as γ-butyrolactone and ε-caprolactone, tetraglyme, .

Using the above-mentioned solvents, the reaction can be carried out either in a homogeneous system or in a heterogeneous suspension system.

Although a reaction temperature of 700 to 300°C is adopted, a more preferable temperature range is io.

~230°C]W. The reaction pressure is not limited to 50 volumes.

Oxide ph,,p (=o)c+, 2g field O1 and N-methylpyrrolidone iomi were charged, and further Ic
- Equal volume mixed gas of carbon oxide and hydrogen at 300 ky/cr
Filled up to /l. The initial pressure value when the autoclave temperature is raised to 220°C is approximately II 20 k (1/
ad -11-hr methanol, 0.9 A mo1154-ato
m Ru-hr of ethanol, and 0. A5
The same reactants as in Example 1 were prepared except that mol/9-atom Ru-hr was not modified, and the same operations were performed. As a result, the turnover number was 0. 'l J
mol/%-atom Ru-hr of methanol, 0
．． /Omol/7-atom Ru·'hr of ethanol was produced, and the production of ethylene glycol was not detected.

EXAMPLE A reaction product 12-glycol was produced in the same manner as in Example 1, except that dibutylchlorophosphine oxyto:LmTl01 was used instead of diphenylchlorophosphine oxyto.

Example 3 The same reactants as in Example 1 were prepared, except that 2 hmmol of dimorpholinochlorophosphine oxide was used instead of diphenylchlorophosphine oxide, and the same operation was performed. The result was the turnover number: / 0/m
Methanol in ol/ji'-atom Ru-hr, l/5 mol/ji'-atom Ru-hr
of ethanol, and /Sgmol/! il-ato
mRu-hr of ethylene glycol was produced.

Example The same reactants as in Example 1 were prepared, except that 2y-mmol of diphenoxychlorophosphine oxide was used instead of diphenylchlorophosphine oxide, and the same operations were performed. The results were as follows: θ/m
ol/LiP-atom Ru-hr', Knoll,
l 29 mol/j7-atom Ru -hr and θ93 mol/jil-atom
Ru-hr ethylene glycol was produced.

Example f: The same reactants as in Example 1 were used, except that triphenyllithium oxyphosphonium bromide 'I Orrrno+ formed from tributylphosphine oxide and lithium bromide was used instead of diphenylchlorophosphine oxide. Prepared and produced by the same.

Example 2 The same reactants as in Example 3 were charged and the same operations were performed, except that sulfolane/θml was used instead of N-methylpyrrolidone. What is the result as the number of turnovers?
, 02 mol/j9'-atom Ru-hr methanol, 09 mol/jil-atom Ru-
hr of ethanol, and 0 l g mol/ji
Ethylene glycol of l'-atom Ru-hr was produced.

applicant Makoto Ishizaka, Director of the Institute of Industrial Science and Technology -

Claims (1)

[Claims] (]) - In a method for producing an oxygen-containing compound by reacting carbon oxide and hydrogen in a liquid phase, ruthenium and/or a ruthenium-containing compound and a salt of phosphine oxyto and/or a phosphine having a rogen-phosphorus bond are used as catalysts. A method for producing oxygen-containing compounds, which uses oxyto.