JPS58172332A - Production of oxygen-containing compound - Google Patents

Abstract

PURPOSE:After the liquid-phase reaction between carbon monoxide and hydrogen in the presence of a catalyst containing ruthenium, at least a part of the reaction product is removed from the reaction product by distillation and the remaining fraction is recycled to the above reaction zone to produce oxygen-containing compounds effectively. CONSTITUTION:After the liquid-phase reaction between carbon monoxide and hydrogen in the presence of a catalyst containing ruthenium into oxygen-containing compounds such as methanol, ethanol or ethylene glycol, the reaction mixture is subjected to distillation at temperatures lower than 250 deg.C, preferably lower than 200 deg.C to separate at least a part of the reaction product. Then, the reaction mixture containing the catalyst, after the distillation, is recycled to the reaction zone, thus producing oxygen-containing compounds using a catalyst of ruthenium, more inexpensive than rhodium, moreover, permitting steady separation and recovery of the catalyst without any adverse effects on its intrinsically high catalyst activity with advantage.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for producing oxygenated compounds such as methanol, ethanol, ethylene glycol, etc. from synthesis gas, ie a mixture of carbon oxide and hydrogen. Methanol is used as a raw material to produce formaldehyde, acetic acid, and hydrocarbons, etc. - Rhodium catalysts are used as a method to react carbon oxide and hydrogen to produce oxygenated compounds such as methanol, ethanol, and ethylene glycol. Many examples have been proposed.

However, these methods, as exemplified in Japanese Patent Publication No. 53-3//22, etc., have not yet developed enough catalytic activity to justify the use of expensive rhodium, so it is difficult to put them into practical use on an industrial scale. As a method, it has problems such as being difficult to adopt.

As one measure to avoid these drawbacks of rhodium catalysts, a method of using ruthenium catalysts, which are cheaper than rhodium catalysts, has been proposed. For example, US Patent 'I, /70.60! Mu salts, alkali metal halides, alkaline earth metal halides, etc. are specified. On the other hand, JP-A-56-/tattt, tt,
Publication No. 22 describes a method for producing methanol in which a Lewis acid is used as a promoter together with ruthenium.

Examples of the Lewis acid in this case include alkali metal halogenides and boric acid. In addition, Unexamined Japanese Patent Publication No. 6-
100,72L! Publication No. R proposes a method for producing oxygen-containing compounds using a catalyst in which ruthenium is dispersed in a molten salt medium made of a 9th class phosphonium salt or a 9th class ammonium salt.

However, the ruthenium catalyst shown in the above-mentioned prior art cannot necessarily be said to have a sufficiently high activity level, so when implementing these technologies on an industrial level, it is necessary to use the ruthenium catalyst component. It is inevitably required to efficiently separate the product from the product and recycle it. However, extremely unfortunately, in the field of catalytic reactions that produce oxygen-containing compounds from carbon oxide and hydrogen, the technology for recovering ruthenium catalysts and recycling them remains completely undeveloped. It is.

In general, transition metal compound catalysts such as ruthenium, rhodium, palladium, and cobalt, which have the function of producing oxygen-containing compounds from carbon oxide and hydrogen, are often used as homogeneous liquid phase catalysts. Although it is a convenient method, it becomes even more difficult. In other words, most noble metal-based homogeneous liquid phase catalysts are composed of compounds collectively called organometallic complexes, but their thermal stability and oxidation resistance are not necessarily sufficient, so it is possible to Separating, recovering, and recycling the and products poses significant difficulties. In view of these facts, the present inventors have repeatedly carried out precise experiments on the characteristics of the ruthenium catalyst, and as a result have discovered a new fact that carbon oxide and hydrogen should be blown away.

That is, the present invention is a method for producing an oxygen-containing compound, characterized in that (1) a reaction solution containing a ruthenium-containing nium catalyst is circulated back to the reaction zone;

The present invention will be explained in more detail below.

The sources of carbon monoxide and hydrogen, which are the raw material gases used in the present invention, are not particularly limited.
Further, as the small amount of nitrogen or ruthenium, both metal ruthenium and ruthenium compounds can be used.

Examples of the addition form of the ruthenium compound include oxides, hydroxides, inorganic acid salts, organic acid salts, and complex compounds.

Specifically, examples include ruthenium dioxide, ruthenium tetroxide, engineered ruthenium hydroxide, ruthenium chloride, ruthenium bromide, ruthenium iodide, ruthenium nitrate, ruthenium acetate, tris(acetylacetone)ruthenium, sodium hexachlororuthenate, and tetracarbonylruthenium. acid dipotassium, beta/tacarponyl ruthenium,
The amounts of cyclopentadienyldicarponylruteridoruthenium, bis(trilobylphosphine)tricarbonylruthenium, dodecacarbonyltriruthenium, tetrahydridodecacarbonyltetraruthenium, and octadecacarruthenium are expressed as concentrations in the reaction solution. 0.0 ruthenium atoms per 7 liters of solution
00/~100 mol, preferably 00001~70 mol.

As a means for carrying out the present invention more advantageously, various forms of bases, onium salts, or various metal compounds are additionally added to the catalyst system.As the base compounds, various phosphines, bosphites, amines, etc. , alkali metal salt,
Examples include alkaline earth metal salts. Specifically, trirobetylphosphine, dimethyl-n-octylphosphine, tricyclohexylphosphine, triphenylbosphine, dimethylphenylphosphine,
/1. Bosphines such as 2-bis(diphenylphosphino)ethane, triethylphosphite, tri-buterpocohydroxypyridine, N-ethylpyrrolidine, N-methylpiperidine, N,N'-dimethylpiperazine amines such as, alkali metal salts such as lithium acetate, sodium acetate, potassium acetate, potassium propionate,
These include alkaline earth metal salts such as magnesium acetate and magnesium butyrate.

The amount of these basic compounds to be used is θ, θl to 1, θθO mol per mol of ruthenium atom, preferably θ, / to 1
It is in the range of 0θ mole.

Examples include compounds. Examples of salts of anionic components include halogen salts, sulfonates, perchlorates, sulfates,
Inorganic acid salts such as phosphates, silicates, borates, substituted borates, potassium fluoride such as carboxylates, lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride.

Alkali metal compounds such as lithium bromide, sodium bromide, potassium iodide, cesium iodide, potassium perchlorate, sodium tetrafluoroborate, sodium acetate, potassium acetate, calcium chloride, magnesium chloride, barium chloride, -nium acetate ρ-class phosphonium compounds such as, compounds in which the phosphonium groups of these compounds are bonded to insoluble polymers, iminium compounds such as bis(triphenylphosphine) iminium chloride, bis(triphenylphosphine) iminium chloride, These include positive ammonium compounds such as tetra-n-butylammonium tetraphenylborate, tetraphenylammonium chloride, hensyltrimethylammonium chloride, tetra-n-butylammonium bromide, and tetraphenylammonium iodide.

Among onium salts, halogenated compounds are slightly preferred. The amount of onium salt to be used is in the range of o, i~:/, ooo mol, preferably from 0.5 to 110 mol as diionium base per mol of ruthenium atom.

Examples of other metal compounds additionally added by Shintaku include iron, osmium, cobalt, rhodium, iridium, nickel, and parafluoride. Examples include group Ⅰ compounds such as chromium, molybdenum, platinum, group Ⅰ compounds such as manganese and platinum, and group Ⅰ compounds such as chromium, molybdenum, lipden, and tungsten. Among them, the addition of group (I) compounds is preferable, and the addition of rhodium and cobalt compounds often brings about favorable results.

Specific examples of compounds include pentacarbonyl iron and dodecacarbonyl triiron. decacarbonyl triosmium, octacarbonyl dicobalt, acetylacetone dicarbonyl rhodium, dodeca carbonyl tetrarhodium, dodeca carbonyl tetra rhodium, tetracarbonyl nickel, palladium acetate, bis(acetylacetone) platinum, decacarbonyl dimanganese, deca Hexacarponylsilenium, hexacarponylchromium.

Hexacarbonyl molybdenum, hexacarbonyl tungsten, etc.

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

As the primary temperature, a condition of 100-3007: is sought, but a more preferable range is /ta0-2 - θCp.

For the reaction pressure, a condition of 1000/cd or higher is adopted1.
However, from a practical point of view, 100−/, θ
00 ky/ad, more preferably a
/rθ-50oky, /crA range.

As the reaction solvent '1, the following can be used. For example, diethyl ether, anisole,
Ethers such as tetrahydrofuran, ethylene glycol dimethyl ether and dioxane, ketones such as acetone, methyl ethyl ketone and acetophenone, methanol, ethanol, n-butanol, benzyl alcohol,
Alcohols such as phenol, ethylene glycol, and diethylene glycol; carboxylic acids such as formic acid, acetic acid, propionic acid, and toluic acid; esters such as methyl acetate, n-butyl acetate, and benzyl benzoate; benzene, toluene, ethylbenzene, and tetralin; aromatic hydrocarbons,
Aliphatic hydrocarbons such as n-hexane, n-octane, and cyclohexane, halogenated hydrocarbons such as dichloromethane, trichloroethane, and chlorobenzene, nitrol compounds such as nitromethane and nitrobenzene, triethylamine,
Primary amines such as tri-buty-A amine, benzyldimethylamine, pyridi/, 1-picoline, co-hydroxyviridine, N,N-dimethylformamide, 1N-dimethylacetamide, hexamethylphosphoric triamide, N
-Amides such as methylpyrrolidone, N,N'-diothylimidazolitone, N,N,N',N'-tetramethylurea, sulfones such as dimethylsulfone and tetramethylenesulfone, dimethylsulfoxide, diphenylsulfoxide, etc. Sulfokinds, lactones such as γ-butyrolactone and ε-caprolactone, polyethers such as tetraglyme, / and tirilau/-6, nitriles such as acetonitrile and benzonitrile, dimethyl carbonate,
These include carbonate esters such as ethylene carbonate.

Among the above solvents, it is preferable to use aprotic polar solvents, that is, amines, amides, sulfones, sulfokinds, lactones, polyethers, nitriles, and carbonate esters, and polar solvents with a dielectric constant of 20 or more. Solvents are particularly preferred.

In the present invention, the reaction is carried out by the method described above using a ruthenium-containing catalyst to produce a quaternary-containing compound, specifically, a compound such as methanol, ethanol-4, and ethylene glycol. There is no limit to the production of oxygen from a reaction solution containing oxygen, but an atmosphere containing a gas containing an oxygen concentration higher than necessary is undesirable. A desirable atmosphere is under an oxygen-9 element mixture gas with an oxygen concentration of 27 or less, or under an inert gas such as nitrogen, helium, argon, or carbon dioxide, or under a mixture of -carbon oxide or monooxide/carbon-hydrogen. It's under gas.

Since the catalyst is deactivated if the distillation temperature is too high, the distillation is carried out at a temperature of 2 OC or lower, more preferably ldλooC or lower.

Although the pressure can be appropriately selected depending on the type of reaction solvent, it is preferable to carry out the reaction under reduced pressure so as not to make the temperature too high. Specifically, normal pressure to 0. /Cocoon Hy level.

Although the degree of distillation is not particularly limited, it is practical to carry out the distillation until substantially all of the products are removed. ? θmmo
Charge 10 ml of t- and N-methylpyrrolidone, and then add 300 ky/ml of an equal volume mixed gas of carbon monoxide and hydrogen.
(Filled to @.The temperature of the autoclave was set to 220C.
The initial value of the pressure when raised to 9 tons is θkg/
Ty! Met. After continuing the reaction for -4 hours, the autoclave was cooled and the contents were analyzed by gas chromatography. As a result, the following values were obtained as the number of product turnovers per unit time.

Methanol t, q3mat/l-a, tomRu
*hr ethanol θ,? 3 Ethylene Glycol 8/6 The reaction product solution analyzed as above was evaporated with nitrogen. This solution was charged into the autoclave again, and the mixture of -carbon oxide and hydrogen was charged in the same manner as before, and the reaction was repeated for 9 hours under the conditions of 220C1 initial pressure u20ky/crfl. As a result of cooling the autoclave and analyzing the contents by gas chromatography, the following results were obtained.

Methanol-A/q, 66mot/y-atomR
u@hrEthanol 009 Ethylene glycol 0.9 / Example 2 Nibis substituted by tetraphenylphosphonium bromide (
Triphenylphosphine)iminium chloride 7.2
A reaction using a homogeneous catalyst was carried out in the same manner as in Example 1, except that mmot was used, and the following results were obtained.

Example 3 The following results were obtained except that lithium chloride, 4tmm07, was used in place of tetraphenylphosphonium bromide.

Example Dabis(triphenylphosphine)iminium It is known that the reaction rate of ruthenium-based palpation decreases when the reaction product ethylene glycol accumulates, so considering this, the results of the second reaction were as follows: It is judged to be in good condition.

Example J Instead of using tetrabutylphosphonium bromide, a compound in which 9 moles of butyldiphenylphosphonium bromide groups relative to styrene were fixed to a two-bit crosslinked styrene-divinylbenzene copolymer was used, with the amount of phosphorus being θ, The reaction was carried out in the same manner as in Example/Kichi except that ¥mmol was used, and the results of the first reaction were as follows.

Methanol 7, titi mat/? -atomRu
*hr ethanol θ, ethylene glycol θλ The remaining F after separating the solid copolymer from this reaction solution
After distilling off virtually all of the liquid substance under the conditions of 2θC and lrrrmHy, N-methylpyrrolidone/θm was added again.
1 was added to obtain a homogeneous catalyst solution again, and the reaction was carried out. The reaction results for the second and third times when such an operation was performed were as follows.

Example 6 *) A slight black precipitate of metallic ruthenium was observed during distillation.

Example? The same procedure as in Example λ was used except that 10 ml of γ-pterolactone was used instead of N-methylpyrrolidone.
As a result of performing the reaction in this order, the following results were obtained.

Examples and catalysts include dodecacarbonyl triruthenium A, ruthenium as o, <t mmot, octacarbonyl dicobalt, cobalt as 0. /33mmot was used, and tetraphenylphosphonium iodide 2. 'l
The following results were obtained as a result of carrying out the same reaction as in Example except that rnrnol was used.

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Claims (1)

[Claims] (1+■ In the presence of a catalyst containing ruthenium, -carbon oxide and hydrogen are reacted in a liquid phase to produce an oxygen-containing compound; ■ At least one of the reaction products is produced by distillation from the nuclear reaction liquid. A method for producing an oxygen-containing compound characterized by separating and removing a portion of the ruthenium, and recycling the reaction solution containing ruthenium into the reaction zone again after distillation. (2) Performing the distillation at a temperature of 2 IOC or less. A method according to claim 1, characterized in that: