JPS5973532A - Preparation of aliphatic alcohol - Google Patents

Abstract

PURPOSE:To prepare an aliphatic alcohol, especially ethylene glycol from synthesis gas, in high efficiency, by adding a proper amount of substituted or unsubstituted o-phenylenediamine to the gas, and reacting the gas in the presence of an Ru compound. CONSTITUTION:An aliphatic alcohol is prepared directly by reacting a mixture of carbon monoxide and hydrogen in liquid phase in the presence of a ruthenium compound. The reaction is carried out in the presence of a substituted or unsubstituted o-phenylenediamine (espeically preferably o-phenylenediamine, tolylene-3,4-diamine, 4,5-dimethyl-o-phenylenediamine, 2,3-diaminonaphthalene, etc.). The molar ratio of o-phenylenediamine compound to the Ru compound is 1/100- 1,000/1.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for the direct production of aliphatic alcohols from a mixture of carbon monoxide and hydrogen (hereinafter referred to as synthesis gas) in the liquid phase. More specifically, the present invention relates to a novel method for producing lower aliphatic alcohols or long aliphatic alcohols such as methanol, ethanol, and ethylene glycol.

Many studies have been conducted on methods for directly producing lower aliphatic alcohols from synthesis gas in the liquid phase -C. As a result, it has been known that catalysts containing Group I elements of the periodic table, especially rhodium or ruthenium, are active in producing aliphatic alcohols, especially ethylene glycol. However, the
These catalysts have not been used commercially for several reasons, such as the fact that their activity 9 selectivity is extremely insufficient and the recycling of the catalyst is unreliable.

The present inventors have intensively studied the use of a ruthenium compound catalyst for the synthesis reaction L, and as a result, they have found w1-substituted or unsubstituted orthophenylenedi.

The present invention was achieved based on the discovery that aliphatic atrecols, particularly ethylene glycol, can be efficiently obtained from synthesis gas by appropriately adding amines (hereinafter abbreviated as orthophenylene diamines).

In addition, Japanese Patent Application Laid-open No. 115,884/1984 and special edition No. 57/1983
-82. In '828, a method is described in which a mono-Lewis base-containing compound is used as a co-catalyst in the solubilized ruthenium carbonyl complex of the main catalyst. The selectivity is extremely low, which is unsatisfactory from the standpoint of effective use of synthetic forces.

Furthermore, since there are no examples of reactions using amines as Lewis base-containing compounds in Publication E, it is presumed that their promoter effects are insufficient.

However, the present inventors have discovered the novel fact that among amines, orthophenylenediamines have a specifically effective function.

That is, the present invention is capable of producing aliphatic alcohols by reacting synthesis gas in the presence of a ruthenium compound, by adding especially Iζ orthophenylene diamines among amines. The present invention provides an industrially useful method that overcomes the drawbacks of known methods.

The ruthenium compounds used in the present invention include oxides, hydroxides, inorganic acid salts, halides, carboxylic acid salts, and complex compounds having various ligands containing nitrogen, phosphorus, one oxygen boron, etc. Can be mentioned.

Specific examples thereof include ruthenium dioxide, ruthenium tetroxide, engineered ruthenium hydroxide, ruthenium nitrate, ruthenium chloride, ruthenium bromide, ruthenium iodide, ruthenium formate, ruthenium acetate, tris(ayathylacetonate)ruthenium, dodecacarbonyltri Ruthenium, pentacarbonylruthenium, bis(tri-butylphosphine)tricarbonylruthenium, dibromotricarbonylruthenium, undecacarbonylhydridotriruthenium tetraphenylphosphonium, dibotacium tetracarbonylruthenate, octadecacarbonylhexarthenate These include cesium, cyclobentadienyl divalent ruthenium, ruthenocene, etc.

Among these ruthenium compounds, carbonyl compounds or compounds that can be converted into carbonyl compounds in the reaction system are particularly preferred.

These ruthenium compounds can be used in the form of either homogeneous or heterogeneous catalysts in the liquid phase. When used in a heterogeneous form, it is usually supported on a suitable carrier and subjected to the reaction.

In the method of the present invention, the catalyst performance, particularly the selectivity to ethylene glycol, can be significantly improved by adding substituted or unsubstituted orthophenylenediamine to the main catalyst consisting of the above-mentioned ruthenium compound.

Substituted ortho-phenylene diamines are highly valued. Among these substituted orthophenylene diamines, those in which the hydrogen atoms of the benzene ring are substituted with 1 to 4 alkyl groups are preferred.

Specific examples of preferred phenylenediamines include orthophenylenediamine tolylene-8°(5)4-diamine, 4,5-dimethylorthophenylenediamine, and 2,8-diaminonaphthalene.

The type of solvent used in the method of the present invention is not particularly limited, but preferred solvents are ketones, alcohols, ethers, carboxylic acids, carboxylic anhydrides, esters,
Lactones, amides, sulfones, sulfoxides,
Aliphatic or aromatic hydrocarbons or solid salts that melt below the reaction temperature and mixtures thereof.

In the method of the present invention, the concentration of the ruthenium compound in the reaction system is in the range of 0.001 to 1 mol/1(7).

The amount of orthophenylenediamines added is 1/1,000 to 10,000/1, expressed as the ratio of the number of moles of orthophenylenediamines to the number of moles of ruthenium compound.
1, preferably 1/100 to 1.0
(It is 10/1.

The reaction pressure is 50 to 8.00014/cd when expressed as the sum of the partial pressure of -carbon oxide and hydrogen partial pressure (6)
preferably from 100 to 1.500&
g/d.

The molar ratio of carbon monoxide to hydrogen is suitably within the range of 1/10 to 10/1. Also, nitrogen, argon,
Gases inert to the reaction, such as methane and carbon dioxide, may be present.

The reaction temperature is preferably in the range of 100 to 450°C,
More preferably, the temperature is 200 to 850°C.

The reaction according to the present invention can be carried out either continuously or batchwise.

Products such as methanol, ethanol, and ethylene glycol obtained according to the method of the present invention can be separated from the reaction solution by known separation operations (e.g., distillation, extraction, and in the case of a heterogeneous catalyst, e.g., P separation). Can be easily separated.Also,
In the case of a homogeneous catalyst, the residual liquid from which the desired product has been separated can be recycled as it is to the reaction system and reused.

The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited thereto.

Examples 1 to 5 and Comparative Examples 1 to 8 After thoroughly purging the inside of a 4480 wl shaking type Hastelloy C autoclave with nitrogen, 0.1 mmol of a predetermined ruthenium compound and a predetermined amount of orthophenylenediamine as a cocatalyst were added. and 7.5 ml of the specified solvent were transferred, the contents were mixed well, and the autoclave was closed.

Synthesis gas with a molar ratio of CO/)i of 1/1 was pressurized into the autoclave until the amount reached approximately 220 kg/d. 60
The reaction was carried out by heating at 280° C. for 8 hours while shaking the autoclave at a rate of 1 stroke/min.

Further, for comparison, the reaction was carried out in the same manner as above except that no promoter was used.

After the reaction was completed, the autoclave was cooled to room temperature, most of the gas was slowly released, the pressure was returned to normal pressure, and the reaction mixture was taken out. A portion of the reaction mixture and released gas was collected, and the product was analyzed by gas chromatography.

The results are shown in Tables 1 and 2. The value of "reaction pressure" in the table indicates the maximum pressure reached during the reaction and the pressure at the end of the reaction.

In addition, in the table below, EG stands for ethylene glycol, M
eOH and EtOH represent methanol and ethanol, respectively. Also Ru, (CO)B and Ru(acac)1
are dodecacarbonyltriruthenium (0) and tris(acetylacetonato)ruthenium (dis), respectively, and NMP and TGM represent N-methylpyrrolidone and tetraethylene glycol dimethyl ether, respectively.

(9) Procedural amendment (voluntary) December 3, 1980 Commissioner of the Japan Patent Office 1 Kazuo Wakasugi 1, Indication of the case 1988 Patent 1i1@188740 2, Name of the invention Process for producing aliphatic alcohols 8. 1? Ministry of rIi correction.

Relationship to the case Patent applicant address: 8-1 Kasumigaseki-chome, Chiyoda-ku, Tokyo, package 5 of the detailed description of the invention, content of the supplement, as shown in the attached sheet, the subject of the oke-work, +) +5 iJv outside (”
- A method for producing aliphatic alcohols, which comprises adding substituted or unsubstituted orthophenylenediamine in producing IF alcohols.

8. Detailed Description of the Invention The present invention relates to a process for the direct production of aliphatic alcohols from a mixture of carbon monoxide and hydrogen (hereinafter abbreviated as synthesis gas) in the liquid phase. More specifically, the present invention relates to a novel method for producing lower aliphatic alcohols or polyhydric alcohols such as methanol, ethanol, and ethylene glycol.

Many studies have been conducted on methods for directly producing lower aliphatic alcohols from synthesis gas in the liquid phase. As a result, it has been known that catalysts containing Group I elements of the periodic table, especially rhodium or ruthenium, are active in producing aliphatic alcohols, especially ethylene glycol. However, the present inventors have discovered that aliphatic alcohols can be extracted from synthesis gas by adding an appropriate amount of lute (abbreviated as lute) to the above synthesis reaction.
In particular, we have discovered that ethylene glycol can be obtained efficiently, and have arrived at the present invention.

In addition, JP-A-55-115.884 and JP-A-57
Publication No. 82,828 describes a method in which a Lewis base-containing compound is used as a co-catalyst in the solubilized ruthenium carbonyl complex of the main catalyst, but as far as the examples are concerned, (2) synthesis gas The selectivity from ethylene glycol to ethylene glycol is extremely low, which is unsatisfactory from the standpoint of effective use of synthesis gas.

Furthermore, since there are no practical examples of reactions using amines as Lewis base-containing compounds in the above publication, it is presumed that their promoter effects are insufficient.

However, the present inventors have provided a method that is generally useful among amines.

Ruthenium compounds used in the present invention include oxides, hydroxides, inorganic acid salts, halides, carboxylic acid salts, and complex compounds (3) having various ligands containing nitrogen, phosphorus, oxygen atoms, etc. can be mentioned.

Specific examples thereof are ruthenium dioxide, ruthenium tetroxide, ruthenium dioxide, ruthenium nitrate, ruthenium chloride, ruthenium bromide, ruthenium iodide, ruthenium formate, ruthenium acetate, tris(acetylacetonate)ruthenium, dodecacarbonyltriruthenium. , pentacarbonylruthenium, bis(tri0-butylphosphine)tricarbonylruthenium, dibromotricarbonylruthenium, untecacarbonylhydridotrirutheniumtetraphenylphosphonium, dibotacium tetracarbonylruthenate, cesium octadecacarbonylhexarthenate, cyclo These include pentagenyldicarbonylruthenium, ruthenodecane, and the like.

Among these ruthenium compounds, carbonyl compounds or compounds that can be converted into carbonyl compounds in the reaction system are particularly preferred.

When these ruthenium compounds are leveled in a liquid phase, they are usually supported on a suitable carrier and subjected to the reaction.

In the method of the present invention, the catalyst performance, particularly the selectivity to ethylene glycol, can be significantly improved by adding substituted or unsubstituted orthophenylenediamine to the main catalyst consisting of the above-mentioned ruthenium compound.

Substituted orthophenylenediamines include alkyl groups, cycloalkyl groups, and cycloalkyl groups in which the benzene ring has 1 to 4 hydrogen atoms.
Included are those substituted with an aryl group, an aralkyl group, an alkoxy group, a hydroxy group, a carboxyl group, an amino group, a nitro group, a halogen atom, etc. Among these substituted orthophenylene diamines, those in which the hydrogen atom of the benzene ring is substituted with 1 to 4 alkyl groups are preferred.

A specific example of preferred phenylenediamines is orthophenylenediamine tolylene-8°.

Phonic acid anhydrides, esters, lactones, amides, sulfones, sulfoxides, and aliphatic compounds are aromatic hydrocarbons or solid salts that melt at or below the reaction temperature, and mixtures thereof.

In the method of the present invention, m of the ruthenium compound in the reaction system is
w is in the range 0.001-1 mol/J CD.

The amount of orthophenylenediamines added is expressed as the ratio of the number of moles of orthophenylenediamines to the number of 1-atoms of ruthenium contained in the ruthenium compound: l/1,
000 to to, oo.

/l, preferably from L/100 to 1,
000/l.

The reaction pressure, expressed as the sum of the partial pressures of -carbon oxide and hydrogen, is in the range of 50 to 8.000 Kg/J, preferably 100 to 350°C.

The reaction according to the present invention can be carried out either continuously or batchwise.

Products such as methanol, ethanol, and ethylene glycol obtained according to the method of the present invention can be easily separated from the reaction solution by known separation operations (eg, distillation, extraction, etc.). If the catalyst used is a heterogeneous catalyst, it can be easily 'rh-separated, for example, from door to door. In the case of a homogeneous catalyst, the residual liquid from which the desired product has been separated can be recycled to the reaction system and reused.

The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited thereto.

Examples 1 to 5 and Comparative Examples 1 to 8 After sufficiently purging the inside of a shaking type Hastelloy C autoclave with an internal volume of 80 - with nitrogen, Q, l + v-at
A predetermined ruthenium compound containing ruthenium, a predetermined number of orthophenylene diamines as a cocatalyst, and a predetermined solvent of 7,5 tItt were transferred, the contents were thoroughly mixed, and the autoclave was closed.

Synthetic residue with a CO/H2 molar ratio of 1/l was injected into the autoclave at a rate of about 220 kg/(M).6
The reaction was carried out by heating at 230° C. for 8 hours while shaking the autoclave at a rate of 0 strokes/min.

Further, for comparison, the reaction was carried out in the same manner as above except that no promoter was used.

(8) After the reaction was completed, the autoclave was cooled to room temperature, most of the gas was slowly released, the pressure was returned to normal pressure, and the reaction mixture was taken out. A portion of the reaction mixture and released gas was collected, and the product was analyzed by gas chromatography.

The results are shown in Tables 1 and 2. The value of "reaction pressure" in the table indicates the maximum pressure reached during the reaction and the pressure at the end of the reaction.

In addition, in the table below, EG stands for ethylene glycol, M
e OH represents methanol, and EtOH represents ethanol. Also, Ru3 (Co)12 and Ru (aca
c) 3 are dodecacarbonyltriruthenium (0) and tris(acetylacetonatocortenium (In)), respectively, and NMP and TGM are N-methylpyrrolidone and tetraethylene glycol dimethyl ether, respectively.

(Q) Transfer dodecacarbonyl triruthenium (0) containing ruthenium of 4,8■-atom, 289.9 mmol of 0-phenylenediamine, and 120 mmol of tetraglyme to an autoclave, seal it, and adjust the Co/H2 molar ratio. 1
Synthesis gas of 1/1 was injected under pressure to approximately 850 kg/2.

The autoclave was set in an electric furnace, and the temperature was raised to 250° C. in 1 hour while stirring, and the reaction was allowed to proceed at the same temperature for 3 hours.

At this time, the reaction pressure was adjusted to 440 Kf using a pressure regulator.
/Ql12, and the gas absorbed by the reaction was replenished by synthetic scum with a molar ratio of 00/H2 of 1/2. After the reaction was completed, gas and liquid components were sampled and the products were analyzed. The results were as follows.

(11) Dregs component H264,2vo1%, Co21.5v
o1%, CB4O,08vol=, CO214,8v
ow% liquid component methanol 602.6 E
Rimol ethylene glycol 480. Oj methyl rimorformate 18.5 mmol ethanol
8.6 mmol methyl acetate
11.8 mmol propylene glycol 8,9
mmol ethylene glycol monophotate 4.92 mmol ethylene glycol monoacetate 8.4 mmol glycerin 37.6 mmol Patent applicant: A Akabe (19♀)

Claims (1)

[Claims] Aliphatic alcohols are produced by reacting a mixture of carbon monoxide and hydrogen in the presence of a ruthenium compound. Manufacturing method.