JPS647975B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION The present invention relates to a process for the catalytic production of ethylene glycol from synthesis gas, ie a mixture of carbon monoxide and hydrogen. Ethylene glycol is a raw material for polyester fibers,
It is an extremely important chemical product industrially as a raw material for organic solvents and non-volatile antifreeze. [Prior Art] Conventionally, ethylene glycol has been produced by an oxidation reaction of ethylene. In recent years, as a method for producing ethylene glycol, a technology is being developed that uses synthesis gas, which is a cheaper and more abundant raw material than ethylene, as a raw material. For example, the
No. 31122, Special Publication No. 55-43821, Special Publication No. 15047-1983
No., JP-A-50-32118, JP-A-56-401131,
Special Publication No. 55-5497, Special Publication No. 55-33694, Special Publication No.
No. 55-33697, JP-A-51-125203, JP-A-56-
No. 10894, JP 56-40698, JP 52-42808
No., JP-A-52-42809, JP-A-52-42810, JP-A-56-40132, JP-A-53-121714, JP-A-Sho.
No. 54-71098, JP-A-54-48703, JP-A-54-
No. 92903, JP-A-54-16415, JP-A-54-122211
No., JP-A-55-9065, JP-A-57-128645, JP-A-56-75498, JP-A-57-130941, JP-A-Sho
57-130942 and Japanese Patent Application Laid-open No. 53-108889, and U.S. Patent No. 4013700, 4199520, 4133776
No. 4151192, 4153623, 4225530, 4199521
As described in the specifications of No. 1, No. 4190598, No. 4302547, and No. 4211719, a method of reacting carbon monoxide and hydrogen using a rhodium catalyst under high temperature and high pressure conditions is well known. ing. [Problems to be Solved by the Invention] However, the methods of the prior art exemplified above have not yet achieved catalytic activity commensurate with the use of expensive rhodium, and therefore cannot be applied on an industrial scale. It has problems such as difficulty in adopting it as an implementation method. [Means for Solving the Problems] Taking the above circumstances into consideration, the inventors of the present invention have conducted extensive studies to increase the activity of rhodium catalysts, and as a result, have arrived at the present invention. That is, the gist of the present invention is to provide a method for producing ethylene glycol by reacting carbon monoxide and hydrogen in a liquid phase in the presence of a rhodium-containing catalyst. Let the heterocycle be 1
A method for producing ethylene glycol characterized by the presence of a tertiary phosphine having only a phosphorus atom and no fused heterocycle having a phosphorus atom as a heteroatom, and monoxide in the presence of a rhodium-containing catalyst. In a method for producing ethylene glycol by reacting carbon and hydrogen in a liquid phase, one heterocyclic ring having a phosphorus atom bonded to an alkyl group as a heteroatom is added to the reaction system.
A method for producing ethylene glycol, characterized by the presence of tertiary phosphines and organic amine compounds having only a phosphorus atom and no fused heterocycle having a phosphorus atom as a heteroatom. According to the method of the present invention, it is possible to produce ethylene glycol at a high level of yield that could not be achieved using conventional catalyst systems. Hereinafter, the present invention will be explained in detail. The source of the raw material gases used in the present invention, ie, carbon monoxide and hydrogen, is not particularly limited, and may contain a small amount of inert gas such as nitrogen gas or carbon dioxide. The volume ratio of hydrogen to carbon monoxide is usually in the range of 1/10 to 10/1, and it is particularly preferable to use a composition in the range of 1/5 to 5/1. In the present invention, rhodium is used as a catalyst component. As the supply form of the rhodium component, either rhodium metal or a rhodium compound that forms a rhodium carbonyl compound in the reaction zone can be used. Specific examples of rhodium compounds include zero-valent compounds such as dirhodium octacarbonyl; monovalent complex compounds such as acetylacetonatobis(carbonyl)rhodium and bromotris(pyridine)rhodium; rhodium trichloride, rhodium nitrate, rhodium acetate, etc. Salts; Oxides such as rhodium trihydroxide; Trivalent complex compounds such as tris(acetylacetonato)rhodium; Clusters such as tetrarhodium dodecacarbonyl and hexalodium hexadecacarbonyl; rhodium tetracarbonyl anion, carbide hexalodium Examples include anion complexes such as pentadecacarbonyl dianion. Furthermore, in the present invention, it is also possible to use a rhodium compound to which a tertiary phosphine used as a reaction accelerator has been coordinated in advance, as described below. The amount of rhodium used is expressed as the concentration in the reaction solution.
It ranges from 0.0001 to 100 gram atoms, preferably from 0.001 to 10 gram atoms per reaction solution. In the present invention, further, as a catalyst component, a fused heterocycle having only one heterocycle having a phosphorus atom as a heteroatom and having a phosphorus atom as a heteroatom to which an alkyl group is bonded is used as a catalyst component. Use tertiary phosphines that do not have Preferable examples of the tertiary phosphines have the general formula (): (In the formula, R ₁ represents a chain or cyclic alkyl group, and R ₂ represents a saturated or unsaturated group that may be substituted with an alkyl group, an oxo group, a hydroxyl group, an alkoxy group, or an alkylene dioxy group. represents an aliphatic hydrocarbon chain). In the tertiary phosphines represented by the above general formula (), the size of the heterocycle containing a phosphorus atom as a heteroatom is usually a 3- to 10-membered ring, preferably a 4- to 7-membered ring, and R ₂ is When substituted with an alkyl group, alkoxy group or alkylenedioxy group, the number of carbon atoms in the substituent is 1 to 10, preferably 1.
-5, and those in which R ₁ has carbon atoms of 1 to 20, preferably 1 to 10, more preferably 1 to 7 are used. Specific examples of the above tertiary phosphines include 1
- Phosphiranes such as methylphosphirane, 1-isopropylphospherane, 1-t-butylphosphirane; 1-methylphosphethane, 1-isopropylphosphethane, 1,2,2,3,4,4-
Hexamethylphosphethane, 1-isopropyl-
2,2,3,4,4-pentamethylphosphetane, 1-t-butyl-2,2,3,4,4-pentamethylphosphetane, 1-n-butyl-2,
Phosphethanes such as 2,3,3-tetramethylphosphethane; 1-methylphosphorane, 1-isopropylphosphorane, 1-cyclohexylphosphorane, 1-n-butylphosphorane, 1-t-butylphosphorane, 1 -sec-butylphosphorane, 1,
Phosphoranes such as 3-dimethylphosphorane and 1,2-dimethylphosphorane; Phosphorenes such as 1-methylphosphorene, 1,2-dimethylphosphorene, 1-isopropylphosphorene, and 1-cyclohexylphosphorene; 1- Methylphosphole, 1-
n-butylphosphole, 1-n-butyl-2,5
-Phosphores such as dimethylphosphole; 1-n
-Butylphosphorinane, 1-isopropylphosphorinane, 1-cyclohexylphosphorinane, 1-
t-Butylphosphorinane, 1-sec-butylphosphorinane, 1-n-butyl-2,2,6,6-tetramethylphosphorinane, 1-cyclohexyl-
2,2,6,6-tetramethylphosphorinane, 4,4-ethylenedioxy-2,2,6,6-
Tetramethyl-1-n-butylphosphorinane Phosphorinane such as; 1-methyl-2,2,6,6-tetramethylphosphorinan-4-one 1-n-butyl-2,2,6,6-tetramethylphosphorinan-4-one 1-isopropyl-2,2,6,6-tetramethylphosphorinan-4-one 1-Cyclohexyl-2,2,6,6-tetramethylphosphorinan-4-one 1-n-hexyl-2,2,6,6-tetramethylphosphorinan-4-one Phosphorinanones such as; 1-isopropylphosphorinan-4-ol 1-cyclohexylphosphorinan-4-ol 1-n-butyl-2,2,6,6-tetramethylphosphorinan-4-ol 1-isopropyl-2,2,6,6-tetramethylphosphorinan-4-ol 1-Cyclohexyl-2,2,6,6-tetramethylphosphorinan-4-ol Phosphorinanols such as; 1-isopropyl-1,2,5,6-tetrahydrophosphorine 1-t-butyl-1,2,5,6-tetrahydrophosphorine 1-n-butyl-1,4-dihydrophosphorin-4-one 1-cyclohexyl-1,4-dihydrophosphorin-4-one Hydrophospholines such as 1-methylphosphepane, 1-n-propylphosphepane, 1-isopropylphosphepane, 1
Examples include phosphepanes such as -t-butylphosphepane and 1-cyclohexylphosphepane. The amount of these tertiary phosphines used varies depending on the type of compound, but is usually 0.1 to 1000 mol, preferably 0.5 to 1000 mol, per 1 gram atom of rhodium.
The amount is preferably 500 mol, more preferably 0.5 to 100 mol. In the present invention, the activity of the rhodium catalyst can be further improved by adding an organic amine compound together with the above-mentioned tertiary phosphines. Specific examples of the organic amine compounds include methylamine, ethylamine, n-propylamine, isopropylamine, octylamine, dimethylamine, diethylamine, di-n-propylamine, methylethylamine, trimethylamine, triethylamine, triisopropylamine, and trimethylamine. Aliphatic amines such as isobutylamine and tridecylamine; alicyclic amines such as cyclohexylamine, dicyclohexylamine, tricyclohexylamine, and dicyclohexylmethylamine; ethyleneimines such as ethyleneimine and methylethyleneimine; piperidine, 1- Piperidines such as methylpiperidine, 2-methylpiperidine, 3-methylpiperidine, 4-ethylpiperidine; pyridine, 2-methylpyridine, 3-methylpyridine, 4-ethylpyridine, 2,4,6-trimethylpyridine, 4- Aminopyridine, 2-aminopyridine, 2-(dimethylamino)pyridine, 2-
Pyridines such as (methylamino)pyridine, 4-anilinopyridine, 4-(methylamino)pyridine, 4-(dimethylamino)pyridine; quinoline,
Quinolines such as 2-(dimethylamino)quinoline and 4-(dimethylamino)quinoline; Phenanthrolines such as 4,5-phenanthroline and 1,8-phenanthroline; Piperazine, 1-methylpiperazine, 1 - Piperazines such as phenylpiperazine; cyclic amines such as diazabicycloundecene and diazabicyclooctane; imidazole, 1-methylimidazole, 1-ethylimidazole, benzimidazole, 1-methylbenzimidazole, 1-ethylbenz Imidazole such as imidazole, 5,6-dimethylbenzimidazole, 1,5,6-trimethylbenzimidazole, 2-methylbenzimidazole; triazole, 1
-benzyltriazole, 1-methyltriazole, benzotriazole, 1-methylbenzotriazole, 1-ethylbenzotriazole, 2-
Polyazoles such as methylbenzotriazole, 5,6-dimethylbenzotriazole, tetrazole, 1-methyltetrazole, etc.; aniline, 1-naphthylamine, 2-naphthylamine,
Aromatic amines such as o-toluidine, p-toluidine, o-3-xylidine, benzylamine, diphenylamine, dimethylaniline, diethylaniline, 1,8-diaminonaphthalene, 1,8-bis(dimethylamino)naphthalene, etc. ;1,
2-ethanediamine, 1,3-propanediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetraethylethylenediamine, N,N,N',N'-tetra Methylhexamethylene diamine, tetrakis(dimethylamino)ethylene, tetrakis(piperidino)ethylene, tetrakis(morpholino)ethylene, tetramethyl-Δ _2,2′ -bis(imidazolidine), tetrabenzyl-Δ _2,2′ -bis( imidazolidine), o
-Aliphatic and aromatic polyamines such as phenylenediamine, p-phenylenediamine, o-toluidine, N,N,N',N'-tetramethyl-p-phenylenediamine; ethanolamine, diethanolamine, morpholine , methylmorpholine, 2-hydroxypyridine, 1-methoxypyridine, 4-hydroxypyridine, 4-methoxypyridine, 4-phenoxypyridine, 2-methoxyquinoline, 2-hydroxyimidazole, 2-methoxybenzimidazole, etc. Examples include amines. When using the above organic amine compound, the amount used varies depending on the type of the compound and the type and amount of tertiary phosphine used, but it is usually used per gram atom of rhodium.
The amount ranges from 0.001 to 1000 mol, preferably from 0.1 to 500 mol, and more preferably from 1 to 100 mol. Furthermore, it is generally preferable to use tertiary amines among the above-mentioned organic amine compounds, although it varies depending on the type of tertiary phosphine used in combination. However, as will be described later, when an organic amine compound is used as a solvent, it is not necessarily necessary to limit the amount of the organic amine compound added to the above range. Although the invention can be carried out in the absence of a solvent, ie the reaction raw materials and catalyst components themselves serve as reaction medium, it is also possible to use a solvent. Examples of such solvents include ethers such as diethyl ether, anisole, tetrahydrofuran, ethylene glycol dimethyl ether, and dioxane; ketones such as acetone, methyl ethyl ketone, and acetophenone; methanol, ethanol, n
-Alcohols such as butanol, benzyl alcohol, phenol, ethylene glycol, diethylene glycol; formic acid, acetic acid, propionic acid,
Carboxylic acids such as toluic acid; esters such as methyl acetate, n-butyl acetate, benzyl benzoate;
Aromatic hydrocarbons such as benzene, toluene, ethylbenzene, and tetralin; Aliphatic hydrocarbons such as n-hexane, n-octane, and cyclohexane; Halogenated hydrocarbons such as dichloromethane, trichloroethane, and chlorobenzene; Nitro compounds such as nitromethane and nitrobenzene; triethylamine,
Tertiary amines such as tri-n-butylamine, benzyldimethylamine, pyridine, α-picoline, 2-hydroxypyridine; N,N-dimethylformamide, N,N-dimethylacetamide, N
-Carboxylic acid amide such as methylpyrrolidone; hexamethylphosphoric acid triamide, N,N,N',N'-
Inorganic acid amides such as tetraethylsulfamide;
N,N'-dimethylimidazolidone, N,N,N',
Ureas such as N′-tetramethylurea; Sulfones such as dimethylsulfone and tetramethylenesulfone; Sulfoxides such as dimethylsulfoxide and diphenylsulfoxide; γ-butyrolactone,
Lactones such as ε-caprolactone; polyethers such as tetraglyme and 18-crown-6; nitriles such as acetonitrile and benzonitrile;
Examples include carbonate esters such as dimethyl carbonate and ethylene carbonate. Among the above solvents, aprotic polar solvents,
That is, it is preferable to use tertiary amines, amides, ureas, sulfones, sulfoxides, lactones, polyethers, nitriles, and carbonate esters. Particularly preferred are aprotic polar solvents with a dielectric constant of 20 or more. Note that among the above, when tertiary amines are used, they also act as catalyst components. The reaction of the present invention can be carried out in either a homogeneous system or a heterogeneous suspension system. The reaction temperature is
Usually, conditions of 100 to 300°C are employed, but a more preferable temperature range is about 100 to 250°C. The reaction pressure used is 50Kg/ ^cm2 or higher, but usually
It is more common to carry out at about 150 to 600 Kg/ ^cm2 . This method can be carried out in any of the batch, semi-continuous, or continuous reaction formats.
Oxygen-containing compounds produced by the reaction, ie, ethylene glycol, methanol, etc., can be separated by conventional separation methods, such as distillation. Furthermore, the distillation residue can be recycled and reused as a reaction catalyst liquid. [Examples] The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to the following Examples unless the gist thereof is exceeded. In addition, the amount of each product produced in the examples is expressed as the number of moles produced per gram atom of rhodium and the number of moles produced per hour as the turnover number (mol/g-atomRh·hr). Example 1 Internal volume 40ml with pressure resistance up to 600Kg/cm ² G
In a Hastelloy C autoclave under an argon gas atmosphere, 0.1 mmol of acetylacetonate bis(carbonyl)rhodium, 0.2 mmol of 1-isopropylphosphorinane, 3 mmol of N,N,N',N'-tetramethylhexamethylenediamine and a solvent. 5 ml of tetraethylene glycol dimethyl ether was charged. After sealing the reactor, the gas in the reaction system was replaced several times with a mixed gas of carbon monoxide and hydrogen at a molar ratio of 1:2, and the mixed gas was introduced into the reactor until the concentration reached 370 Kg/cm ² G at room temperature. Enclosed. The reaction solution was stirred using an external magnetic induction rotation system and heated using an electric furnace until the temperature of the reaction solution reached 220°C. When this temperature was maintained for 1 hour to carry out the reaction, gas absorption was observed over time. The maximum pressure reached was 516 Kg/cm ² . After the reaction was completed, the reactor was rapidly cooled to room temperature, and unreacted gas was purged to obtain a homogeneous reaction solution. As a result of quantitative analysis of this by gas chromatography, the main product was ethylene glycol 29.8 mol/g-atomRh.
hr and methanol 78.1mol/g-atomRh・hr
was gotten. Examples 2 to 6 Table showing the amount of 1-isopropylphosphorinane used.
The reaction was carried out in the same manner as in Example 1 except for the changes shown in Table 1. The results are shown in Table 1.

[Table] Examples 7 to 11 1-instead of 1-isopropylphosphorinane
The reaction was carried out in the same manner as in Example 1 except that t-butylphosphorane was used in the amount shown in Table 2. The results are shown in Table 2.

[Table] Examples 12 to 16 1-isopropylphosphorinane instead of 1-
The reaction was carried out in the same manner as in Example 1 except that isopropylphosphorane was used in the amount shown in Table 3. The results are shown in Table 3.

[Table] Examples 17-21 1-isopropylphosphorinane instead of 1-
The reaction was carried out in the same manner as in Example 1 except that n-butylphosphorane was used in the amount shown in Table 4. The results are shown in Table 4.

[Table] Examples 22 to 26 The results were obtained by carrying out the reaction in the same manner as in Example 1, except that the reaction pressure, water gas composition (H ₂ /CO ratio) and reaction temperature were changed as shown in Table 5. It is shown in Table-5.

[Table] Examples 27-28 Amount of 1-isopropylphosphorinane used, N,
Table 6 shows the results of a reaction carried out in the same manner as in Example 1, except that the amount of N,N',N'-tetramethylhexamethylenediamine (TMHDA) used and the type of solvent were changed as shown in Table 6. -6.

[Table] Example 29 Acetylacetonatobis(carbonyl)rhodium Rh(CO) ₂ acac containing 0.1 mg-atom of rhodium in a Hastelloy C autoclave with an internal volume of 35 c.c.
4,4-ethylenedioxy-2,2,6,6-tetramethyl-1-n- as tertiary phosphine
Butylphospholinane 0.093 mmol and N,N'-dimethylimidazolidone (DMI) 10 as solvent
I prepared ml. 300 mL of an equal volume mixture of carbon monoxide and hydrogen at room temperature.
It was press-fitted up to Kg/ ^cm2 . autoclave temperature
The initial value of the reaction pressure when raised to 220℃ is 480
It was Kg/ ^cm2 . The reaction pressure is increased to 480 to 460 Kg/cm ² by intermittently supplying an equal volume mixed gas of carbon monoxide and hydrogen.
The reaction was carried out at 220°C for 2 hours while maintaining the temperature within the range of . After the reaction, the autoclave was cooled and the contents were taken out and analyzed by gas chromatography, which revealed that 10.5 mol/g-atomRh・hr of ethylene glycol and 4.8 mol/g-atomRh・hr of methanol were produced. was confirmed. Comparative example 1 4,4-ethylenedioxy-2,2,6,6-
The reaction was carried out in the same manner as in Example 29 except that tetramethyl-1-n-butylphospholinane was not added. As a result, 4.5 mol/g-atomRh・hr of ethylene glycol and 1.9 mol/g-atomRh・hr It was confirmed that methanol was produced. Examples 30-32 4,4-ethylenedioxy-2,2,6,6-
Table 7 shows the results of the reaction carried out in the same manner as in Example 29, except that the amount of tetramethyl-1-n-butylphosphorinane (ETBP) used and the reaction temperature were changed as shown in Table 7. .

[Table] Example 33 The amount of Rh(CO) ₂ acac used was changed to 0.5mg-atomRh,
Results obtained by carrying out the reaction in the same manner as in Example 29, except that the amount of 4,4-ethylenedioxy-2,2,6,6-tetramethyl-1-n-butylphosphorinane used was changed to 0.5 mmol. , 5.2mol/g-
atomRh・hr ethylene glycol and 13.7mol/
It was confirmed that methanol of g-atomRh·hr was produced. Examples 34-47 The amount of Rh(CO) ₂ acac used was changed as shown in Table 8, and 4,4-ethylenedioxy-2,2,6,6-tetramethyl-1 was used as the tertiary phosphine.
-1-isopropyl-2,2,6,6-tetramethylphosphorinan-4-one or 1-cyclohexyl-2, instead of n-butylphosphorinane;
Table 8 shows the results of the reaction carried out in the same manner as in Example 29, except that 2,6,6-tetramethylphosphorinan-4-one was used in the amount shown in Table 8.

[Table] Examples 48 to 49 Example 29 except that the compounds shown in Table 9 were used in the amounts shown in Table 9 as organic amine compounds.
The reaction was carried out in the same manner. The results are shown in Table-9.

[Table] Examples 50 to 56 As shown in Table 10, the amount of Rh(CO) ₂ acac used and the type and amount of tertiary phosphines used were changed, and 1-methylimidazole or triethylamine was used as the organic amine compound. The reaction was carried out in the same manner as in Example 29 except for the addition of the following. Display the results -
Shown in 10.

[Table] Examples 57-60 Tetrarhodium dodecacarbonyl instead of acetylacetonatobis(carbonyl)rhodium
Using 0.1 mmol (0.4 mg-atom as rhodium atom), 1-n-hexyl-2,2,6,6-tetramethylphosphorinan-4-one (HTMPO) was added instead of 1-isopropylphosphorinane.
N,N,N',N'-tetramethylhexamethylenediamine (TMHDA) was used in the amount shown in 11.
The amount used was changed as shown in Table 11, and the solvent was replaced with tetraethylene glycol dimethyl ether.
Add 7.5ml of DMI to a molar ratio of carbon monoxide and hydrogen of 1:
1, and the reaction was carried out in the same manner as in Example 1 except that the reaction temperature was changed to the temperature shown in Table 11.
The results are shown in Table-11.

〔Effect of the invention〕

According to the method of the present invention, it is possible to produce ethylene glycol at a high level of yield that could not be achieved using conventional catalyst systems.

Claims (1)

[Claims] 1. In a method for producing ethylene glycol by reacting carbon monoxide and hydrogen in a liquid phase in the presence of a rhodium-containing catalyst, a phosphorus atom to which an alkyl group is bonded is added to a heteroatom in the reaction system. 1. A method for producing ethylene glycol, which comprises the presence of a tertiary phosphine having only one heterocycle having a phosphorus atom as a heteroatom and having no fused heterocycle having a phosphorus atom as a heteroatom. 2 In a method for producing ethylene glycol by reacting carbon monoxide and hydrogen in a liquid phase in the presence of a rhodium-containing catalyst, a heterocyclic ring having a phosphorus atom to which an alkyl group is bonded as a heteroatom is added to the reaction system. A method for producing ethylene glycol, characterized in that a tertiary phosphine compound and an organic amine compound having only a phosphorus atom and not having a fused heterocycle having a phosphorus atom as a heteroatom are present.