JPS60139633A - Production of ethylene glycol - Google Patents

Abstract

PURPOSE:To produce the titled substance useful industrially e.g. as a raw material of polyester fiber, etc., economically in high yield, by adding a tetraaminoethylene compound to the reaction system in the reaction of carbon monoxide with hydrogen in liquid phase in the presence of a catalyst containing rhodium. CONSTITUTION:The objective compound is produced by reacting carbon monoxide with hydrogen in liquid phase at 100-300 deg.C, preferably 100-250 deg.C and a reaction pressure of usually 150-600kg/cm<2>, in the presence of a rhodium-containing catalyst and a tetraaminoethylene compound. The tetraaminoethylene compound used as a reaction accelerator in combination with the above catalyst is the compound of formula (R<1>-R<8> are H, alkyl, aryl, etc. or may be bonded together to form a saturated or unsaturated ring), and its amount is 0.001- 100mol, preferably 0.01-10mol per 1g-atom of rhodium.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for the catalytic production of ethylene glycol from a synthesis residue, namely a mixture of carbon monoxide and hydrogen.

1. Ethylene glycol is an extremely important chemical chemical as a polyester fiber raw material, an organic solvent raw material, a non-volatile antifreeze liquid, etc.

Traditionally, ethylene glycol has been produced using ethylene and oxidation reactions. 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 (compared to ethylene), as the raw material 2. For example, Tokuko Shoj J-3//Coco, Tokuko Sho 33
-uJl, No. 2I, Special Public ShojtJ-/No. 10447, %
Kaisho 30-32/ No. 11, special public show! 6-4AI/3/
No., Special Public Show 1j-jμ27 Special Public Show! j, -JJt reference, Tokuko Shou 13-33697, Tokukai Sho! /-/2!2
No. 03, special public show j4-10r? U issue, Tokuko Akira! 6-san〇6ri No. 1, Tokukai Shoj No. 4A, 2to2 No., Tokukai Shoj J
-4A, 2r10, JP 16-110/32, JP 3-/Kot'yiv, JP ≠ -710, JP 1703, JP JP j4'-ta λ2
No. 03, Japanese Patent Application Publication No. 1983-1 tatj, %translation No. 11-9061, No. 33-1
0♂gzari issue, Japanese Patent Publication No. 167711191, Shoj
7-/u, f641j, JP-A-17-/30P Ko-1, and JP-A-7-/309≠λ, as well as U.S. Patent No. 0/J, 700,! , /99,120,
Chi / J J, No. 774, 4I, / j /, /夛λgo, each /j 萬6ko3ki, II, 2koj, No. 130, 4
, No. 1951121, II, No. 90.191, et al.
2//, 77 P and 30υ17, using a rhodium catalyst, however, the prior art methods exemplified above do not require the use of expensive rhodium. Since sufficient catalytic activity has not yet been achieved, there are serious problems that make this method difficult to implement on an industrial scale.

In the rhodium-containing catalysts shown in the above-mentioned prior art, it has been proposed to use a promoter, and the use of a Lewis base compound is exemplified as one of them, but nothing proposed so far is not always fully satisfactory. In consideration of the above facts, the inventors have
The gist of this invention is a method for producing ethylene glycol, which is characterized by using rotitraaminoethylenes.

-Hereinafter, the present invention will be explained in more detail.

The raw material gases used in the present invention, namely carbon monoxide and hydrogen, are not particularly limited (although they may contain some amount of inert gas such as nitrogen gas or carbon dioxide). The volume ratio of hydrogen to carbon monoxide is usually //10-
/0//, especially /, Q~! Either rhodium metal or a rhodium compound forming a carbonyl compound having a composition within the range of about 100 ml can be used.

Specific examples of the rhodium compound include θ-valent compounds such as dirhodium octacarbonyl; 1iIlli complex compounds such as rhodium acetylacetonatodicarbonyl and bromotris(pyridine)-dium; salts such as rhodium trichloride, rhodium nitrate, and rhodium acetate; ;Oxide such as rhodium trihydroxide;J value such as tris(acetylacetone)rhodium'
The amount of rhodium used is usually 0.000/-/00 gram atoms per reaction solution as a concentration in the reaction solution.
Favori L < l-j O, 001-1'0 is a gram-atom category crystal. □ In the present invention, tetraaminoethylenes are used as a reaction promoter together with the above-mentioned rhodium-containing catalyst. The general formula of the tetraaminoethylenes is as follows.

In the general formula (1) above, ul', R2, R8', x4
, x@, R@.

R7 and R@ may be the same or different and represent hydrogen, an alkyl group, an aryl group, or the like. As the alkyl group, a lower alkyl group is preferred. Examples of the aryl group include a phenyl group and a naphthyl group. The aryl group may further have a substituent such as a lower alkyl group, a lower alkoxyl group, or a halogen. Other examples include WR, nitrogen, and sulfur. Among the above-mentioned tetraaminoethylenes, tetraaminoethylenes substituted with a tertiary alkylamino group are particularly preferred. Examples of such tetraaminoethylenes include tetraamineethylene and tetrakis(methylamino)ethylene, /,! -diamino-/, J-bis(butylamino)ethylene, tetrakis(dimethylamino)ethylene, tetrakis(methylbutylamino)ethylene, 1
．． l-bis(methylamino)-2,2-bis(butyramite ethylene, l-dimethylamino-/-methylamino-co-amino-λ-diptylaminoethylene, tetrakis(diphenylamino)ethylene, l,/-bis( phenylamino) -J,, 2-bis(methylamino)ethylene, tetrakis[bis(p-methoxyphenyl)amine]ethylene, tetrakis(pyrrolidinyl)ethylene:
Tetrakis(piperidino)ethylene: Tetrakis(morpholino)ethylene: Tetrakis(a-methylpiperazinyl)ethyl/,/-dipyrrolidinyl-λ,λ-bis(dimethylamino)ethylene, ll, 2-divirolidinyl-7, corbis(dimethylamino) ) ethylene, i,i-dibiperidino-2,2-
Dimorpholinoethylene, etc.; Δ2″′-bisimidazolidine and Δ2′2′-bis(l,3-dimethylimidazolidine): Δ2′2′-bis(l,3-diethylimidazolidine)
Δ2,2'-bis(/,3-di-I-propylimidazolidine): Δ2I2'-bis(l,3-di-n-butylimidazolidine): Δ''''-bis,3-di 180-Propylimidapolysine): Δ2′2′-bis(l,3-di5ec-butylimidazolidine): Δ212′-bis(l,3-c-t-butylimidazolidine): Δ2″′-bis(l , 3-dibenzylimidazolidine)
: Δ2″′-bis('IJ-diphenylimidazolidine)
: Δ2″′-bis(l,3-di1)-)lylimidazolidine): /, J-dimethyl-7′,3′-diethyl-Δ2″′2′glΔ2″′-bis(/-methyl- 3-ethylimidazolidine): /, 3-dimethyl-i/, J/-diphenyl-Δ212
′-bisimidazolidine: Δ””-His(/-ethyl-3-phenylimidazolidine): Δ2″′-bis(l,j-dimethylpexahydrobyrimidine): ・′,p12′-His(t , 3-diethylhexahydropyrimidine): Δ2″'-biX(t,3-diphenylhexahydropyrimidine): /, J-dimethylrube3'-diethyl-Δ2″'-bis(hexahydropyrimidine) ): /, /'-diethyl-3,3'-diphenyl-Δ2p2
'-Bis(5-dimethyl-V-imidazo-): Symmetrically and asymmetrically substituted bis(hexahydropyrimidine)s such as:
1+): ";2,2'-bis(/, J-diphenyl-guimida-19in): Δ2,2'-bis(l-ethyl-3-methyl-q-imidacillin): Asymmetrically substituted bisimidacillin;
, 7,10-tetramethy, luco, j, 7. /θ-tetraazabicyclo IJ1. O) Dec-1(6)-ene: and other tetraazabicycloalkenes.

The amount of these tetraaminoethylenes to be used is 0.00/-100 mol <,
Preferably 0.0/~iomol, more preferably θ
, lN co, σ mole.

Although the present invention can be carried out in the absence of a solvent, that is, the reaction raw materials and catalyst components themselves can be used as solvents, a solvent can also be used.

Examples of such solvents include diethyl ether,
Anisole, tetrahydrofuran, ethylene glycol dimethyl ether, dioxane-based ethers; ketones such as acetone, methyl ethyl ketone, acetophenone; methanol, ethanol, n-7' tanol, benzyl alcohol, alcohol, phenol, ethylene glycol,
Alcohols such as diethylene glycol; formic acid, acetic acid,
Carboxylic acids such as propionic acid and toluic acid; Esters such as methyl acetate, n-nibutyl acetate, and benzyl benzene; Aromatic hydrocarbons such as benzene, toluene, ethylbenzene, and tetralin; n-hexane, n-octane,
Aliphatic hydrocarbons such as cyclohexane; dichloromethane,
Halomenated hydrocarbons such as trichloroethane and chlorobenzene; nitromethane, nitrobenzene, etc.1. "of·)
tertiary amine; triethylamine, tri-n; 4: decathylamine, benzyldimethylamine, dimethylamine, a-picoline, co-hydroxypyridine; N,N-dimethylformamide , N, N-dimethylacetamide, N-methy, carboxylic acid amide such as pyrrolidone; hexamethylphosphoric acid triamide, N,
11. Amides of inorganic acids such as N',N'-tetraethylsulfamide;N,N'-dimethylimidazolitone, N
, M, N', N'-Ureas such as tetramethyl urea; sulfones such as dimethylform□hole, tetra□tra□:) A::-dinesulfone; Examples include sulfoxides; lactones such as r-butyrolactone and C-caprolactone; =tolyls such as tetraglyme, tolyl, and bentanil; carbonic acid esters such as dimethyl carbonate and ethylene carbonate; and the like.

Among the above-mentioned solvents, it is preferable to use aprotic polar solvents, ie, amines, amides, ureas, sulfones, sulfoxides, lactones, polyethers, nitriles, and carbonic esters. Particularly preferred are aprotic polar solvents having a dielectric resistivity of 0 or more.

``Using the above solvent in the Ht valley, the reaction is homogeneous -
It can be carried out either in a heterogeneous suspension system or in a heterogeneous suspension system.

As for the reaction temperature, conditions of 100-300°C are adopted, but a preferable temperature range is 100°C! It is about θ°C. Regarding the reaction pressure, either a general semi-continuous reaction type or a continuous reaction type can be used. Oxygenated compounds produced during the reaction, namely methanol and ethanol.

Ethylene glycol etc. can be separated using conventional separation methods, such as distillation. Furthermore, the distillation residue can be recycled and reused as a reaction catalyst liquid.

Hereinafter, the present invention will be explained in more detail by way of examples.
The invention is not limited by the following example VC.

Lambdodecacarbonyl Hh4(00)u and tetrakis (
dimethylamino) ethylene 0.0! mmo1 work IJ
-Methylpyrrolidinone lO- was charged, and then an equal volume mixed gas of -carbon oxide and hydrogen was charged to 3"OO at room temperature. Autoclave temperature JP-A-139G33
(6) When the temperature was increased to 2≠θ°C, the initial value of the reactor pressure was surprising. After continuing the reaction for 2 hours, the autoclave was cooled and 5//, 2 mo
Production of methanol of 1/g-atom Rh@hr was confirmed.

Examples, except that the amount of the 2-70ium compound tetrakis(dimethylamino)ethylene (TDMAE) used and the solvent were changed.
As a result of conducting the reaction in the same manner as in Example 1, the results shown in Table 1 were obtained.

Follow the same procedure as in Example D, except for changing the dose of tetrakis(dimethylamino)ethylene! The results were as follows: Table 1. , Table 6--12 Reactivity Corro, carried out at 0°C.

Example/J.

,,tetrakis(dimethylamino)ethylene0.08
Instead of using 1 mol of fr, Δ2″′-bis(l, 3
-diphenylimidazolidine)0. As a result of carrying out the reaction in the same manner as in Example 1 using 1-cho rD1, the turnover number was 0, tμmoVg-atomRh
shr ethylene glycol and/1. JtmoVg-
Methanol of atom RhIIhr was obtained.

Examples 1g to 17 Δ2 instead of tetrakis(dimethylamino)ethylene
″′-bis(l,3-dimethylimidazolidine) (BD
The reaction was carried out in the same manner as in Example G, except that Mtech M) was used, and the results shown in Table 3 were obtained.

Table 3 Comparative Example 1-λ The reaction was carried out in the same manner as in Example 1 without using tetrakis(dimethylamino)ethylene. The results are shown in Table 3.

table - group

Claims (1)

[Claims] (1) A method for producing an oxygenated food by reacting carbon monoxide and hydrogen in a liquid phase in the presence of a rhodium-containing catalyst, characterized by the presence of nato-2-aminoethylenes in the reaction system. Method for producing ethylene glycol.