JPS60146839A - Preparation of ethylene glycol - Google Patents

Abstract

PURPOSE:To obtain the aimed compound in high yield, by using a rhodium catalyst and a specific trialkylphosphine as a reaction accelerator in reacting carbon monoxide with hydrogen in the liquid phase to produce the ethylene glycol. CONSTITUTION:Carbon monoxide is reacted with hydrogen in the liquid phase in the presence of a catalyst containing (A) rhodium and (B) a compound expressed by the formula PR1R2R3 (R1 is primary alkyl; R2 is secondary - tertiary alkyl or cycloalkyl; R3 is primary - tertiary alkyl or cycloalkyl) to give ethylene glycol useful as a raw material for polyester fibers, etc. in a high level of yield which has not been realizable in the conventional catalyst system. The amount of the compondnt (A) to be used is 0.0001-100g atom, preferably 0.001-10g atom expressed in terms of Rh atom based on 1l reaction solution. The amount of the component (B) to be used is 0.2-1,000mol, preferably 0.2-500mol, particularly 0.5-10mol based on 1g atom Rh.

Description

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

Ethylene glycol is a raw material for polyester fibers.

As an organic solvent raw material or non-volatile antifreeze.

It is an extremely important chemical product industrially.

Traditionally, ethylene glycol has been produced by the oxidation reaction of ethylene. In recent years, Ethylene Glyco 4T3♂-/No., Tokuko Shoj j-/, T0417 No., Tokuko Sho! θ-3/
/♂ issue, IIF! i Kimiaki! 6-ri No. 0737.

Special public Akira! ! -Ta 4t97, Tokuko Akira! j −Jj, <
No. 91, IJf! J Kosho J-33427, JP Kosho J
/-/, 2j20j issue, Tokko Akira! Goichi/(#9 da issue, Tokko Sho! Niichi 4to ty r -@, Tokukai Sho tko<t, ztori issue.

Tokuko Shoj, 2-412♂10, Tokko Sho! Goichigu0/
J- issue, JP-A-13-/, 2/7/-RI, JP-A-5G-71097, JP-A-J4T-4TR70J, JP-A-J (T-9,2903 1% Kaisho !Goo/gg/! issue.

Tokukai Akira! Boots 2.22 Fufu issue, Tokukai Sho, TJ-20 Otsu! Issue, #Kaisho 63-107♂/No. 9, Tokukaisho! Go-17
j4t? ? No., JP-A No. 1B17-/2RTITJ, Japanese Patent Application Publication No. 700, and US Pat.

Da-liri? , jko No. 0, 4t, /37,77 Otsu No., 4t
, /11. /tar issue, u, /j issue 3,423, g...
2.2 j, j No. 30.

da, / tata, j, 2/ issue, g, / 9117. As described in the specifications of No. 1, @, 2//, 7/R.

under high temperature, high pressure conditions using rhodium catalysts.

- Methods of reacting carbon oxide and hydrogen are well known.

However, the prior art methods exemplified above have not yet achieved sufficient catalytic activity to justify the use of expensive rhodium.

When this method is implemented on an industrial scale, there are problems such as koji molding.

The present inventors took into account one or more circumstances and made extensive studies to increase the activity of the rhodium catalyst.
In the formula, the group R1 represents a primary alkyl group, and the group R2 represents a secondary alkyl group, making it possible to produce ethylene glycol at a high level of yield as compared to a tertiary alkyl group.

The composition is preferably in the range of 15 to 5/l.

In the present invention, it is first necessary to contain rhodium as a catalyst component. As the supply form of the rhodium component, any rhodium metal or rhodium compound capable of forming a rhodium-carbonyl compound in one reaction zone can be used.

Specific examples of 20dium compounds include O-valent compounds such as dirhodium octacarbonyl, niacetylacetonatobis(
rhodium (carbonyl), bromo, tris(pyridine)rhodium, chlorotris(triphenylphosphine)rhodium/value compounds; rhodium trichloride, rhodium nitrate, rhodium acetate, etc. - oxides such as rhodium trihydroxide; tris(acetylacetone) Trivalent complex compounds such as rhodium; cluster compounds such as tetrarhodium dodecacarbonyl and hexalodium hexadecacarbonyl; anion complexes of the rhodium tetracarbonyl anion and carbide hexalodium pentadeca luponyl dianions;

The amount of rhodium used is 1 anti-o, ooi in concentration in one reaction solution.
~/θ gram atom range.

The present invention requires the use of specific trialkylphosphines as catalyst components, which act as reaction promoters. This is thought to have the function of coordinating with rhodium, the main catalyst, and controlling its electronic state. The details of the mechanism are not necessarily clear.

For example, the electron donating ability j of trialkylphosphine and its selectivity to ethylene glycol vary greatly depending on the type of phosphine. Therefore.

class alkyl group or cycloalkyl group (hereinafter referred to as "α")
-branched alkyl group), and the group represents a primary alkyl group or an α-branched alkyl group]. In this case, as a result of the electronic interaction between the alkyl groups in the trialxy primary phosphine molecule, the above-mentioned physical property constant of electron donating ability is reduced to the desired state by 1 cm, and suitable properties as a promoter are exhibited. be understood.

Specific examples of trialkylphosphines used in the present invention include di-1so-propyl-ethylphosphine, di-1eo-propyl-n-butylphosphine, di-t-
Butyl-methylphosphine, di-t-butyl-ethylphosphine, di-t-butyl-n-propylphosphine,
Di-t-phthyl-n-butylphosphine, dicyclopentyl-ethylphosphine, dicyclopentyl-n-propylphosphine, dicyclopentibire-n-butylphosphine, dicyclohexyl-methylphosphine, dicyclohexyl-ethylphosphine, dicyclo Xyl-
n-butylphosphine, diadamantyl-ethylphosphine, diadamantyl-n-butylphosphine.

dinorbornyl-ethylphosphine, dinorbornyl-
7 1M alkyl groups such as n-butylphosphine, 1sO-propyl-t-butyl-n-butylphosphine, 1-butyl-cyclohexyl-ethylphosphine, and
Trialkylphosphine with two α-branched alkyl groups; 1sO-propyl-diethylphosphine, 1eo
-Proyl-di-n-butylphosphine, 1F3o-1
0 pyr-ethyl-n-butylphosphine, t-butyl-
Diethylphosphine, t-butyl-cy-n-7'-tylphosphine, cyclobenthyl-diethylphosphine, cyclohexyl-di-n-octylphosphine, adamantyl-diethylphosphine, adamantyl-di-n-butylphosphine, norbornyl-diethylphosphine,
Examples include trialkylbosphines having one primary alkyl group and seven α-branched alkyl groups such as norbornyl-di-n-butylposphine.

The amount of trialkylphosphine to be used is usually O0-/,000 mol, preferably 09-2-200 mol, more preferably Oo, 2-200 mol, per 7 g atoms of 1r gb.
100 moles, more preferably in the range of o,t to 10 moles.

1. 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 a solvent, but a solvent can also be used.

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.

Alcohols such as ethanol, n-butanol, benzyl alcohol, phenol, ethylene glycol, diethylene glycol; carboxylic acids such as formic acid, acetic acid, propionic acid, toluic acid; methyl acetate, butyl acetate, benzyl benzoate esters; benzene, toluene.

Aromatic hydrocarbons such as ethylbenzene and tetralin; n-
Aliphatic hydrocarbons such as hexane, n-octane, and cyclohexane; halogenated hydrocarbons such as dichloromethane, trichloroethane, and chlorobenzene; nitro compounds such as ditromethane and nitrobenzene; N,N-dimethylformamide.

Carboxylic acid amides such as N,M-dimethylacetamide and N-methylpyrrolidone; hexamethylphosphoric triamide;
Sulfoxides such as N, N, N/, N/-tetraethyl sulfoxide and diphenyl sulfoxide; lactones such as r-butyrolactone and e-caprolactone; carbonate esters such as tetraglyme, /♂1-thyl carbonate, and ethylene carbonate. Can be mentioned.

Among the above solvents, it is preferable to use aprotic polar solvents, such as amides, ureas, sulfones, sulfoxides, lactones, polyethers, nitriles, and carbonate esters.

Particularly preferred are aprotic polar solvents having a dielectric constant of 20 or more.

The reaction of the present invention can be carried out either in a homogeneous system or in a heterogeneous suspension system. The reaction temperature is usually 1/,
Although the conditions of 00 to 300°C are adopted, the more preferable temperature range is /θθ~, 2! It is about θ°C. The reaction pressure is 1 normal! , Okg/, 4 or more is employed, but preferably about 9/l:d for /J'O- and θθ. The method of the present invention can be carried out in any batch, semi-continuous or continuous reaction mode. The oxygenated compounds produced by the reaction, ie, ethylene glycol, methanol, and ethanol, can be separated by conventional separation methods such as distillation. moreover.

The distillation residue of 1゜〈 can be recycled and reused as a reaction catalyst liquid. Below, the present invention will be explained in more detail with reference to Examples.
However, the scope of the present invention does not exceed its gist.

The following examples are not intended to be limiting.

The amount of product produced is expressed as the unit amount of rhodium atoms and the turnover a (moV7-atomRh-hr), which indicates the number of moles of product produced per unit reaction time. 0.0 in a Hastelloy C autoclave with product JjCC.
/ mmoJ rhodium-containing acetylacetonatobis(carbonyl)rhodium (Rh(Co), (aca
c) ), di(t-butyl)n-butylphosphine 0.
/mmoJ- and N-methylpyrrolidinone 10- were charged, and an isostatic mixture gas of carbon monoxide and hydrogen was charged up to 700 kg/- at room temperature. The initial value of the reactor pressure when the autoclave temperature was raised to J4θ°C was 4tJ' j kg764. After continuing the reaction for an hour.

2.2. j moL/ f -atom Rh, h
r ethylene glycol and /θ, /moi/f
-atom Rh, hr, methanol, etc. were reacted in the same manner as in Example-/. As a result, , 20.6
ethylene glycol of mo, J-/f-atomRh, hr and/J, 4tmoJ/f-atomRh, h
It was confirmed that r methanol was produced.

Comparative Example-1 The reaction was carried out in the same manner as in Example-1 without using di(t-butyl)n-butylphosphine, and as a result, /
2J moJ/l-atomRh, hr of ethylene glycol and rj moJ-/f-atomRh-h
It was confirmed that r methanol was produced.

Examples 3-4t Table showing the amount of di(t-butyl)n-butylphosphine used.
Table 7 shows the results of the reaction conducted in the same manner as in Example 2 except for the changes shown in /.

Table-/Example-! ~7 Table- instead of di(t-butyl)n-butylphosphine
The reaction was carried out in the same manner as in Example C, except that the phosphine shown in No. 2 was used and the degree of 1 reaction source and the amount of phosphine used were partially changed as shown in Table I. The results are shown in Table C.

Example-r~9 Table-- instead of di(t-butyl)n-butylphosphine
The reaction was carried out in the same manner as in Example 3, except that the phosphine shown in Example 3 was used and the reaction temperature was 230°C. The results are shown in Table-3.

Table-! Duck Comparative Example - Results of reaction carried out in the same manner as in Example -/, except that di(t-butyl)n-butylphosphine was used (without using di(t-butyl)n-butylphosphine and the reaction temperature was set at 230°C).

7-4 J mo J-/f/-&t Om Rh
-hr of ethylene glycol and! , r mol /
It was confirmed that methanol of f -a ton Rh -hr was generated.

Example-/σ Internal volume J! Suzu's Hastelloy a# θ, t in the autoclave
Acetylacetonatobis(carbonyl)rhodium (Rh(00)t(acac)) containing rhodium of mmoJ
), di(t-butyl)n-butylphosphine 0. t m
moJ and N,N/-dimethylimidazolidiine 4t
d was charged, and then an equal volume mixed gas of carbon monoxide and hydrogen was charged to 3'oo~/c+J at a historical temperature. The temperature of the autoclave is increased to 23θ℃ as the number of over/J,/
j mol/f-atomRh-hr, ethylene glycol and/or J/mol-/9-atomR
It was confirmed that h -hr methanol was produced. The space-time yield of ethylene glycol reached 2θf/t-hr based on the charging solvent. [In the rhodium-cesium benzoate-N-methylmorpholine hesulfolane (solvent) system, which is a typical known rhodium catalyst system, when using a high pressure of /Oj Okg/- and a high temperature condition of 260°C; L < i V 1da1 ) - and w, x, Walker Arrival, inorganic chemistry /
Volume 9, r9 < The reaction was carried out in the same manner as in Example 10 except that mmoJ was used. As a result, ? , 3rimoJ-/y-atoITlRh
-hr of ethylene glycol and/or riJ' mol
-/rate reached /JOf/1-br based on the charged solvent.

Claims (1)

[Claims] (1) - A method for producing ethylene glycol by reacting carbon oxide and hydrogen in a liquid phase, in which rhodium and the general formula PB, R, R are used as catalyst components. (In the formula, the group R8 represents a primary alkyl group. The group R1 represents a secondary alkyl group, a tertiary alkyl group, or a cycloalkyl group, and the group R3 represents a primary alkyl group, a secondary alkyl group. A method for producing ethylene glycol, which comprises using a trialkylphosphine represented by a tertiary alkyl group, a tertiary alkyl group, or a cycloalkyl group.