JPS61291532A - Production of ethylene glycol - Google Patents

Abstract

PURPOSE:To produce the titled substance by the liquid-phase reaction of a synthesis gas in the presence of an Rh-containing catalyst in a reaction system containing an organic amine and a tertiary phosphine having a heterocyclic ring containing an alkyl-bonded P atom as the hetero-atom. CONSTITUTION:Ethylene glycol is produced by the liquid-phase reaction of CO with H2 in the presence of an Rh-containing catalyst (e.g. Rh octacarbonyl). The reaction is carried out in the presence of a reaction accelerator consisting of (A) a tertiary phosphine having one heterocyclic group containing a P atom bonded with an alkyl group as the hetero-atom (e.g. 1-methylphosphilane) and (B) an organic amine (e.g. methylamine), in homogeneous or heterogeneous suspension system at 100-250 deg.C and 150-600 kg/cm<2>. The amounts of the components A and B are 0.5-100mol and 1-100mol per 1g-atom of Rh, respectively. EFFECT:The objective compound can be produced in an extremely high yield.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention 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 an extremely important chemical product industrially as a raw material for polyester fibers, a raw material for organic solvents, and a non-volatile antifreeze solution.

[Conventional technology]

Traditionally, ethylene glycol has been produced by the 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, Tokuko Shojs-J//λλ, Tokuko Shojyo Kazuhiro 31
2/@.

Special public Akira! 3-/jO'17, JP-A-Shoto-3xtir
issue.

Tokuko Showa 14-Hiroshi 0/3/ issue, Tokuko Showa 5r-j41.27
issue.

Special introduction J'! -JJ & 71I, Tokuko Akira! -3362
No. 7.

Tokuko Shoj/-/2Jr No. 203, Tokuko Sho tg-iorr
No. a.

Special Public Sho Jz-4Aotyr, Japanese Patent Public Sho 12-'7210
No. 1.

Tokukai Akira! λ-Hiroshi 2102, Tokukai Shoyo Korg 21110
issue.

Tokko Sho, t4-Hiro ot3λ, Tokko ShojJ-/λ/7/
Gu issue.

1R Kaisho J4A-71091, JP Kaisho 74 (-141
No. 703, Tokukai Sho! Hiro - Octopus No. 203, Tokukai Akira! ≠−/
felt/! No., Tokukai Akira! Goolko 2// issue, Tokukai Akira! Yoichita OTR issue, JP-A-17-/2R61A! No. % JP-A-4-7! No. 1791, JP-A-17-/JOP'l
No. I, JP-A No. 7-7309≠λ, and JP-A No. 3-
Iorrr publications and U.S. Patent No. 013,7
No. 00, ゛gu, l Tata, jko No. 0, ≠, /, 3J, 77
No. 6, Gu, /11. / No. 92, g, / j j, j2
No. 3.

Sails 226. ! No. 30, ≠, l tata, j27, ≠, iy
o, zuri o issue.

As described in the specifications of ≠, 30, j≠7, and ≠, 2//, 7/, using a rhodium catalyst,
A well-known method is to react carbon oxide and hydrogen under high temperature and high pressure conditions.

[Problem that the invention seeks to solve]

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

This method has problems such as difficulty in implementing it on an industrial scale.

[Ninth way to solve the problem]

The inventors of the present invention took into account one or more circumstances, and as a result of conducting intensive studies to increase the activity of the eI radium medium, they arrived at the present invention.

That is, the gist of the present invention is as follows.

In a method for producing ethylene chloride by reacting carbon monoxide and hydrogen in the liquid phase in the presence of a rhodium-containing catalyst, a heterocyclic ring having a phosphorus atom bound to an alkyl group in the reaction system is used. A method for producing ethylene glycol, which comprises the presence of a tertiary phosphine having one phosphine;

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, the reaction system contains one heterocyclic ring having a phosphorus atom bound to an alkyl group as a heteroatom. A method for producing ethylene glycol, characterized in that a tertiary phosphine and an organic amine compound are present.

According to the method of the present invention, it is possible to produce ethylene glycol with a yield that is at a very high level and which cannot be achieved using conventional catalyst systems.

The present invention will be explained in detail below.

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 and carbon monoxide is usually i/
It is preferable to use one having a composition in the range of 10 to 10/l, and particularly in the range of 115 to 5/1.

In the present invention, rhodium is used as a catalyst component. As the supply form of the rhodium component, it is possible to use either rhodium metal or a rhodium compound that forms a rhodium carbonyl compound in the reaction zone.

Specific examples of rhodium compounds include O-value compounds such as diadium octacarbonyl; monovalent complex compounds such as acetylacetonatobis(carbonyl)rhodium, bromotris(pyridine)cldium, rhodium trichloride, rhodium nitrate, acetic acid rhodium, etc. Examples include clusters such as tetrarhodium dodecacarbonyl and hexalodium hexadecacarbonyl; anion complexes such as rhodium tetracarbonyl anion and carbide hexalodium 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 is previously coordinated, as described below.

The amount of rhodium used is in the range of 0.0001 to 700 gram atoms, preferably o, ooi-to gram atoms, as a concentration in one reaction solution/reaction solution.

In the present invention, a tertiary phosphine having one heterocyclic ring having a phosphorus atom bonded to an alkyl group as a heteroatom, which acts as a reaction accelerator, is further used as a catalyst component.

Preferred examples of the tertiary phosphines include the general formula (I): (wherein s R1 represents a chain or cyclic alkyl group, s R2 represents alk, a kyl group, an oxo group, a hydroxyl group,
Represents a saturated or unsaturated aliphatic hydrocarbon chain optionally substituted with an alkoxy group or an alkylene dioxy group. ).

As for the tertiary phosphines represented by the above general formula (1), the size of the heterocycle having a phosphorus atom as a heteroatom is usually a 3- to io-membered ring, preferably a ≠ to 7-membered ring, and %R2 is an alkyl group, alkoxy group or alkylenedioxy group, the number of carbon atoms of the substituent is /-
10, preferably /-j, and the number of carbon atoms in t7tR+ is 1. Specific examples of the above tertiary phosphines include:

Phosphyranes such as /-methylphosphyrane, l-inpropylphosphyrane, /-1-butylphosphyrane;
/-Methylphosphetane, l-isopropylphosphetane% 't2,43#≠, Hiro-hexamethylphosphetane% l-isopropylphosphetane, 2. J,≠,4! -pentamethylphosphetane, /-t-7'thyl-λ, 2,
3. Phosphetanes such as ≠, ≠-pentamethylphosphetane, /-n-butylco,co,3,3-tetramethylphosphetane; l-methylphosphorane, /-4soprobylphosphorane, l-cyclohexyl Phosphorane, /-n
-butylphosphorane, /-1-butylphosphorane.

/ -5ec-butylphosphorane, /,! -dimethylphosphorane s 'e Phosphoranes such as coco-methylphosphorane; phosphoranes such as l-butylphosphorane, ``/, J-dimethylphospholene, l-isopropylphosphorene, l-cyclohexylphosphorene; l -Methylphosphole, t-n-7'tylphosphole, /-n-butyl-
Phosphores such as λ, t-dimethylphosphole* /
-n-furphosphorinan, l-isopcubylphosphorinan, l-cyclohexylphosphorane, /-1butylphosphorinane% / -5ea-butylphosphorinane-/
Phosphores such as -n-butylphospholinane; l-methyl-co, λ, 6,6-titramethylphosphorinane-hiro-one/-n-butyl-λ, λ, otsu, 6-titramethylphosphorinane-hiro -one u-n l-isobuvir-2,co,t,6-titramethylphosphorinane-≠-one Pr-↓ 06H11-C70'lO /-n-hexyl-λ,J,4,4- Phosphepanes such as tetramethylphospholinan-Hiro-one IIHIII-n; /-isoprobylphosphorinan-7-ol FK r-1 1-cyclohexylphosphorinane-≠-ol ff 01HII-Cμm0 /-n-butyl- ,2,2,t,t-tetramethylphosphoritin-l-ol H u-n l-imp avir-2,λ, O, 6-titramethylphosphorinan-≠-ol H r-1 1-cyclohexyl -2,2,t,t-tetramethylphosphorinan-Hol-ol E O@H11-ayel.

Suphorin ■ r-1 /-1-butyl-/, 2. ! , 6-titrahydrophosphorine u-t /-n-7'thyl-l, Hiro-dihydrophosphorine-≠-
on u-n l-cyclohexyl-/, 4t-dihydro a phosphorine-
≠-one 06E[11-(37010 etc. Hydrophosphorines; "l-Methylphosphepane, /-n-propylphosphepane% l-Isofurovirphosphepane, /-1-butylphosphepane , phosphepanes such as l-cyclohexylphosphepane, and the like.

The amount of these tertiary phosphines to be used varies depending on the type of compound, but is usually 0.1-7000 mol, preferably 0.1 to 7000 mol per gram atom of rhodium. j −j 00
moles, more preferably in the range of 0.2 to ioo moles.

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 compound include methylamine,
Alicyclic amines such as ethylamine, n-20 pylamine, isopropylamine, octylamine, dimethylamine, diethylamine, di-n-propylamine, methylethylamine, trimethylamidicyclohexylamine, tricyclohexylbumine, dicyclohexylmethylamine; ethyleneimine , ethyleneimines such as methylethyleneimine; piperidine, l-methylpiperidine,
Piperidines such as comethylpiperidine, 3-methylpiperidine, ≠-ethylpiperidine; pyridine, -1methylpyridine, 3-methylpyridine, l-ethylpyridine, J, F, j-trimethylpyridine% Go 72 nobilidine, λ- Aminopyridine, Co(dimethylamino)pyridine,! Pyridines such as -(methylamino)pyridine Sguanilinopyridine%4', (methylamino)pyridine, U-(dimethylamino)pyridine; quinoline, co(dimethylaξ))quinoline%l-(dimethylai))
Quinolines such as quinoline;≠,! -phenanthroline,
/, 7 enanthrolines such as r-7 enanthroline; piperazine, l-methylbiperazine.

Piperazines such as /-phenylpiperazine; Formula amines such as diazabicycloundecene and diazabicyclooctane; imidazole, l-methylimidazole, l-ethyl imidazole, benzimidazole, l-methylbenzimidazotol, l- ethylbenzimidazole, t,
a-dimethylbenzimidazole, /,! , 1-) Imidazoles such as dimethylbenzimidazole and -1methylbenzimidazole; triazole, l-benzyltriazole, l-methyltriazole, benzotriazole, l-methylbenzotriazole, l-ethylbenzotriazole, λ-methyl Benzotriazole%! ,
6-dimethylpenzotriazole, tetrazole, l-
Polyazoles such as methyltetrazole; aniline, /-f7 thylamine, conaphthylamine, 0-)
Luidine, p-toluidine, 0-3-xylidine, benzylamine, diphenylamine, dimethylaniline, diethylaniline, i, r-diaminonaphthalene, t, r
- Aromatic amines such as bis(dimethylamino)naphthalene, etc.; l, λ-ethanediamine, /, J-propanethiaine, H, N, N', N'-tetramethylethylenediamine, N, M, M 'Ken'-tetramethylethylenediamine, N,M,N',H'-tetramethylhexamethylenediamine, tetrakis(dimethylamino)ethylene, tetrakis(piperidino)ethylene, tetrakis(morpholino)ethylene, tetramethyl-Δ11'- Bis(imidazolidine), tetrabenzyl-Δ42'-bis(imidazolidine), 0-phenylenediamine, p-7 22-diamine, o-toluidine S
Aliphatic and aromatic polyamines such as N, N, N', M'-tetramethyl-p-phenylenediamine: ethanolamine, jetanolamine, morpholine, methylmorpholine, co-hydroxypyridine, l-methoxychloride Pyridine% goohydroxypyridine% goomethoxypyridine, 4t-phenoxypyridine, comethoxyquinoline, -monohydroxyimidazole.

Examples include oxygen-containing amines such as 2-methoxybenzimidazole.

When using the above organic amine compound, the amount used varies depending on the group of the compound, the type and amount of tertiary phosphine used, but is based on 1 gram atom of rhodium.

Usually 0.00/~toooo mol, preferably 0.1~3
00 mol, more preferably in the range of /-700 mol.

Although it also varies depending on the type of tertiary phosphine used in combination, 1. Among the above organic amine compounds, it is generally preferable to use tertiary amines.

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 present invention can be carried out in the absence of a solvent, ie the reaction raw materials and the catalyst components themselves serve as the reaction medium, 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, engineered ethanol, n-butanol, and benzyl alcohol; -ru, phenol,
Pulcols such as ethylene glycol and diethylene glycol; formic acid and acetic acid.

Carboxylic acids such as propionic acid and toluic acid; Esters such as methyl acetate, n-butyl acetate, and benzyl benzoate; Aromatic hydrocarbons such as benzene, toluene, ethylbenzene, and tetralin; n-hexane, n-octane, and cyclohexane Aliphatic hydrocarbons such as dichloromethane,
Nohalokenated hydrocarbons such as ethane and chlorobenzene; nitro compounds such as nitromethane and nitrobenzene; phosphoric acid triamides such as triethylamine, tri-n-butylamine, benzyldimethylamine, pyridine, α-picoline%--hydroxypyridine, l/
e -Ureas such as methyl urea; Sulfones such as dimethyl sulfone and tetramethylene sulfone; Sulfoxides such as dimethyl sulfoxide and diphenyl sulfoxide; r-Petitlactone% -lactones such as monocaprolactone; tetraglyme, it-crown-
Polyethers such as No. 6; nononitriles such as acetonitrile and benzonitrile; carbonate esters such as dimethyl carbonate and ethylene carbonate.

Among the above solvents, aprotic polar solvents, namely tertiary amines, amides, and ureas.

Preference is given to using sulfones, sulfoxides, lactones, polyethers, nitriles and carbonic esters. Particularly preferred are aprotic polar solvents with a dielectric constant of 40 or more. In the above, when tertiary amines are used, they also act as catalyst components.

The reaction of the present invention is a homogeneous system or a heterogeneous suspension system. As for the reaction pressure, a pressure of JO or higher is employed, but it is more common to carry out the reaction at about /'10-600. This method is a batch method.

・Rose oxygen compound produced by 4 reactions that can be carried out in either semi-continuous or previously continuous reaction form,
i.e. ethylene glycol.

Methanol and the like can be separated by conventional separation methods, such as distillation. Furthermore, the distillation residue can be recycled and reused as a reaction catalyst liquid.

〔Example〕

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to the following Examples unless it exceeds the gist thereof.

In addition, the production amount of each product in the examples is a of 1 Durham atom.
The number of moles of sodium produced per hour was expressed as the number of turnovers (mol/g-atom Rh'hr).

Example-1 Acetylacetonatobis(carbonyl) eIdium Q, /
mmol, /-isopropylphosphorinane o, 4mm
ol, N, N, N', N'-tetramethylhexamethylenediamine J mmol, and tetraethylene glycol dimethyl ether J- as a solvent were charged. After sealing the reactor, the gas in the reaction system was replaced several times with a mixed gas of -carbon oxide and hydrogen at a molar ratio of 1, and the mixed gas was sealed in the reactor until the temperature reached 370-G at room temperature. The reaction solution was stirred using an external magnetic induction rotation method 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 is ti
Short and hot light.

After the reaction was completed, the reactor was rapidly cooled down to room temperature, and unreacted gas was purged to obtain a homogeneous reaction solution.

Quantitative analysis of this by gas chromatography revealed that the main products were ethylene glycol,
mol/V-atom Rh-hr and methanol 7
r, / mol/P-atomRk-hr dl.

Example -t The amount of l-inopropyl small sulfolinane used was changed as shown in Table 1, and the reaction was carried out in the same manner as in Example 1, and the optical results are shown in Table 1.

Table-1 Example-7 ~ // The reaction was carried out in the same manner as in Actual Example-1, except that 1-1-butylphosphorane was used in the amount shown in Table-1 instead of l-isopropylphosphorane. The experimental results are shown in Table-C.

Table 2 Actual Examples 1λ to 16 The reaction was carried out in the same manner as in Example 1 except that 1-isopropylphosphorane was used in the amount shown in Table 3 instead of 1-isopropylphosphorane. are shown in Table-3.

Table-3 "+P" The results are shown in Table-μ.

The reaction was carried out in the same manner as in Example-/ except for the north, with the temperature changed as shown in Table-Y. Show it! Shown below.

Example-27~, 2r Amount of l-improvirphosphorinan used, N.

The reaction was carried out in the same manner as in Example t, except for changing the amount of N,N',N'-tetramethylhexamethylenediamine (TMHDA) used and the type of solvent as shown in Table 6.Results are shown in Table-6.

Example - Acetylacetonatobis(carbonyl)ef lysium h(
00).

aCaol as tertiary phosphine ≠, 4c-ethylenedioxy-2λ, G, 4-tetramethyl-/-n
-butylphosphorinane 0.0? J mmol and N,N'-dimethylimidazolitone (DM) towt as a solvent were charged.

Pressure-inject an equal volume mixed gas of carbon monoxide and hydrogen up to 300℃ at room temperature. When the temperature of the autoclave was raised to 0°C, the initial value of the reaction pressure was ≠10~. - Intermittently supplying an equal volume mixed gas of carbon oxide and hydrogen to increase the reaction pressure to ≠10, 1 mol/f-at mouth Rheh
It has been confirmed that the methanol force 1 of r is generated.

Comparative example-7 ≠, 41. -Ethylenedioxyco,co,a,a-tetramethyl-/-n-butylphosphorinane was not added and photoremoval was carried out in the same manner as in Example - Kota. As a result,
It was confirmed that 4t, jm: +Vf-atamRh.hr of ethylene glycol and t, 2t, 1/f-atanRh.hr of methanol were produced.

Examples 30 to 32 Gu, Hiro-ethylene dioxy-2. Ko, 6. Bu-tetramether/-n-butylphosphorinane (]!l'l"BP
) and the reaction temperature were changed as shown in Table 7, and the reaction was carried out in the same manner as in Example λ for light removal. Table 7 shows the experimental results.

Table-7 Example-33 The amount of Rh(Co)2acac used was 0.7 jy-at
omRh K% Hiro.

The amount of μ-ethylene dioxyco, co, 6,6-titramethyl-/-n-butylphosphorinane used was 0.6 m per 1 time.
The reaction was carried out in the same manner as in Example-Kota except that 2 rrDl/$'-atomRh*
hr of ethylene glycol and tJ, 7 moVf-
It was confirmed that methanol was being produced by A-Ko M Co., Ltd.

Example-3 μ to Hiro 7 The amount of Rh (Co)2 aoac used was changed as shown in Table-t, and the tertiary phosphine was Hiro,≠-ethylenedioxy-2-2-2-2,6-titramethyl-/- n-
l-impukupir λ instead of butylphosphorinane,
λ,6,6-titramethylphosphorinane-≠-one or ha/-cyclohexylruco,λ,j,4-tetramethylphosphorinane-one was used in the amounts shown in Table-r, and the optical removal was The reaction was carried out in the same manner as in Example 1. The results are shown in Table t.

Example -≠rA-≠Reaction was carried out in the same manner as in Example 22, except that the compounds shown in Table 1 were used in the amounts shown in Table 2 as organic amine compounds. The results are shown in the table.

Example-! The amount of KRh(00)2acaa used and the type and amount of tertiary phosphines used were changed as shown in Table IO.
The reaction was carried out in the same manner as in Example-λ except that l-methylimidazole or triethylamine was added as the organic amine compound.

The results are shown in Table-10.

Example-! 7-10 Acetylacetonatobis(carbonyl) r: 1 Instead of dium, tetrarhodium dodecacarbonyl o, t m
mol (O0≠thiatom as rhodium atom)
Table 1 shows the amount of l-isopropyl phosphorinane used.
/l, and the solvent was replaced with tetraethylene glycol dimethyl ether by KDM FJ d K,
-The ratio of carbon oxide and hydrogen was changed to /:/, and the reaction temperature was changed to the temperature shown in Table-//IIC except for Example-1.
The reaction was carried out in the same manner. The results are shown in Table IIC.

〔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 (2)

[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 heterocyclic ring containing 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 one tertiary phosphine is present. (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 bonded to an alkyl group as a heteroatom is added to the reaction system. A method for producing ethylene glycol, characterized in that one tertiary phosphine and an organic amine compound are present.