JPS6041660B2 - Method for producing ethylidene diacetate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing ethylidene diacetate, which is characterized by subjecting methyl acetate or dimethyl ether, carbon monoxide, and hydrogen to a hydrocarbonylation reaction.

More specifically, ethylidene diacetate is produced by reacting methyl acetate or dimethyl ether with carbon monoxide and hydrogen in the presence of a nitrogen-containing organic nitrogen group compound and a catalyst consisting of nickel. The present invention relates to a method for producing ethylidene diacetate, characterized in that the method uses a specific palladium-supported catalyst as a co-catalyst. Conventionally,
Generally known methods for synthesizing ethylidene diacetate include a method using acetylene and acetic acid as raw materials and a method of synthesizing ethylidene diacetate by reacting acetaldehyde and acetic anhydride.

Recently, in the presence of halides, a liquid-phase homogeneous catalyst system using rhodium or palladium salts or complexes soluble in the reaction solution as the main catalyst and a specific organic nitrogen group compound or inorganic metal compound as a co-catalyst has been developed. A method for synthesizing ethylidene diacetate from methyl acetate or dimethyl ether was disclosed in JP-A-51-11540. In contrast to this method using expensive precious metals, we have developed a method using a new catalyst system using nickel or cobalt as Japanese Patent Application No. 1176/1982. The present inventors previously filed a patent application for a method using a solid catalyst in which palladium metal is supported on a porous inorganic material in Japanese Patent Application No. 55-28433. The former method is superior in that it uses an inexpensive catalyst, and the latter method is superior in that it is easy to separate and recover the product and catalyst, but the present inventors have As a result of intensive research aimed at further increasing the yield of acetate, they discovered a catalyst system that uses palladium metal as a co-catalyst in a catalyst consisting of a halide and nickel, and completed the present invention. That is, the present invention provides at least one type of halide such as an iodide or a bromide, an organic nitrogen group compound containing phosphorus or nitrogen,
and a method for producing ethylidene diacetate by reacting methyl acetate or dimethyl ether with carbon monoxide and hydrogen in the presence of a catalyst made of nickel,
As a cocatalyst, a solid catalyst in which 0.01 to 30% (by weight) of palladium metal is supported on a porous inorganic material with a pore volume of 0.03 to 2.5 d/g and a surface area of 0.1 to 15007 Tf/g is used as a cocatalyst. This is a method for producing ethylidene diacetate, characterized in that palladium is used in a molar ratio of 1 to 1/30.

Although the detailed reaction operation of the hydrocarbonylation reaction of methyl acetate or dimethyl ether according to the present invention is not clear, the overall reaction can be represented by the following chemical reaction formula.

(1) When methyl acetate is used as a raw material (2) When dimethyl ether is used as a raw material The catalyst of the present invention uses a halide, which is at least one type of iodide or bromide, and inexpensive nickel as the main catalyst, and a small amount of palladium is supported on this. Some use solid catalysts as promoters.

As the nickel or nickel compound component used as the main catalyst metal, organic or inorganic nickel compounds can be used. For example, various nickel compounds such as nickel powder, nickel acetate, nickel iodide, nickel acetylacetone, nickel tetracarbonyl, nickel dicarbonyl, nickel dicarbonyl bistriphenylphosphine, and tetramethylammonium nickel iodide are used. Even when the nickel or nickel compound component is used alone, it is effective as a main catalyst, but the activity is low, and when used in combination with palladium metal, the activity becomes extremely high. That is, the combined use of nickel and insoluble palladium metal very significantly affects the progress of the reaction, and the interaction between the two makes it possible to obtain a fast reaction rate and a high yield of ethylidene diacetate. The palladium metal used with nickel as a cocatalyst is palladium-supported solid metal. The palladium supported catalyst in the present invention will be explained.

The supporting method may be, for example, a conventional immersion method, kneading method, adsorption method, coprecipitation method, ion exchange method, etc., but other methods may also be used. For example, a porous inorganic material is impregnated with a solution containing palladium metal or a palladium compound and other components as necessary, and then formaldehyde, hydrogen, sodium formate, carbon monoxide, and sodium borohydride are impregnated. This is carried out by modifying the palladium compound into palladium metal using a conventional ring-forming means such as hydride, lithium aluminum hydride, or hydrazine, and then drying it; however, it is not limited to these methods. The method is not particularly limited as long as palladium metal can be supported. still,
The form of palladium used for support can be any convenient form of zero or high valence, to name a few: Pd metal, PdO, Pd(0H)2, Pd(N
O3)2Pd(NO2)2,PdS04,Pd3(PO
4) 2, [Pd(NH3)4]X2, (NH4)2Pd
X1, Na2PdX4, K2PdX4, L12PdX4
, PC1X2, Pd(0AC)2, Pd(AcAc)2
, PdX2(PhCN)2 (X in the formula is F, Cl, Br
Or I, Ph is a phenyl group, 0Ac is an acetoxy group,
AcAc represents an acetylacetonate group). The carrier used in the catalyst of the present invention is
As this is used in a fluidized bed or solid bed reactor,
For example, it is composed of a porous inorganic material with a particle size of 400 mesh to 1 inch. The pore volume, which is proportional to solid weight, ranges from 0.03 to 2.5 d/g, preferably from 0.05 to 1.5 d/g. Similarly, the range of surface area proportional to solid weight is from 0.1 to 1500 rr1/g, preferably from 1 to 1500 rr1/y. The average pore radius ranges from 0.1 to 20,000A, preferably from 1 to 2
000 people, and 5 to 1500A is particularly effective.
Further, although the amount of palladium metal supported on the support of the obtained solid catalyst can be varied within a wide range, a particularly preferable range of support is 0.01 to 30% (by weight) in consideration of the surface area of the support. Porous inorganic materials used in the present invention include carbon, graphite, bone char, alumina, silica, silica alumina, barium sulfate, zeolite, spinel,
Alumina with magnesia, thoria, titanium oxide, zirconium oxide, thorium oxide, lanthanum oxide, cerium oxide, zinc oxide, tantalum, clay, diatomaceous earth, celite, asbestos, pumice, hawklite, white clay, Supe
Natural and treated clays such as r-FiltrOI, silicon carbide, zeolite and zeolite molecular sieves, ceramic honeycombs, poria, cement, etc. are used, but preferably carbon, graphite, bone char, alumina, silica, silica alumina, barium sulfate, Zeolite, spinel, alumina with magnesia, and more preferably carbon, graphite, bone charcoal, alumina, silica, silica alumina, and barium sulfate, with carbon being particularly effective.

The above-mentioned porous inorganic material is used as particles of uniform particle size, non-uniform particle size, and capillary shape, and molded products,
Used in molds such as extrusions, ceramic rods, balls, broken pieces, tiles and the like. The solid catalyst composition according to the present invention described above can be easily manufactured using commercially available compounds. It is clear that the production thereof does not require the specific conditions described above, but at the same time, the metal component can be easily separated from the carrier, allowing isolation of palladium metal and regeneration of the catalyst. The palladium metal used as a co-catalyst has been described above, but the elution resistance of the palladium metal in the solid catalyst of the present invention is very low, which will be discussed later! As is clear from the examples, 90.0% or more per time, usually 99.0%
As described above, under suitable conditions, 99.9% or more of palladium metal is retained as a solid catalyst. The reaction requires the presence of a halide along with a metal catalyst, but the preferred halide is bromide or! Iodide or mixtures thereof. Usually, the halides are mostly used in the form of alkyl halides such as methyl iodide, acid halides such as acetyl iodide, hydrogen halides such as hydrogen iodide, or any mixture thereof, and are reacted directly. It can be introduced into the liquid. Furthermore, these halides, namely,
It is also effective to introduce into the reaction solution a substance that generates any one or more of alkyl halides, acid halides, and hydrogen halides in the reaction solution. Substances that react with other components in the reaction solution to produce alkyl halides, acid halides, or hydrogen halides include inorganic halides, such as alkali metal halides such as lithium, sodium, and potassium, and magnesium;
There are alkaline earth metal halides such as calcium or metal halides such as aluminum, zinc, copper, lanthanum or cerium, and bromine or iodine. Among the above halides, the contact resistance of the reactor,
Alternatively, from the standpoint of separation and purification of the reaction product, it is a particularly preferred embodiment to use methyl halides such as methyl bromide and methyl iodide. In the present invention, the above main catalyst and co-catalyst are used in combination, and in order to further speed up the reaction rate, an organic nitrogen group compound containing phosphorus or nitrogen is used as a promoter. Non-limiting examples of compounds effective as accelerators are grouped into groups.

(1) Trivalent nitrogen group compound (4) Nitrogen group compound represented by the general formula M÷R2 (where M represents N or P).

) (a) Rl, R2. R3 is hydrogen or has 1 to 1 carbon atoms
0 saturated alkyl group, cycloalkyl group or aryl group, each of which may be the same or different from each other M=N Ammonia, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, dimethylethylamine , tri-n-propylamine, tri-IsO-propylamine, tri-n-butylamine, tri-tert-butylamine, aniline, dimethylaniline, diethylaniline, dimethylbenzylamine, toluidine, triphenylamine,
Amines such as cyclohexylamine M=P Phosphine such as tri-n-propylphosphine, tri-1s0-propylphosphine, tri-n-butylphosphine, tri-tert-butylphosphine, tri-cyclohexylphosphine, tri-phenylphosphine (b) R1 represents hydrogen or a saturated alkyl group, cycloalkyl group, or aryl group having 1 to 10 carbon atoms, and R2 and R3 are connected to a polymethylene group having 1 to 5 carbon atoms Pyrrolidine, N-methylpyrrolidine, piperidine, N- Cyclic compounds such as phenylpiperidine (c) Rl and R2 represent hydrogen or a saturated alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, a cycloalkyl group, or an aryl group, and may be the same or different from each other.

R3 is a compound representing a saturated fatty acid acyl group having 1 to 10 carbon atoms, and R1 is hydrogen or a saturated alkyl group, cycloalkyl group, or aryl group having 1 to 10 carbon atoms;
2. Lactam compounds in which R3 is linked with a carboxypolymethylene group Carboxylic acid amides such as acetamide, N,N-dimethylceacetamide, acetalinide, N-methyl-N-phenylacetamide, and lactams such as N-methyl-pyrodinone (d) Compounds in which at least one of Rl, R2, and R3 is a carboxymethyl group, and the remainder represents hydrogen or a saturated alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or an aryl group, which may be the same or different. Carboxylic acid derivatives such as N,N-dimethylglycine, N,N-diethylglycine, iminodiacetic acid, N-methyldiiminoacetic acid, nitrilotriacetic acid, etc. (e) R1 is a saturated alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or an aryl group represents R2. R3 is a nitrile bonded to M=N Nitriles such as acetonitrile, probionitrile, benzonitrile (B) General formula 21>M "R5-M2<Engineering 3
An organic nitrogen group compound represented by (however, Ml, M2 are N
, P, which may be the same or different.

) (a) Rl, R2, R3, R4 represent hydrogen or a saturated alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or an aryl group, and R5 is a polymethylene group having 1 to 10 carbon atoms, a phenylene group, or Compounds representing a squid carbonyl group 119M2 or N9P Ethylenebis(diphenylphosphine), phenylenebis(dimethylphosphine), bis(diphenylarsino)ethane, bis(di-1s0-propylarsino)hexane, bis(diethylstivino)pentane, N ,N,N
″,N″-tetramethylethylenediamine, N,N,N
″,N″-tetraethylethylenediamine, N,N,N
! , N'-tetra n-propylethylenediamine, N
,N,N'',N''-tetramethylmethylenediamine, N
, N, N'', N''-tetramethylurea, N-methyl-2
-Compounds (b) such as pyrodinone and triethylenediamine
Rl and R3 are hydrogen, a saturated alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or an aryl group, and R2
, R4 is connected with a polymethylene group having 1 to 5 carbon atoms, and R
Compounds in which 5 is a polyalkylmethylene group having 1 to 5 carbon atoms Cyclic compounds such as piperazine, N-methyl-piperazine, N-ethyl-piperazine, 2-methyl-N-N''-dimethylpiperazine (c) Other compounds 2, 5-dicarboxypiperazine, cyclohexane-1
, 2-diamine-N,N,N'', N-tetraacetic acid and salts and tetramethyl ester, ethylenediaminetetraacetic acid and salts and tetramethyl ester, 1,4-azabicyclo(2,2,2]octane, methyl substituted 1, 4
Compounds such as -diazacyclo[2,2,2]octane, adiponitrile, N-methylmorpholine etc.) Heterocyclic compounds pyridine and alkylpyridines: pyridine, α-picoline, β-picoline, γ-picoline, 2-ethylpyridine, 3 -Ethylpyridine, 4-ethylpyridine, 2-propylpyridine, 4-propylpyridine, 4-butylpyridine, 4-isobutylpyridine, 4-t-butylpyridine, 2,6-lutidine, 2,4-lutidine, 2, 5-
Lutidine 3,4-lutidine, 3,5-lutidine, 2,4
, 6-collidine, 2-methyl-4-ethylpyridine, 2
-Methyl-5-ethylpyridine, 3-methyl-4-ethylpyridine, 3-ethyl-4-methylpyridine, 3,4
-diethylpyridine, 3,5-diethylpyridine, 2-
Methyl-5-butylpyridine, 4-pentylpyridine,
4-(5-nonyl)-pyridine, 2,6-dipropylpyridine, 2-methyl-3-ethyl-6-propylpyridine, 2,6-diethylpyridine, 2,6-dipropylpyridine, 2,6-dibutylpyridine, 2 ,6-G-t-
Butylpyridine; Pyridines containing functional groups: 2-cyanopyridine, 3-cyanopyridine, 4-cyanopyridine,
2,6-dicyanopyridine, 3,5-dicyanopyridine, 2-cyano6-methyl-pyridine, 3-cyano5
-Methyl-pyridine, picolinic acid amide, nicotinic acid amide, isonicotinic acid amide, picolinic acid, nicotinic acid, isonicotinic acid, divicolinic acid, dinicotinic acid, cinchometronic acid, 5-butyl-picolinic acid, nicotinic acid alkyl ester , 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2,3-diaminopyridine, 2,5-diaminopyridine, 2,6-diaminopyridine, 2,3,6-triaminopyridine, 2- Amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino6
-methylpyridine, 2-amino-4-ethylpyridine,
2-amino-4-propylpyridine, 2-amino-4-
(5-nonyl)-pyridine, 2-amino-4,6-dimethylpyridine, 2,6-diamino-4-methylpyridine, 2,2″-dipyridylamine, 4-(N,N-dimethylamino)pyridine, 2- Hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine, 2,6-
Dihydroxypyridine, 3-hydroxy-6-methylpyridine, 2-chloropyridine, 2,6-dichloropyridine, 4-chloropyridine, 2-amino-5-chloropyridine, 2-amino-3,5-dichloropyridine, 2-methyl-3 , 5-dichloro-6-methylpyridine, 2-amino-5-chloro-3-methyllysine, 2-amino-3
．． 5-dichloro-4-methylpyridine, 22-amino-3,5-dichloro-4,6-dimethylpyridine, 4-amino-3,5-dichloropyridine, pyridine-N-oxide, α-picoline-N-oxide, β-picoline N-
oxide, γ-picoline-N-oxide, 2,6-lutidine-N-oxide, 3,5-lutidine-N-oxide, 4-phenylpropylpyridine-N-oxide, 1,
3-di(4-pyridyl)-propane-N-oxide, 4-(5-nonyl)-pyridine-N-oxide, 2-
Chloropyridine-N-oxide, 4-cyanopyridine-N-oxide, 2-pyridinemethanol, 3-pyridinemethanol, 4-pyridinemethanol, 2,6-pyridinemethanol, 2-pyridineethanol, 4-pyridineethanol, 3-picolylamine, 4 -Picolylamine, 2-methylaminoethylpyridine, 4-alkylaminoethylpyridine, 4-piperidinoethylpyridine, 4
-(4-pipecolinoethyl)-pyridine, 4-morpholinoethylpyridine; pyridines containing cyclic compounds; 2-
Phenylpyridine, 4-phenylpyridine, 2-benzylpyridine, 4-benzylpyridine, 4-phenylpropylpyridine, 4,4"-dipyridyl, 4,4"-dimethyl-2,2"-dipyridyl, 1,3-di(4- pyridyl)propane, 1,2-di(4-pyridine)monoethane, 1,2-di(4-pyridyl)monoethylene, 1,2
, 3-tri(4-pyridyl)propane, 2,4,6-
tri(4-pyridyl)-S-triazine, 2,4-di(4-pyridyl)-6-methyl-S-triazine, 2
, 5-di(4-pyridyl)-S-tetrazinialkenylpyridine and high molecular weight pyridines: 2-vinylpyridine, 4-vinylpyridine, 2-vinyl-6-methyl-pyridine, 2-vinyl-5ethylpyridine, 4 -Butenylpyridine, 4-vinylpyridine homopolymer, 2-vinylpyridine homopolymer, 2-vinylpyridine copolymer, 4-vinylpyridine-acrylotrilue copolymer, 4-vinylpyridine-styrene-copolymer, 4-vinylpyridine-divinylbenzene- Copolymers, 2-vinylpyridine-divinylbenzene copolymers, 4-vinylpyridine homopolymers N-oxidonipyrroles:
Pyrrolines: Pyrimidines: Pyrazines: Pyrazoles: Pyrazolyl: Pyritadines: Imidazole: 1,
10-phenanthroline and its derivatives: 1,10-phenanthroline, 4-chloro-1,10-phenanthroline, 5-(thiaventyl)-1,10-phenanthroline Nikinoline and its derivatives: quinoline, 2 -(dimethylamino)-6-methoxyquinoline, 8-hydroxyquinoline, 2-carboxyquinoline (■) Pentavalent nitrogen group compounds ammonium acetate, ammonium propionate, triphenylphosphineiminium chloride Especially among the above compound groups Organic nitrogen group compounds containing nitrogen or phosphorus are preferred.

More preferred organic accelerators are phosphine compounds containing trivalent phosphorus or heterocyclic compounds typified by pyridine. In the present invention, the amount of nickel used as the main catalyst is 10 -/e based on the total volume of the reaction solution.
6 to 5 mol, preferably 10-4 to 4 mol, more preferably 10-3 to 2 mol, most preferably 5 x 10-3
The range from 1.0 mole to 1.0 mole is generally selected.

The amount of the insoluble palladium metal catalyst used in the present invention differs depending on whether the reaction is carried out in a fluidized bed or a fixed bed, but in general, it is 1 % to the reaction solution based on palladium metal. x10-4 to 25% by weight, preferably 5 x 10-4 to 20% by weight, more preferably 1
A range of x10-3 to 15% by weight is selected, and a range of 2.5 x10-3 to 10% by weight is particularly effective.
The ratio of palladium to nickel is 1 to 1/30 (
molar ratio). The total reaction pressure need only be sufficient to maintain the volatile reaction medium in the liquid phase and carbon monoxide and hydrogen at appropriate partial pressures. The preferred partial pressure of carbon monoxide and hydrogen is 0.5 to 700 atm, the optimum partial pressure is 1 to 600 atm, and the most suitable partial pressure is 3 to 5 atm, but wider than this.
．． A partial pressure in the range of 0.05 to 10 tapping pressure may also be used.
Further, the amount of the halogen compound used together with the metal catalyst is 10-3 to 15 mol per 1e, preferably 10-2 to 15 mol, based on the total volume of the reaction solution based on the halogen atom.
It is used in an amount of 5 mol, more preferably in a range of 10-1 to 3 mol.

The reaction temperature for carrying out the method of the present invention is from 20 to
Suitable range is 5000C1, preferably 30 to 3500C, more preferably 40 to 2500C.

Dimethyl ether, which is a raw material used in the present invention,
Methyl acetate obtained by any method can be used. For example, dimethyl ether is supplied by the dehydration dimerization reaction of methanol, and methyl acetate is usually supplied by the ester reaction between methanol and acetic acid, or by the transesterification reaction between methanol and acetic acid ester. In this case, the basic raw material, acetic acid, is produced by the reaction of methanol and carbon monoxide (for example, JP-A-54-592).
11, JP-A-54-63002, JP-A-54-6661
4) Alternatively, in the method of converting ethylidene diacetate to vinyl acetate according to the method of the present invention [for example, U.S. Pat.
971), HydroOcarbOnPrOcess44
(11) 287 (1965), etc.], it is also possible to use the co-produced acetic acid. Alternatively, methyl acetate can be produced by the reaction of methanol and synthesis gas [for example, Japanese Patent Publication No. 48-2525, 1977-149213, Japanese Patent Publication No. 5
2-136110, JP-A-52-136111, etc.] may be used. The methyl acetate supplied by the above method will be contaminated with impurities such as methanol, dimethyl ether, acetic acid, acetaldehyde, dimethyl acetal, halides represented by iodides such as methyl iodide, etc. However, as long as the overall balance of the reaction is not disturbed, the above-mentioned impurities can be tolerated and the reaction can proceed suitably. In addition, using acetic acid, which is co-produced in the method of converting ethylidene diacetate to vinyl acetate, as a raw material for methyl acetate is a preferred embodiment in the overall process of producing vinyl acetate from methanol and synthesis gas, and it is also a preferred embodiment for producing vinyl acetate from methanol and synthesis gas. It is also possible to produce ponyvinyl alcohol and methyl acetate from the vinyl acetate polymer and methanol, and use the by-produced methyl acetate as a raw material for the present invention. The stoichiometric amount of the raw material gas in the above reaction formula for producing ethylidene diacetate is the molar ratio of carbon monoxide to hydrogen of 2: depending on whether methyl acetate, dimethyl ether, or a mixture is used as the raw material. It varies between 1 and 4:1. However, in practice the molar ratio of carbon monoxide to hydrogen ranges much wider, from 1:10 to 100:1, preferably from 1:50 to
50:1, more preferably 1:10 to 10:1 can be used. A molar ratio of carbon monoxide to hydrogen in the range 0.5:1 to 5:1 is particularly preferred since the best results are obtained when the gas mixture is close to the stoichiometric ratio of carbon monoxide to hydrogen. . Further, carbon monoxide and hydrogen used in the present invention may be injected into the reaction zone individually, or may be introduced in the form of a mixture of carbon monoxide and hydrogen, so-called "synthesis gas." These raw material gases do not necessarily have to be of high purity and may contain carbon dioxide, methane, nitrogen, rare gases, etc. However, raw material gases of extremely low purity will increase the pressure of the reaction system. In the method of the present invention, the raw materials methyl acetate and dimethyl ether and the product ethylidene diacetate themselves also serve as reaction solvents, so a solvent does not necessarily have to be used. It is also possible to use soluble organic solvents and diluents.

Commonly used solvents include organic acids such as acetic acid, acetic anhydride, propionic acid, butyric acid, octanoic acid, phthalic acid, benzoic acid, methyl acetate, ethylene glycol diacetate, propylene glycol diacetate, phenyl acetate,
Organic acid esters such as tolyl acetate, hydrocarbons such as dodecane, hexadecane, benzene, naphthalene, and biphenyl, and inorganic acids such as triphenyl phosphate, tricresyl phosphate, dibutylphenyl phosphate, tetramethyl orthosilicate, and tetrabutyl silicate. Examples include acid esters, aromatic ethers such as diphenyl ether, and ketones such as acetone, methyl ethyl ketone, dibutyl ketone, methyl isobutyl ketone, acetophenone, and benzophenone. A preferred embodiment is to use acetic acid or acetic anhydride, which are analogs of ethylidene diacetate, which is a reaction product, as the solvent. The reaction of the present invention is intended to produce ethylidene diacetate, but since ethylidene diacetate has the property that its decomposition is promoted by water, it is particularly difficult to use solvents and raw material esters or ethers that are likely to contain water. It is important to supply the reaction system in an anhydrous state and to bring the reaction system itself into a substantially anhydrous state.

The presence of water in the reaction raw materials is a common phenomenon, but the presence of a small amount of water, such as that contained in commercially available synthesis gas and methyl acetate or dimethyl ether, is acceptable and does not cause any problems.

However, the presence of water in an amount of 10 mol % or more in any one or more reaction raw materials should generally be avoided, as introducing a large excess of water into the reaction system tends to cause decomposition of the product. 5 mol% in this respect, more preferably 3 mol%
It is desirable that the water content is as follows. The method of the present invention is preferably carried out in a reaction liquid enclosed in a certain reaction zone, but the method itself can be carried out batchwise, semi-continuously or continuously.

In continuous operation, the reactants and catalyst are preferably fed to a suitable reaction zone, the reaction mixture is continuously distilled to separate a predetermined amount of volatile organic components, and the distillation bottoms containing the catalyst are recycled. It can also be used in circulation. Another preferred method is to convert vinyl acetate to acetic acid by feeding the reaction mixture containing ethylidene diacetate continuously flowing out of the reaction zone to another suitable reaction zone, and distilling these reaction mixtures to form acetic acid. Methyl, acetic acid and vinyl acetate can be separated and recovered, and the distillation bottoms containing catalyst can be recycled for further reaction. In the present invention, acetic acid, acetic anhydride, and acetaldehyde may be produced as by-products along with the target product ethylidene diacetate, and in the continuous operation, acetic anhydride and acetaldehyde are circulated to the reaction zone. The method of the present invention described in detail above produces ethylidene diacetate through a hydrocarbonylation reaction using an inexpensive catalyst, and has extremely high industrial significance.

Hereinafter, this will be explained in more detail with reference to Examples.

Example 1 Methyl acetate 59.2 g 1 acetic acid 48.
0g 1 methyl iodide 29.7g 12,6-lutidine 9.7
4g1 1.78g of nickel powder and 4.45g of palladium metal supported on powdered activated carbon (manufactured by Nippon Engelhardt, palladium loading amount 5%) were added, and the inside of the container was filled with a mixed gas of carbon monoxide and hydrogen. (CO:H2=2:1
), the pressure was further increased to 60 kg/CFlfG, and the mixture was heated with stirring. When the temperature rose to 180℃, a mixed gas of carbon oxide and hydrogen (CO:H2=2:1)
was press-fitted to give a weight of 100 kg/DG, and the temperature and pressure were set to 3.
It kept time.

During this time, a decrease in pressure was observed, so the mixed gas was supplemented by that amount to maintain the pressure at 100 kg/DG. After the reaction was cooled, the reaction solution was analyzed and found that 24.0% of ethylidene diacetate was found along with unreacted methyl acetate, acetic acid, and methyl iodide.
It contained 6.7 gb of g1 acetic anhydride. Further, as a result of atomic absorption spectrometry, it was found that 99% of the palladium used was retained in the activated carbon.

Examples 2 to 10 The results obtained by performing the same operations as in Examples are shown in Table 1 as in Example 1.

Comparative Example 1 N1 powder 0.587g. ．． L110.67g. sCH31
13.4g1 (n-Bu)3P (tri-n-butylphosphine) 4.5g1 A reaction vessel was filled with 16g of acetic acid as a solvent and 19.8g of methyl acetate as a raw material, and at room temperature hydrogen 100kg/d1 carbon monoxide 100k9/ Cll was press-fitted.

The temperature of the reactor was raised to 2001C, and the reaction was carried out at this temperature for 7 hours. After cooling, the reaction solution was analyzed and found to contain 18n10e% of acetic anhydride and 0.0% ethylidene diacetate.
015g was detected.

Comparative Example 2 Methyl acetate 20.0g1 in a 100ml autoclave
Add 15.0 g of acetic acid, 8.0 g of methyl iodide, 0.320 g of 2-vinylpyridine, and 0.0647 g of palladium black (manufactured by Engelhard Japan), and use a mixed gas of carbon monoxide and hydrogen (CO:H2 = 2:1). Then, the inside of the container was replaced, the pressure was further increased to 60k9/DG, and the mixture was heated while stirring.

After raising the temperature to 175DC, a mixed gas of carbon monoxide and hydrogen (CO:H2, = 2:1) was injected and the temperature was increased to 100K.
9/CItG, and this temperature and pressure were maintained for 4 hours.

When analyzed by gas chromatography, no formation of ethylidene diacetate was observed.

Comparative Example 3 The reaction was carried out in the same manner as in Example 6 except that N1 powder was not used.

The amount of ethylidene diacetate produced was 1.1 g, and the amount of acetic anhydride produced was 0.4 g. The yield of ethylidene diacetate based on methyl acetate is calculated to be 1.9%. Comparative Example 4 The reaction was carried out in the same manner as in Example 6 except that 0.90 g of chromium powder was used instead of 0.90 g of Ni powder.

The amount of ethylidene diacetate produced was 1.0 g.
The yield of ethylidene diacetate based on methyl acetate is 1.
It is calculated as 7. Comparative Example 5 Ni/l (0.90g of chromium carbonyl instead of 0.90g)
The reaction was carried out in the same manner as in Example 6 except that 90 g was used.

Claims (1)

[Claims] 1 Ethylidene diacetate is produced by reacting methyl acetate or dimethyl ether with carbon monoxide and hydrogen in the presence of a catalyst consisting of at least one halide such as iodide or bromide, an organic nitrogen group compound containing phosphorus or nitrogen, and nickel. In the method for producing palladium metal as a cocatalyst, 0.01 to 30% ( 1. A method for producing ethylidene diacetate, characterized in that the solid substance is used in such a manner that the molar ratio of palladium to nickel is 1 to 1/30 (by weight).