JP6059822B2 - Method for preparing methyl acetate - Google Patents

Description

  The present invention relates to a process for preparing methyl acetate, and more particularly to a process for preparing methyl acetate by carbonylation of dimethyl ether.

Methyl acetate is an important organic chemical industry raw material and solvent. Methyl acetate is used to synthesize acetic acid and acetic anhydride and acetic acid derivatives such as vinyl acetate. At present, acetic acid is industrially produced mainly by the carbonylation method of homogeneous phase methanol by Monsanto and BP. In the reaction process, noble metal catalyst containing Rh or Ir and co-catalyst such as CH ₃ I having corrosivity [J . Catal. 245 (2007) 110-123] is used. Methyl acetate can also synthesize ethanol by hydrogenation reduction [ChemSusChem3 (2010) 1192-1199]. Ethanol has a higher octane number than gasoline, can be burned completely in an internal combustion engine, and can be used alone or mixed with gasoline as a fuel for automobiles. Currently, ethanol gasoline with an ethanol content of 5% to 85% Has been commercialized. If gasoline is mixed with ethanol, greenhouse gas emissions can be reduced. At present, ethanol is industrially produced mainly in two ways: biological fermentation of corn and sugarcane and ethylene hydration. In the production of ethanol by biological fermentation, generally only about 14% low-concentration ethanol can be obtained, so if you do not perform rectification by investing a large amount of money and consuming a large amount of energy, you can use fuel-grade ethanol. Although it cannot be obtained, and biofermentation pays for consumption of economic crops such as food, it does not affect food safety, so ethanol production by biofermentation is limited. The ethylene used in the ethylene hydration process is mainly from the petrochemical industry, however, as the petroleum resources have been depleted and prices have remained high, this process has gradually lost economic competitiveness. It will be. Methyl acetate can also be widely used as a green solvent in industries such as spinning, perfume, medicine and food.

  Methyl acetate can be obtained by carbonylation reaction of dimethyl ether and carbon monoxide, and dimethyl ether can be synthesized in one step by dehydration of methanol or synthesis gas. Can be obtained. Currently, synthesis gas can be produced by gasification of non-petroleum resources such as coal, natural gas and biomass, and the technology for industrial production is very mature.

  The currently reported catalyst for the preparation of methyl acetate by carbonylation of dimethyl ether is the most well studied and most active is mordenite with 8-membered or 10-membered ring structure. Iglesia et al. [J. Am. Chem. Soc. 129 (2007) 4919-4924], it was found that the active center of catalytic carbonylation is at the B-acid site of the 8-membered ring, and the selectivity of methyl acetate exceeds 99%. Lifespan and inactivation have not been studied in detail. Shinbun Jie et al. [Chin. J. et al. Catal. 31 (2010) 729-738], by preliminarily adsorbing pyridine on mordenite, the stability of the carbonylation reaction of dimethyl ether can be greatly improved, and after reacting at 200 ° C. for 48 hours. Can maintain a methyl acetate yield of about 30%, and pyridine is adsorbed in the 12-membered ring, which suppresses the formation of carbon deposits in the 12-membered ring. It turns out that it has no effect. However, under the reaction conditions, the pyridine adsorbed on the mordenite gradually desorbs and the carbon deposits on the zeolite molecular sieve gradually increase, leading to a gradual decrease in the activity of the catalyst. Its performance is reduced and its lifetime is shortened, and its application in large-scale industrial production is severely limited.

  In the method of producing methyl acetate by carbonylation of dimethyl ether, the present invention employs a hydrogen mordenite adsorbed with an organic amine, and the raw material gas is dimethyl ether containing organic amine, carbon monoxide, and any An object of the present invention is to provide a method for producing methyl acetate, which is a mixed gas of hydrogen gas, and is characterized in that methyl acetate can be produced stably and efficiently by passing a raw material gas through a catalyst under reaction conditions. In the present invention, by adding an organic amine component to the raw material gas, the stability of the catalyst is further improved and the life of the catalyst is greatly extended.

In order to achieve the above object, the present invention passes a raw material gas containing an organic amine, dimethyl ether, carbon monoxide and an optional hydrogen gas through a reaction zone in which a hydrogen-type mordenite molecular sieve catalyst is placed, and a reaction temperature of 150 to 320. The reaction is carried out at a temperature of 0.1 ° C., a reaction pressure of 0.1 to 8 MPa, and a gas volume space velocity of 500 to 10000 h ⁻¹ to prepare methyl acetate. The organic amine is one or a mixture of pyridines organic amines, aromatic amines and alicyclic organic amines, and the hydrogen mordenite molecular sieve catalyst adsorbs organic amines The hydrogen-type mordenite is acidic mordenite, and in the raw material gas, carbon monoxide and dimethyl ether The molar ratio of the organic amine to dimethyl ether is 0.00001: 1 to 0.2: 1, and the molar ratio of hydrogen gas to dimethyl ether is 0: 1 to A method is provided for preparing methyl acetate that is 20: 1.

  In a preferred embodiment, the reaction temperature is 200 to 280 ° C.

  In a preferred embodiment, the reaction pressure is 3 to 5 MPa.

In a preferred embodiment, the gas volume space velocity is 2000 to 5000 h ⁻¹ .

  In a preferred embodiment, the molar ratio of carbon monoxide to dimethyl ether is preferably 2: 1 to 10: 1.

  As a preferred embodiment, the molar ratio of the hydrogen gas to dimethyl ether is preferably 1: 1 to 10: 1.

  In a preferred embodiment, the molar ratio of organic amine to dimethyl ether in the raw material gas is 0.0001: 1 to 0.01: 1.

  As a preferred embodiment, the preparation process of the hydrogen-type mordenite molecular sieve catalyst adsorbed with the organic amine is charged with hydrogen-type mordenite in a reactor, and at an adsorption temperature of 90 to 420 ° C., the organic amine, carbon monoxide, After adsorbing to saturation through one or a mixture of hydrogen gas, air, nitrogen gas, helium gas and argon gas, carbon monoxide, hydrogen gas, air, nitrogen at this temperature It is to obtain hydrogen type mordenite on which organic amine is adsorbed by purging with a mixture of one or more selected from gas, helium gas and argon gas for 0.5 to 6 hours.

  In a preferred embodiment, the preferred adsorption time is 0.5 to 48 hours.

  In a preferred embodiment, the adsorption temperature is 160 to 320 ° C.

  In a preferred embodiment, the hydrogen-type mordenite catalyst has a silica / alumina atomic ratio of 4: 1 to 60: 1, and more preferably 5: 1 to 20: 1.

  In a preferred embodiment, the pyridine-based organic amine is one or more selected from pyridine and pyridine-substituted products.

In a preferred embodiment, the pyridine substituent is one of five H in the pyridine ring, two or three are independently F, Cl, Br, I, CH ₃ , CH ₃ CH ₂ , CF ₃ , or It is substituted with a substituent selected from NO ₂ .

  In a preferred embodiment, the aromatic amine is one or more selected from aniline and substituted aniline.

In a preferred embodiment, the aniline-substituted product is one, two, three, four, five, six out of a total of seven H of five H in the benzene ring and two H in the amine group. Or seven are independently substituted with a substituent selected from F, Cl, Br, I, CH ₃ , CF ₃ or CH ₃ CH ₂ .

  In a preferred embodiment, the alicyclic organic amine is an organic amine in which hydrogen in an amine molecule is substituted with an aliphatic group and the molecular structure has a ring structure.

等の様である；前記脂環式有機アミンにおけるアミン基中の窒素原子は環内に位置してもよく、例えば、

等の様である。 As a preferred embodiment, the nitrogen atom in the amino group in the alicyclic organic amine may be located outside the ring, for example,

The nitrogen atom in the amine group in the alicyclic organic amine may be located in the ring, for example,

And so on.

  In a preferred embodiment, the alicyclic organic amine is one or more selected from an alicyclic organic amine containing a 5- to 8-membered ring and a substituted alicyclic organic amine containing a 5- to 8-membered ring. .

、ピペリジン

、シクロヘキシルアミン置換体及びピペリジン置換体から選択される一種又は複数種である。 In a preferred embodiment, the alicyclic organic amine is cyclohexylamine.

Piperidine

, One or more selected from cyclohexylamine-substituted and piperidine-substituted.

As a preferred embodiment, any 1-13 amino is independently F of thirteen H the cyclohexylamine substitutes are in cyclohexylamine, Cl, Br, I, CH 3, CF 3, CH 3 CH 2 or It is substituted with a substituent selected from NO ₂ .

In a preferred embodiment, in the piperidine substituent, any one of 11 Hs in the piperidine ring is independently F, Cl, Br, I, CH ₃ , CF ₃ , CH ₃ CH ₂ or NO. A substituent selected from ₂ is substituted.

  In a preferred embodiment, the organic amine adsorbed on the catalyst and the organic amine in the raw material gas may be the same or different.

  In a preferred embodiment, the organic amine adsorbed on the catalyst is any one kind or a mixture of plural kinds selected from pyridine, 2-methylpyridine, aniline, 4-methylaniline, cyclohexylamine, and piperidine.

  In a preferred embodiment, the organic amine in the raw material gas is any one kind or a mixture of plural kinds selected from pyridine, 2-methylpyridine, aniline, 4-methylaniline, cyclohexylamine, and piperidine.

  In a preferred embodiment, the organic amine adsorbed on the catalyst is pyridine and / or 2-methylpyridine; the pyridines organic amine in the raw material gas is pyridine and / or 2-methylpyridine.

  In a preferred embodiment, the organic amine adsorbed on the catalyst is aniline and / or 4-methylaniline; the aromatic amine in the source gas is aniline and / or 4-methylaniline.

  In a preferred embodiment, the organic amine adsorbed on the catalyst is cyclohexylamine and / or piperidine; the alicyclic organic amine in the source gas is cyclohexylamine and / or piperidine.

  As a preferred embodiment, the organic amine in the raw material gas may be a newly added organic amine, or the organic amine obtained in the product separation process may be recycled.

  In a preferred embodiment, the reactor is a continuously flowing fixed bed reactor, moving bed reactor or fluidized bed reactor. A person skilled in the art can select an appropriate number of reactors, types of reactors and connection method between the respective reactors according to actual industrial production demands.

  In a preferred embodiment, the product methyl acetate can be used for the production of ethanol by hydrogenation reduction.

  In the present application, the organic amines of pyridines include aminopyridine, bromopyridine, methylpyridine, iodopyridine, chloropyridine, nitropyridine, hydroxypyridine, benzylpyridine, ethylpyridine, cyanopyridine, fluoropyridine, dihydropyridine, and other alkylpyridines. It may be expressed as a pyridine compound including a halogenated pyridine.

  According to common knowledge in the technical field, the hydrogen-type mordenite is acidic mordenite.

  According to known common knowledge in the technical field, examples of the bromopyridine include 2-fluoro-5-bromopyridine, 2-amino-3-iodo-5-bromopyridine, 4-bromopyridine hydrochloride, 2- Chloro-4-bromopyridine, 4-amino-3-bromopyridine, 2-hydrazino-5-bromopyridine, 2-fluoro-3-bromopyridine, 2,3,5-tribromopyridine, 5-bromopyridine-2 -Methyl carboxylate, 2-fluoro-4-methyl-5-bromopyridine, 2-acetyl-5-bromopyridine, 3,5-dibromopyridine, 2,3-dibromopyridine, 2-hydroxymethyl-4-bromopyridine 2,4-dibromopyridine, 2,6-dimethyl-3-bromopyridine, 2,6-dibromopyridine, 2,5-dichloro-3 Bromo pyridine.

  According to known common knowledge in the field, examples of the iodopyridine include 4- (BOC-amino) -3-iodopyridine, 2-amino-3-methyl-5-iodopyridine, 2-bromo-5- Iodopyridine, 5-bromo-2-iodopyridine, 2-amino-5-chloro-3-iodopyridine, 2-chloro-4-iodopyridine-3-carbaldehyde, 3-amino-4-iodopyridine, 2- Fluoro-3-aldehyde-4-iodopyridine, 3-fluoro-4-iodopyridine, 2,6-dichloro-4-iodopyridine, 2-iodopyridine, 2-chloro-5-trifluoromethyl-4-iodopyridine 3-bromo-5-iodopyridine, 2,5-diiodopyridine, 2-bromo-4-iodopyridine, 4-amino-3-iodopyridine, - Amino-3-iodopyridine, 2-fluoro-3-iodo pyridine.

  According to known common knowledge in the technical field, examples of the nitropyridine include 2-amino-4-methyl-5-nitropyridine, 2,4-dichloro-6-methyl-3-nitropyridine, and 3-chloro. 2-nitropyridine, 2-fluoro-3-nitropyridine, 2,4-dichloro-5-nitropyridine, 2-methoxy-4-methyl-5-nitropyridine, dichloro-3-nitropyridine, 4-chloro- 3-nitropyridine, 3-ethoxy-2-nitropyridine, 3,5-dimethyl-4-nitropyridine-2-methanol, 2,6-dibromo-3-nitropyridine, 1- (5-nitropyridine-2- Yl) piperazine, 4-methoxy-3-nitropyridine, 3-bromo-4-nitropyridine-N-oxide, 5-bromo-2-nitropyridine, 2, - dibromo-3-nitropyridine, 3-amino-2-nitropyridine, 5-methyl-2-amino-3-nitropyridine, and the like.

  According to known common knowledge in the technical field, examples of the methylpyridine include 2,5-dibromo-3-methylpyridine, 2-fluoro-6-methylpyridine, 2- (chloromethyl) -4-methoxy- 3,5-dimethylpyridine, 2-amino-3-bromo-6-methylpyridine, 2-methyl-6-trifluoromethylpyridine-3-carbonyl chloride, 6-bromo-3-hydroxymethylpyridine, 2-bromo- 4-methylpyridine, 2- (chloromethyl) -4- (3-methoxypropoxy) -3-methylpyridine, 3-chloromethylpyridine hydrochloride, 2-amino-5-bromo-4-methylpyridine, 2-methoxy -5-trifluoromethylpyridine, 5-cyano-2-methylpyridine, 3-aldehyde-6-methylpyridine, 2,5-dibu Mo-6-methylpyridine, 5-bromo-2-hydroxymethylpyridine, 3-amino-2-methylpyridine, 2-fluoro-6-trifluoromethylpyridine, 3-trifluoromethyl pyridine.

  According to known common knowledge in the technical field, examples of the ethylpyridine include 1-ethyl-1,2-dihydro-6-hydroxy-4-methyl-2-oxo-3-pyridinecarboxamide, 3- (2 -Aminoethyl) pyridine, 3- (2-chloroethyl) -6,7,8,9-tetrahydro-2-methyl-4H-pyrido [1,2-a] pyrimidin-4-one, 2-bromo-4- Ethylpyridine, 2- (2-aminoethyl) pyridine, 2-amino-4-ethylpyridine, diethyl (3-pyridyl) -borane 5- {4- [2- (5-ethyl-2-pyridyl) -ethoxy] -Benzyl} -2-imino-4-thiazolidinone, 1-ethylpyridinium bromide, 1-ethylpyridinium chloride, 6- (t-butyl) -3-ethyl-2-amino-4,7- Hydrothiophene [2,3-C] pyridine di3,6 (5H) -dicarboxylate, 3- (2-chloroethyl) -6,7,8,9-tetrahydro-9-hydroxy-2-methyl-4H-pyrido [1,2-a] pyrimidin-4-one, 1-dimethylcarbamoyl-4- (2-thioxoethyl) pyridine inner salt, 5-ethyl-2-pyridineethanol, 2-ethyl-6-methyl-3-hydroxy Examples include pyridine, 5-ethylpyridine-2,3-dicarboxylic acid 3-ethylpyridine, 2-hydroxyethylpyridine and the like.

  According to known common knowledge in the technical field, examples of the aminopyridine include 2,6-diaminopyridine, 2-chloro-4-aminopyridine, 2-acetamidopyridine, 3-chloro-2-aminopyridine, 4 -Methylaminopyridine, 2,6-dichloro-3-aminopyridine, 4- (3-methylphenyl) aminopyridine-3-sulfonamide, 2-chloro-5-aminopyridine, methyl 6-aminopyridinecarboxylate, 2 -Methoxy-6-methylaminopyridine, 2,4-diaminopyridine, 6-methoxy-2,3-diaminopyridine dihydrochloride, 2-benzylaminopyridine, ethyl 3-aminopyridine-4-carboxylate, 3-methyl -4-aminopyridine, 2,6-dibromo-3-aminopyridine, 2-bromo-3-aminopyridine, - acetamido-5-aminopyridine, and the like.

  According to known common knowledge in the technical field, examples of the fluoropyridine include 2-fluoropyridine-5-carbaldehyde, 2,6-difluoropyridine-3-boronic acid, 2-chloro-3-fluoropyridine- 4-boronic acid, 2-methoxy-3-bromo-5-fluoropyridine, 2-fluoropyridine-6-carboxylic acid, 5-chloro-2-fluoropyridine, 2-bromo-4-fluoropyridine, 3,5- Dichloro-2,4,6-trifluoropyridine, 4-amino-3,5-dichloro-2,6-difluoropyridine, 2-amino-3-fluoropyridine, 2-fluoropyridine, 2-chloro-3-fluoro Pyridine, 2-chloro-3-nitro-5-fluoropyridine, 3-fluoropyridine-2-carboxylic acid, 3-chloro-2,4,5, - tetrafluoro pyridine, 4-bromo-2-fluoropyridine, 2-bromo-3-fluoropyridine, and the like.

  According to known common knowledge in the field, examples of the chloropyridine include 2-amino-6-chloropyridine, 2- [N, N-bis (trifluoromethylsulfonyl) amino] -5-chloropyridine, -Amino-3-nitro-6-chloropyridine, 5-amino-2,3-dichloropyridine, 2-chloropyridine-4-boronic acid pinacol ester, 2,3-diamino-5-chloropyridine, 2-amino- 3,5 dichloropyridine, 2-chloropyridine-N-oxide, 2-methoxy-3-bromo-5-chloropyridine, 2-amino-5-chloropyridine, 3-acetyl-2-chloropyridine, 2-methyl- 6-chloropyridine, 4-amino-3,5-dichloropyridine, 6-chloro-2-carboxylic acid, 2,6-dichloropyridine, 2-chloro Lysine-5-sulfonyl chloride, 3,5-dichloro-4-carboxylic acid, 3-amino-2,4-dichloropyridine, and the like.

  According to known common knowledge in the technical field, examples of the hydroxypyridine include 4-hydroxy-6-methyl-3-nitro-2-pyridinol, 3-bromo-2-hydroxy-5-methylpyridine, 6-hydroxypyridine, Methyl-2-hydroxypyridine, 1,2-dimethyl-3-hydroxy-4-pyridone, 2-amino-3-hydroxypyridine, 2-hydroxy-4- (trifluoromethyl) pyridine, 2-hydroxy-5-iodo Pyridine, 2-hydroxy-4-methylpyridine, 2-hydroxy-5-methyl-3-nitropyridine, 2-hydroxy-6-methyl-5-nitropyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 3-amino-4-hydroxypyridine, 2-hydroxy-3-nitropyridine, 2-hydroxypyridine, 5 Nitro-2-hydroxy-3-chloropyridine, 2-hydroxypyridine -N- oxide, 4-hydroxy-3-methylpyridine, 2-bromo-6-hydroxypyridine and the like.

  According to known common knowledge in the technical field, examples of the cyanopyridine include 3-cyano-6-trifluoromethylpyridine, 5-bromo-2-cyano-3-nitropyridine, 2-amino-3-cyano. Pyridine, 3-nitro-2-cyanopyridine, 4-cyanopyridine, 3-cyano-2-fluoropyridine, 3-cyano-6-hydroxypyridine, 4-chloro-3-cyanopyridine, 3-cyano-4-methyl Pyridine, 3-amino-6-cyanopyridine, 2-cyano-5-hydroxypyridine, 2-cyano-3-fluoropyridine, 3-chloro-4-cyanopyridine, 4-cyanopyridine, N-oxide, 2-chloro -3-cyanopyridine, 3-amino-4-cyanopyridine, 2-cyanopyridine-5-boronic acid pinacol ester, 5-butyl Model 2-cyanopyridine, and the like.

  According to known common knowledge in the art, examples of the dihydropyridine include 2,3-dihydropyrido [2,3-d] [1,3] azol-2-one, 4-oxo-1,4-dihydro -2,6-pyridinedicarboxylic acid, 6,7-dihydro-5H-pyrrolo [3,4-b] pyridine, 5-bromo-2,3-dihydro-1H-pyrrolyl [2,3-B] pyridine, -Oxo-1,2-dihydro-3-pyridinecarboxylate methyl, 2,4-dichloro-5,6-dihydropyrido [3,4-D] pyrimidine-7 (8H) -tert-butylcarboxylate, 2,3 -Dihydro-1,4-dioxyno [2,3-b] pyridine, 9-methyl-3,4-dihydro-2H-pyridopyrimidin-2-one, N-benzyloxycarbonyl-3,6-dihydro-2H -Pyridine 4-boronic acid pinacol ester, 3,4-dihydro-2H-pyrido [1,2-D] pyrimidin-2-one, 4,5-dihydro-4-oxofuran [3,2] pyridine, 6,7-dihydro -5H-cyclopenta [B] pyridin-5-one, 6,7-dihydro-5H-pyrrolo [3,4-b] pyridine hydrochloride, 1,4-dihydro-2,4,6-trimethyl-3,5 -Diethyl pyridinedicarboxylate, 1-methyl-6-oxo-1,6-dihydropyridine-3-carboxylic acid, 2-chloro-7,8-dihydropyrido [4,3-D] pyrimidine-6 (5H) -carboxylic acid t-butyl, 3- (1-acetyl-1,4-dihydropyridin-4-yl) -1H-indole, 2-chloro-6,7-dihydro-5H-pyrrolo [3,4-B] pyridine and the like. Et That.

  According to known common knowledge in the technical field, examples of the benzylpyridine include 2-benzylpyridine, 4- (4-nitrobenzyl) pyridine, 2-p-chlorobenzylpyridine, 4-benzylpyridine, 1-benzyl. Pyridine-3-carboxylate, 6-benzyl-2,4-dichloro-5,6,7,8-tetrahydropyrido [4,3-D] pyrimidine, 7-benzyl-4-chloro-5,6 7,8-tetrahydropyrido [3,4-D] pyrimidine, 4- (4-chlorobenzyl) pyridine, 7-benzyl-5,6,7,8-T tetrahydropyrido [3,4-D] pyrimidine -4 (3H) -one, 4- (2,4-dinitrobenzyl) pyridine, 3-benzylpyridyl, 6-benzyl-5,7-dioxo-octahydropyrrolo [3,4B] pyridine (4-Chlorobenzyl) pyridin-3-ylmethylamine, (4-fluorobenzyl) pyridine-3-methylamine, 7-benzyl-5,6,7,8-tetrahydropyrido [3,4-D] pyrimidine -2,4- (1H, 3H) -dione, 1- (4-nitrobenzyl) -4- (4-diethylaminephenylazo) bromopyridine, 2-amino-3-nitro-6- (4-fluorobenzylamino) ) Pyridine, benzylpyridin-2-ylmethylamine and the like.

  A person skilled in the art can select an appropriate pyridine compound according to actual industrial production demand.

  According to known common knowledge in the technical field, the aromatic amine refers to a compound in which a benzene ring in an aromatic compound is bonded to N in an amine group, and the structure of the aromatic compound includes one or more benzene rings. But it ’s okay. Commonly used aromatic amines include 4-isopropylaniline, N-methylaniline, 2,4,6-trichloroaniline, 2,4-dinitroaniline, 2-ethylaniline, 2-chloro-4-nitroaniline. N-ethylaniline, N, N-dimethylaniline, orthotoluidine, metaphenylenediamine, diphenylamine, 2,6-dimethylaniline, 3-nitroaniline, 1-naphthylamine, N, N-diethylaniline, 4-methyl-2 -Nitroaniline, 4-nitroaniline, 3,3'-diaminobenzidine, 4-chloro-2,5-dimethoxyaniline, 4-fluoro-3-nitroaniline, 3-fluoro-N-methylaniline, 2,6- Dinitroaniline, 2-fluoro-4-iodoaniline, 3-bromo-2,4,6 Trimethylaniline, 2-bromo-4-chloroaniline, 2-t-butylaniline, 2-chloro-4-nitro-6-bromoaniline, N-methyl-p-nitroaniline, 4-fluoro-2-nitroaniline, 4-bromo-2-methoxyaniline, 2'-bromo-4'-fluoroacetanilide, N-ethyl-N-benzyl-m-toluidine, 2-fluoro-6-methylaniline, N-methyl-o-toluidine, 2 -Fluoro-3-trifluoromethylaniline, 3,5-dimethoxyaniline, 2-chloro-4-iodoaniline, 4-methyl-3-nitroaniline, 3-fluoro-4-methylaniline, 4-ethylaniline, 2 -Bromo-6-methylaniline, 4-n-butylaniline, N-isopropylaniline, 2-chloro-N-methyl Niline, 2,6-dibromo-4-chloroaniline, 3-bromo-2-methylaniline, 2-iodo-4-chloroaniline, N-methyl-p-toluidine, 2-propylaniline, 4-methyl-3- Trifluoromethylaniline, 2-methyl-4-methoxyaniline, 3-trifluoromethoxyaniline, 2- (difluoromethoxy) aniline, 3-difluoromethoxyaniline, 2,5-dimethoxy-4-nitroaniline, 2,4- Dichloro-6-nitroaniline, 4,5-difluoro-2-nitroaniline, 2-chloro-5-nitroaniline, o-aminoacetanilide, 5-methoxy-2-methylaniline, m-aminoacetanilide, 5-methyl- 2-nitroaniline, 2,4-dimethoxyaniline, 2,4,5-trichloroaniline 2-nitrodiphenylamine, 3,4,5-trimethoxyaniline, 3,5-di-t-butylaniline, 2-bromoaniline, 2,4,6-tribromoaniline, 4-chloro-N-methylaniline N, N-dimethyl-p-toluidine, 4-bromo-N, N-dimethylaniline, 4-vinylaniline, 3-iodo-4-methylaniline, 2-bromo-4-fluoro-6-methylaniline, 2 -Iodo-4-nitroaniline, 2,4-dibromo-6-nitroaniline, 2-bromo-6-chloro-4- (trifluoromethyl) aniline, 2,3,4-trifluoro-6-nitroaniline, 2,5-dibromoaniline, o-aminodiphenylamine, 2-chloro-4,6-dinitroaniline, p-iodoaniline, 2-iodoaniline, 4,5- Chloro-2-nitroaniline, 5-iodo-2-methylaniline, 2-bromo-4,6-dimethylaniline, 2-bromo-5-nitroaniline, 4-bromo-2,6-dichloroaniline, N-methyl 2-nitroaniline, 2-chloro-4-trifluoromethoxyaniline, 3-iodoaniline, 4-decylaniline, 2,6-diisopropylaniline, 3-fluoroacetanilide, 2,6-dichloro-4- (trifluoro Methoxy) aniline, 3-ethylaniline, 2,6-dichloro-N-phenylaniline, 4-bromo-2-nitroaniline, 3,4-dichloroaniline, 2,6-dibromoaniline, 4-heptyloxyaniline, 4 -Bromo-2-fluoroacetanilide, 3,5-dinitroaniline, N-methyldiphenylamino 4-fluoro-2-nitroacetanilide, 3-bromo-4-methylaniline, 3-tetrafluoroethoxyaniline, 2,5-dichloro-4-nitroaniline, 4- (N-BOC-aminomethyl) aniline, 2 -Bromo-N, N-dimethylaniline, 4-bromo-2-methyl-6-nitroaniline, 3-bromo-N, N-dimethylaniline, 4-bromo-3-methoxyaniline, 4-t-butylaniline, 2,6-dibromo-4-nitroaniline, 2,4-dibromoaniline, 2-bromo-4-trifluoromethoxyaniline, 4-bromo-2-chloroaniline, 4-difluoromethoxyaniline, 4-octylaniline, 2 , 4-Dimethylaniline, 2-bromo-5-methylaniline, 3-chloro-N-methylaniline, 2-bromo- 5-trifluoromethylaniline, 2,5-diethoxyaniline, p-propylaniline, N, N-dimethyl-m-toluidine, dodecahydrodiphenylamine, 2,4-dichloroaniline, 4-nitrodiphenylamine, 2-fluoroacetanilide 2-fluoro-4-nitroaniline, 4,4′-diaminodiphenylamine, m-nitroacetanilide, 2,5-bis (trifluoromethyl) aniline, N, N-dimethyl o-toluidine, 3-methyldiphenylamine, 3 -Nitro-4-chloroaniline, 2-cyano-4-nitro-6-bromoaniline, 4,5-dimethyl-2-nitroaniline, 2-chloroaniline, 4-bromo-2- (trifluoromethoxy) aniline, 2-methyl-6-nitroaniline, 2-cyano-4-nitro Niline, N-nitrosodiphenylamine, 2-fluoro-5-nitroaniline, 3-trifluoromethyl-4-bromoaniline, 4-n-pentylaniline, 3-benzyloxyaniline, 5-chloro-2-iodoaniline, tri Phenylamine, 3,5-dichloroaniline, 2-bromo-4,6-dinitroaniline, 2,3-dichloroaniline, 4-iodo-2-methylaniline, 2,6-dichloroaniline, 4-heptylaniline, 4 -Bromoaniline, N-ethyl-m-toluidine, 4-bromo-o-phenylenediamine, N-methyl-1,2-phenylenediamine, 2-nitro-1,4-phenylenediamine, 4,5-dimethyl-1 , 2-phenylenediamine, 4,5-dichloro-1,2-phenylenediamine, N, N′-di-s Butyl-p-phenylenediamine, 1,2-phenylenediamine, m-bromoaniline, 4-bromo-1-naphthylamine, (R)-(+)-1,1′-bi-2-naphthylamine, 1,2, 3,4-tetrahydro-1-naphthylamine, 4-methoxy-m-phenylenediamine, 3-nitro-o-phenylenediamine, 2,4,6-trimethyl-1,3-phenylenediamine, 4-methyl-N-phenyl Aniline, 4'-methoxyacetoacetanilide, 2,6-difluoro-4-methoxyaniline, 2-methyl-3-nitroaniline, benzidine dihydrochloride, 2,6-dimethoxyaniline, 3,3'-dimethylbenzidine dihydrochloride Salt, 5-chloro-2-nitrobenzidine, 3-t-butylaniline, N-acetoacetylanthranilic acid, 4-methyl Tylsulfonylaniline, 2-methyl-4-methoxydiphenylamine, N, N-dibutylaniline, 3-isopropylaniline, 4,4′-dimethyldiphenylamine, 4-methoxy-3-nitroaniline, o-benzylaniline, N, N -Bis (2-hydroxyethyl) -p-toluidine, 3,4-diethoxyaniline, 3,4,5-trichloroaniline, 5-bromo-4-fluoro-2-methylaniline, 4-octyloxyaniline, 2 -Bromo-3-methylaniline, 4,6-dimethyl-2-nitroaniline, 3,4-dichloro-N-methylaniline, 2'-bromoacetanilide, 4,6-dibromo-2,3-dichloroaniline, 4 -Bromo-2-ethylaniline, 4-bromo-N, N-diethylaniline, 3-phenoxyani 4-fluoro-N-methylaniline, 2,6-diiodo-4-nitroaniline, 3-chloro-2,6-diethylaniline, 3-benzylaniline, 2-methoxy-N-methylaniline, 2-methoxy -6-methylaniline, 4-propoxyaniline, N- (4-methoxybenzylidene) aniline, 2-bromo-6-methyl-4-nitroaniline, 3- (N, N-diethyl) amino-4-methoxyacetanilide, 4-amino-N, N-dimethylaniline, N-acetanilide, 2,6-diethylaniline, 1,3-bis (aminomethyl) benzene, 3-hydroxy-N, N-diethylaniline, diaminotoluene, 4-dodecyl Aniline, N1-methyl-2,4-dichloroaniline, N-ethyl-2-nitroaniline, 4-t-butyl N, N-dimethylaniline, 4-trifluoromethyl-N-methylaniline, 4-tetradecylaniline, 4-butoxyacetylaniline, 2,4,6-triphenylaniline, diisopropyl-dimethylaniline, 3-chloro-4 -(4-chlorophenoxy) aniline, 2-chloro-4,6-dimethylaniline, Nt-butyl-3,5-dimethylaniline, 5,6,7,8-tetrahydro-2-naphthylamine, 4-bromo -N-methylaniline, 3-iodo-4-methylaniline, 4'-carbamoylacetoacetanilide, N, N-diisopropylaniline, 4-vinylaniline, (R)-(+)-1,1'-bi-2 -Naphthylamine, 3- (2-methylanilino) phenol, 4-methoxy-2-naphthylamine, 4-methoxy- 2-naphthylamine, 4-benzyloxy-N-methylaniline, 3-bromo-N, N-diphenylaniline, 3-bromo-N-methylaniline, N- (t-butoxycarbonyl) -3-bromoaniline, 2- Bromo-N-methylaniline, N- (t-butoxycarbonyl) -2-bromoaniline, 2,4,6-tri-t-butyl-N-toluidine, 4-octadecylaniline, 4-chloro- (N-BOC ) Aniline, 2,4,6-tri-t-butyl-N- (trimethylsilyl) aniline, 4′-ethyl-3′-methylacetanilide, N-ethyl-p-nitroaniline, 4-hexadecylaniline, 4- Bromo-N, N-bis (trimethylsilyl) aniline, 2,5-di-t-butylaniline, 2,4,6-trimethyl-N-methylaniline , N-N-hexylaniline, 3,3′-dichlorobenzidine, N-ethyl-N-isopropylaniline, 3-nitro-N-methylaniline, 4-iodo-3-nitroaniline, 4-benzyloxy-3- Chloroaniline, 4- (4-bromophenoxy) aniline, 4-chloro-2,6-dinitroaniline, N, N-2-N-hexylaniline, 3,5-dimethyl-1,2-phenylenediamine, N, N-di-BOC-2-iodoaniline, N-methyl-4,4′-methylenedianiline, 4-[(trimethylsilyl) ethynyl] aniline, 4-bromo-2-ethylaniline, 2,6-difluoro-3 -Nitroaniline, methyl 4- (phenylcarbamoyl) benzoate, 2-bromo-5-methylaniline, 5-bromo-4-fluoro-2-me Ruaniline, 4-isopropylaniline, diaminotoluene, 4,4′-diaminodiphenylamine, N, N-dimethylaniline, 2-methoxy-4-methylaniline, 3-chloro-N, N-bis (trimethylsilyl) aniline, 3- (2-methylanilino) phenol, dichloroaniline, m-xylylenediamine and the like.

  One skilled in the art can select an appropriate aromatic amine according to actual industrial production demands.

  In the present invention, methyl acetate was prepared by carbonylation reaction of dimethyl ether using a hydrogen-type mordenite molecular sieve catalyst adsorbed with organic amine, but by adding an organic amine component to the raw material gas, the organic amine was desorbed in the reaction process. It was possible to steadily compensate / suppress the shortage of doing so, thereby improving the stability of the catalyst and extending the life of the catalyst.

In the examples, dimethyl ether conversion and methyl acetate selectivity are both calculated based on the number of carbon moles of dimethyl ether:
Conversion rate of dimethyl ether = [(number of carbon moles of dimethyl ether in the raw material gas) − (number of carbon moles of dimethyl ether in the product)] ÷ (number of carbon moles of dimethyl ether in the raw material gas) × (100%)
Selectivity of methyl acetate = (2/3) × (number of moles of carbon of methyl acetate in product) ÷ [(number of moles of carbon of dimethyl ether in raw material gas) − (number of moles of carbon of dimethyl ether in product)] × (100 %)

  EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

Comparative Example 1:
50 g of hydrogen-type mordenite with a silica / alumina ratio of 4: 1 is roasted at 550 ° C. for 5 hours in an air atmosphere using a muffle furnace, a part of the powder sample is tableted and pulverized to 20 to 40 mesh. And used for activity test. Weigh 10 g of the hydrogen-type mordenite sample, put it in a stainless steel reaction tube with an inner diameter of 8.5 mm, activate it with nitrogen gas at normal pressure and 300 ° C. for 1 hour, lower it to 250 ° C., and add carbon monoxide and dimethyl ether. The reaction pressure was gradually increased to 2 MPa, the reaction space velocity was controlled to be GHSV = 1000 h ^−1, and the exhaust gas was supplied online by gas chromatography. Detection and analysis were performed to calculate the conversion rate of dimethyl ether and the selectivity of methyl acetate, and the reaction results are shown in Table 1.

Comparative Example 2:
50 g of hydrogen-type mordenite with a silica / alumina ratio of 4: 1 is roasted at 550 ° C. for 5 hours in an air atmosphere using a muffle furnace, a part of the powder sample is tableted and pulverized to 20 to 40 mesh. And used for activity test. 10 g of the hydrogen-type mordenite sample was weighed and placed in a stainless steel reaction tube having an inner diameter of 8.5 mm. After being activated with nitrogen gas at normal pressure and 300 ° C. for 1 hour, the pyridine liquid was bubbled with nitrogen gas to give pyridine. Blowing into hydrogen-type mordenite for 2 hours, purging with nitrogen gas for 1 hour, lowering to 250 ° C., passing carbon monoxide and dimethyl ether so that carbon monoxide: dimethyl ether = 15: 1, and setting the reaction pressure to Gradually increase to 2 MPa, control the reaction space velocity to GHSV = 1000 h ⁻¹ , detect and analyze exhaust gas online by gas chromatography, calculate dimethyl ether conversion rate and methyl acetate selectivity The reaction results are shown in Table 1.

Comparative Example 3:
Except for changing the silica / alumina ratio of hydrogen-type mordenite in Comparative Example 1 to 6: 1, the experimental procedure is as in Comparative Example 1, and the reaction results are shown in Table 1.

Comparative Example 4:
Except for changing the silica / alumina ratio of hydrogen-type mordenite in Comparative Example 2 to 6: 1, the experimental procedure is as in Comparative Example 2, and the reaction results are shown in Table 1.

Comparative Example 5:
Except for changing the silica / alumina ratio of hydrogen-type mordenite in Comparative Example 1 to 60: 1, the experimental procedure is as in Comparative Example 1, and the reaction results are shown in Table 1.

Comparative Example 6:
The experimental procedure was the same as in Comparative Example 2 except that the silica / alumina ratio of hydrogen-type mordenite in Comparative Example 2 was changed to 60: 1 and the pyridine adsorbed on the catalyst was changed to pyridine and 2-nitropyridine having a molar ratio of 1: 1. The reaction results are shown in Table 1.

Comparative Example 7:
The experimental procedure is as in Comparative Example 2 except that the adsorbed pyridine in Comparative Example 2 is changed to aniline, and the reaction results are shown in Table 1.

Comparative Example 8:
The experimental procedure is as in Comparative Example 4 except that the adsorbed pyridine in Comparative Example 4 is changed to aniline, and the reaction results are shown in Table 1.

Comparative Example 9:
The experimental procedure was as in Comparative Example 6 except that the adsorption molar ratio of 1: 1 pyridine and 2-nitropyridine in Comparative Example 6 was changed to aniline and 4-ethylaniline in a molar ratio of 1: 1. It is shown in 1.

に変更した以外、実験手順は比較例２の通りであり、反応結果を表１に示す。 Comparative Example 10:
The adsorbed pyridine in Comparative Example 2

The experimental procedure is the same as that of Comparative Example 2 except that the reaction results are as shown in Table 1. Table 1 shows the reaction results.

に変更した以外、実験手順は比較例４の通りであり、反応結果を表１に示す。 Comparative Example 11:
The adsorbed pyridine in Comparative Example 4

The experimental procedure was as in Comparative Example 4 except that the reaction results were changed to, and the reaction results are shown in Table 1.

と

に変更した以外、実験手順は比較例６の通りであり、反応結果を表１に示す。 Comparative Example 12:
In Comparative Example 6, the adsorbed molar ratio of 1: 1 pyridine and 2-nitropyridine was 1: 1 molar ratio.

When

The experimental procedure is as in Comparative Example 6 except that the reaction results are as follows. The reaction results are shown in Table 1.

Example 1:
50 g of hydrogen-type mordenite with a silica / alumina ratio of 4: 1 is roasted at 550 ° C. for 5 hours in an air atmosphere using a muffle furnace, a part of the powder sample is tableted and pulverized to 20 to 40 mesh. And used for activity test. 10 g of the hydrogen-type mordenite sample was weighed and placed in a stainless steel reaction tube having an inner diameter of 8.5 mm. After being activated with nitrogen gas at normal pressure and 300 ° C. for 1 hour, the pyridine liquid was bubbled with nitrogen gas to give pyridine. It was blown into hydrogen-type mordenite for 2 hours, further purged with nitrogen gas for 1 hour, then lowered to 250 ° C., and carbon monoxide, dimethyl ether and pyridine were changed to carbon monoxide: dimethyl ether: pyridine = 15: 1: 0.001. The reaction pressure is gradually increased to 2 MPa, the reaction space velocity is controlled to be GHSV = 1000 h ⁻¹ , exhaust gas is detected and analyzed online by gas chromatography, and dimethyl ether is converted. The rate and selectivity of methyl acetate were calculated and the reaction results are shown in Table 1.

Example 2:
Change the silica / alumina ratio of hydrogen-type mordenite to 6: 1, change the pyridine adsorbed on the catalyst to 2,3-dichloro-5-trifluoromethylpyridine, and change the pyridine in the source gas to 2-fluoropyridine. Except for the above, the experimental procedure is as in Example 1, and the reaction results are shown in Table 1.

Example 3:
The silica / alumina ratio of hydrogen-type mordenite was changed to 60: 1, the pyridine adsorbed on the catalyst was changed to 2-iodopyridine, and the pyridine in the raw material gas was 2-bromopyridine and 2-chloro at a molar ratio of 1: 1. Except for changing to pyridine, the experimental procedure is as in Example 1, and the reaction results are shown in Table 1.

Example 4:
The raw material gas in Example 1 was changed to carbon monoxide: dimethyl ether: 2-methylpyridine = 15: 1: 0.0001, the reaction pressure was changed to 0.1 MPa, and the reaction space velocity was changed to GHSV = 500 h ⁻¹ . Except for the above, the experimental procedure is as in Example 1, and the reaction results are shown in Table 1.

Example 5:
The pyridine adsorbed on the catalyst in Example 1 was changed to 2-ethylpyridine, the raw material gas was changed to carbon monoxide: hydrogen gas: dimethyl ether: pyridine = 1: 10: 1: 0.01, and the reaction temperature was 320. The experimental procedure is as in Example 1 except that the temperature is changed to ° C., the reaction pressure is changed to 8 MPa, and the reaction space velocity is changed to GHSV = 10000 h ⁻¹ . Table 1 shows the reaction results.

Example 6:
The pyridine organic amine previously adsorbed in Example 1 was changed to 2-methylpyridine, and the raw material gas was changed to carbon monoxide: hydrogen gas: dimethyl ether: 2-chloropyridine = 45: 20: 1: 0.2. The experimental procedure was the same as in Example 1 except that the reaction temperature was changed to 150 ° C. Table 1 shows the reaction results.

Example 7:
50 g of hydrogen-type mordenite with a silica / alumina ratio of 4: 1 is roasted at 550 ° C. for 5 hours in an air atmosphere using a muffle furnace, a part of the powder sample is tableted and pulverized to 20 to 40 mesh. And used for activity test. 10 g of the hydrogen-type mordenite sample was weighed and placed in a stainless steel reaction tube having an inner diameter of 8.5 mm. After being activated with nitrogen gas at normal pressure and 300 ° C. for 1 hour, the pyridine liquid was bubbled with nitrogen gas to give pyridine. Blowing into hydrogen-type mordenite for 2 hours, purging with nitrogen gas for 1 hour, lowering to 250 ° C., and converting carbon monoxide, dimethyl ether, and aniline to carbon monoxide: dimethyl ether: aniline = 15: 1: 0.001 The reaction pressure is gradually increased to 2 MPa, the reaction space velocity is controlled to be GHSV = 1000 h ⁻¹ , exhaust gas is detected and analyzed online by gas chromatography, and dimethyl ether is converted. The rate and selectivity of methyl acetate were calculated and the reaction results are shown in Table 1.

Example 8:
The silica / alumina ratio of hydrogen-type mordenite was changed to 6: 1, the aniline adsorbed on the catalyst was changed to 2,6-dichloro-4-trifluoromethylaniline, and the raw material gas was carbon monoxide: dimethyl ether: 4- Except for changing to fluoroaniline = 15: 1: 0.00001, the experimental procedure is as in Example 7, and the reaction results are shown in Table 1.

Example 9:
The silica / alumina ratio of hydrogen-type mordenite was changed to 60: 1, the aniline adsorbed on the catalyst was changed to N, N-dimethyl-m-toluidine, and the aniline in the raw material gas was 2-bromo having a molar ratio of 1: 1. Except for changing to aniline and 3-chloroaniline, the experimental procedure is as in Example 7, and the reaction results are shown in Table 1.

Example 10:
The raw material gas in Example 7 was changed to carbon monoxide: dimethyl ether: 4-methylaniline = 15: 1: 0.0001, the reaction pressure was changed to 0.1 MPa, and the reaction space velocity was changed to GHSV = 500 h ⁻¹ . Otherwise, the experimental procedure is as in Example 7 and the reaction results are shown in Table 1.

Example 11:
The aniline adsorbed on the catalyst in Example 7 was changed to 2-ethylaniline, the raw material gas was changed to carbon monoxide: hydrogen gas: dimethyl ether: aniline = 1: 10: 1: 0.01, and the reaction temperature was 320. The experimental procedure was as in Example 7 except that the temperature was changed to ° C., the reaction pressure was changed to 8 MPa, and the reaction space velocity was changed to GHSV = 10000 h ⁻¹ . The reaction results are shown in Table 1.

Example 12:
The aromatic amine adsorbed in advance in Example 7 was changed to 4-methylaniline, and the raw material gas was changed to carbon monoxide: hydrogen gas: dimethyl ether: 2-chloroaniline = 45: 20: 1: 0.2, Except that the reaction temperature was changed to 150 ° C., the experimental procedure was as in Example 7, and the reaction results are shown in Table 1.

液体を窒素ガスでバブリングして、

を水素型モルデナイトに吹き込んで２時間処理し、さらに窒素ガスで１時間パージした後、２５０℃に下げ、一酸化炭素とジメチルエーテルと

とを一酸化炭素：ジメチルエーテル：

＝１５：１：０．００１となるように通し、反応圧力を徐々に２ＭＰａに上昇させ、反応空間速度をＧＨＳＶ＝１０００ｈ^-1となるように制御し、ガスクロマトグラフィーにより排気ガスをオンラインで検出して分析し、ジメチルエーテルの変換率及び酢酸メチルの選択性を計算し、反応結果を表１に示す。 Example 13:
50 g of hydrogen-type mordenite with a silica / alumina ratio of 4: 1 is roasted at 550 ° C. for 5 hours in an air atmosphere using a muffle furnace, a part of the powder sample is tableted and pulverized to 20 to 40 mesh. And used for activity test. 10 g of the hydrogen-type mordenite sample was weighed and placed in a stainless steel reaction tube having an inner diameter of 8.5 mm. After being activated with nitrogen gas at normal pressure and 300 ° C. for 1 hour,

Bubbling the liquid with nitrogen gas,

Was blown into hydrogen-type mordenite for 2 hours, purged with nitrogen gas for 1 hour, then lowered to 250 ° C., carbon monoxide and dimethyl ether,

And carbon monoxide: dimethyl ether:

= 15: 1: 0.001 is passed, the reaction pressure is gradually increased to 2 MPa, the reaction space velocity is controlled to be GHSV = 1000 h ^−1, and exhaust gas is detected online by gas chromatography The dimethyl ether conversion and methyl acetate selectivity were calculated and the reaction results are shown in Table 1.

に変更し、原料ガスにおける脂環式有機アミンを

に変更した以外、実験手順は実施例１３の通りであり、反応結果を表１に示す。 Example 14:
By changing the silica / alumina ratio of hydrogen-type mordenite to 6: 1, the alicyclic organic amine previously adsorbed on the catalyst

To the alicyclic organic amine in the source gas

The experimental procedure is as in Example 13 except that the reaction results are as shown in Table 1. Table 1 shows the reaction results.

に変更し、原料ガスにおける脂環式有機アミンをモル比１：１の

と

に変更した以外、実験手順は実施例１３の通りであり、反応結果を表１に示す。 Example 15:
By changing the silica / alumina ratio of hydrogen mordenite to 60: 1, the alicyclic organic amine previously adsorbed on the catalyst

The alicyclic organic amine in the raw material gas has a molar ratio of 1: 1.

When

The experimental procedure is as in Example 13 except that the reaction results are as shown in Table 1. Table 1 shows the reaction results.

＝１５：１：０．０００１に変更し、反応圧力を０．１ＭＰａに変更し、反応空間速度をＧＨＳＶ＝５００ｈ^-1に変更した以外、実験手順は実施例１３の通りであり、反応結果を表１に示す。 Example 16:
The raw material gas in Example 13 is carbon monoxide: dimethyl ether:

= 15: 1: 0.0001, except that the reaction pressure was changed to 0.1 MPa and the reaction space velocity was changed to GHSV = 500 h ⁻¹ , the experimental procedure was as in Example 13, and the reaction results were Table 1 shows.

に変更し、原料ガスを一酸化炭素：水素ガス：ジメチルエーテル：

＝１：１０：１：０．０１に変更し、反応温度を３２０℃に変更し、反応圧力を８ＭＰａに変更し、反応空間速度をＧＨＳＶ＝１００００ｈ^-1に変更した以外、実験手順は実施例１３の通りであり、反応結果を表１に示す。 Example 17:
The alicyclic organic amine previously adsorbed on the catalyst in Example 13

The raw material gas is changed to carbon monoxide: hydrogen gas: dimethyl ether:

= 1: 10: 1: 0.01, except that the reaction temperature was changed to 320 ° C., the reaction pressure was changed to 8 MPa, and the reaction space velocity was changed to GHSV = 10000 h ^−1. The reaction results are shown in Table 1.

に変更し、原料ガスを一酸化炭素：水素ガス：ジメチルエーテル：

＝４５：２０：１：０．２に変更し、反応温度を１５０℃に変更した以外、実験手順は実施例１３の通りであり、反応結果を表１に示す。 Example 18:
The alicyclic organic amine previously adsorbed in Example 13 was

The raw material gas is changed to carbon monoxide: hydrogen gas: dimethyl ether:

= 45: 20: 1: 0.2 The experimental procedure was as in Example 13 except that the reaction temperature was changed to 150 ° C, and the reaction results are shown in Table 1.

Claims (12)

A method for preparing methyl acetate, wherein a raw material gas containing an organic amine, dimethyl ether, carbon monoxide and an optional hydrogen gas is passed through a reaction zone in which a hydrogen-type mordenite molecular sieve catalyst is placed, and a reaction temperature of 150 to 320 ° C., Reaction is carried out at a reaction pressure of 0.1 to 8 MPa and a gas volume space velocity of 500 to 10,000 h ⁻¹ to prepare methyl acetate,
The hydrogen type mordenite molecular sieve catalyst adsorbs organic amine,
In the source gas, the molar ratio of carbon monoxide to dimethyl ether is 1: 1 to 45: 1, the molar ratio of organic amine to dimethyl ether is 0.00001: 1 to 0.2: 1, hydrogen The molar ratio of gas to dimethyl ether is 0: 1 to 20: 1,
The reaction zone comprises a plurality of reactors connected as one or in series and / or in parallel,
The method for preparing methyl acetate, wherein the organic amine is one or a mixture of pyridines, organic amines, aromatic amines, and alicyclic organic amines.   The method according to claim 1, wherein the molar ratio of organic amine to dimethyl ether in the source gas is 0.0001: 1 to 0.01: 1. The hydrogen type mordenite molecular sieve catalyst adsorbing the organic amine is:
Hydrogen type mordenite is charged into a reactor, and at one or more kinds selected from organic amine, carbon monoxide, hydrogen gas, air, nitrogen gas, helium gas and argon gas at an adsorption temperature of 90 to 420 ° C. The mixture is adsorbed until it becomes saturated through the mixture of carbon monoxide, hydrogen gas, air, nitrogen gas, helium gas, and argon gas at this temperature, and is mixed with one or more mixtures of 0.5. By purging for ˜6 hours, hydrogen type mordenite adsorbing organic amine is obtained,
The method according to claim 1, wherein the method is prepared by the following process. The method according to claim 3, wherein the adsorption temperature is 160 to 320 ° C.   The method according to claim 1, wherein the hydrogen type mordenite molecular sieve catalyst has a silica / alumina atomic ratio of 4: 1 to 60: 1. The pyridine organic amine is one or more selected from pyridine and pyridine-substituted products, the aromatic amine is one or more selected from aniline and aniline-substituted products, and the alicyclic organic amine is according to claim 1, characterized in that the one or more selected from alicyclic organic amines substituents containing an alicyclic organic amines and 5-8 membered ring containing 5-8 membered ring Method. 2. The method according to claim 1, wherein the alicyclic organic amine is one or more selected from cyclohexylamine, piperidine, a cyclohexylamine substituent, and a piperidine substituent. The pyridine substituent is a substitution in which one, two or three of the five H atoms in the pyridine ring are independently selected from F, Cl, Br, I, CH ₃ , CF ₃ , CH ₃ CH ₂ or NO _2. The aniline-substituted product is one, two, three, four, five out of a total of seven H of five H in the benzene ring and two H in the amine group. Six or seven are independently substituted with a substituent selected from F, Cl, Br, I, CH ₃ , CF ₃ or CH ₃ CH ₂ , and the cyclohexylamine substituent is 1 to 13 of 13 Hs are independently substituted with a substituent selected from F, Cl, Br, I, CH ₃ , CF ₃ , CH ₃ CH ₂ or NO ₂ . The piperidine-substituted product is contained in the piperidine ring. In which 1 to 11 amino either independently F, substituted Cl, Br, I, a substituent selected from _{CH 3, CF 3, CH 3} CH 2 or NO ₂ among the 11 H The method according to claim 6 or 7 , characterized in that   The method according to claim 1, wherein the organic amine adsorbed on the catalyst and the organic amine in the raw material gas may be the same or different.   The organic amine adsorbed on the catalyst is any one or a mixture selected from pyridine, 2-methylpyridine, aniline, 4-methylaniline, cyclohexylamine, and piperidine, and the organic amine in the source gas is The method according to claim 1, wherein the method is any one or a mixture selected from pyridine, 2-methylpyridine, aniline, 4-methylaniline, cyclohexylamine, and piperidine.   The method according to claim 1, wherein the organic amine in the raw material gas may be a newly added organic amine, or the organic amine obtained in the product separation process may be recycled.   The method of claim 1, wherein the reactor is a continuously flowing fixed bed reactor, moving bed reactor or fluidized bed reactor.