# US 10,370,318 B2 · Method for preparing acetic acid by carbonylation of methanol

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- Number: US 10,370,318 B2
- Document ID: US10370318B2
- Status: Granted
- Kind: B2
- Application number: 15/758,572
- Filed: 2015-12-08
- Published: 2018-08-30
- Granted: 2019-08-06
- Earliest claimed: 2015-09-11
- Assignees: Dalian Institute of Chemical Physics, Chinese Academy of Sciences
- Applicants: Dalian Institute of Chemical Physics, Chinese Academy of Sciences
- Inventors: Youming Ni; Wenliang Zhu; Lei Shi; Hongchao Liu; Yong Liu; Zhongmin Liu
- Web page: https://patentgrep.com/patent/US10370318B2

## CPC

- C07C 51/12: on an oxygen-containing group in organic compounds, e.g. alcohols
- B01J 29/18: of the mordenite type
- B01J 29/24: Iron group metals or copper
- B01J 29/65: of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
- B01J 29/67: Noble metals
- B01J 31/0254: {on mineral substrates}
- B01J 31/26: containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J 37/0072: {Preparation of particles, e.g. dispersion of droplets in an oil bath}
- B01J 37/0203: {the impregnation liquid containing organic compounds}
- B01J 37/0207: {Pretreatment of the support}
- B01J 37/08: Heat treatment {(B01J37/0009, B01J37/0018 take precedence)}
- B01J 37/30: Ion-exchange
- C07C 53/08: Acetic acid (pyroligneous acid C10C; preparation of vinegar C12J)
- B01J 29/00: Catalysts comprising molecular sieves {(molecular sieves per se C01B)}
- B01J 2229/183: in framework positions
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS

## Abstract

The present invention provides a method for preparing acetic acid by carbonylation of methanol, which comprises: passing a raw material containing methanol, carbon monoxide and water through a reaction region loaded with a catalyst containing an acidic molecular sieve with an adsorbed organic amine, and carrying out a reaction under the following conditions to prepare acetic acid. The method in the present invention offers high acetic acid selectivity and good catalyst stability. The catalyst in the present invention does not contain noble metals such as rhodium or iridium, and does not need additional agent containing iodine, and thus does not generate a strong corrosive hydroiodic acid and the like.

## Claims

### Claim 1

A method for preparing acetic acid by carbonylation of methanol, which comprises: passing a raw material containing methanol, carbon monoxide and water through a reaction region loaded with a catalyst containing an acidic molecular sieve with an adsorbed organic amine, and carrying out a reaction under the following conditions to prepare acetic acid;
wherein the acidic molecular sieve is one or two molecular sieves selected from the group consisting of molecular sieves with MOR framework and molecular sieves with FER framework;
the organic amine is one or more organic amines selected from the group consisting of pyridine, phenylamine, cyclohexylamine, piperidine, substituted pyridines with one or more substituents, substituted phenylamines with one or more substituents, substituted cyclohexylamines with one or more substituents and substituted piperidines with one or more substituents; and the substituents are independently selected from halogen or C1-3 alkyl group;
the reaction region is constituted by one or more reactors which are connected in series and/or in parallel;
the reaction conditions are listed as follows: the reaction temperature is in a range from 150° C. to 350° C.; and the reaction pressure is in a range from 0.5 MPa to 10 MPa; and the weight hourly space velocity of methanol is in a range from 0.01 h−1 to 10 h−1; and the molar ratio of monoxide to methanol is in a range from 1:1 to 100:1; and the molar ratio of water to methanol is in a range from 0.05:1 to 5:1; and
wherein the acidic molecular sieve is an acidic mordenite molecular sieve.

### Claim 2 (depends on 1)

The method according to claim 1, wherein the atom ratio of Si to Al in the acidic molecular sieve Si/Al is in a range from 3 to 100.

### Claim 3 (depends on 1)

The method according to claim 1, wherein the acidic molecular sieve contains metal; and the mass fraction of the metal is in a range from 0.1% to 10%.

### Claim 4 (depends on 3)

The method according to claim 3, wherein the metal is one or more metals selected from the group consisting of copper, iron, gallium, silver, nickel and cobalt.

### Claim 5 (depends on 3)

The method according to claim 3, wherein the metal is introduced into the acidic molecular sieve by one or more methods selected from the group consisting of in situ synthesis, impregnation and ion exchange.

### Claim 6 (depends on 1)

The method according to claim 1, wherein the acidic molecular sieve contains a forming agent; and the mass fraction of the forming agent is in a range from 1% to 60%.

### Claim 7 (depends on 6)

The method according to claim 6, wherein the forming agent is one or more materials selected from the group consisting of aluminum oxide, silicon oxide and kaolin.

### Claim 8 (depends on 1)

The method according to claim 1, wherein the reaction conditions are listed as follows: the reaction temperature is in a range from 240° C. to 300° C.; and the reaction pressure is in a range from 3 MPa to 7 MPa; and the weight hourly space velocity of methanol is in a range from 0.3 h−1 to 3.0 h1; and the molar ratio of monoxide to methanol is in a range from 5:1 to 20:1 and the molar ratio of water to methanol is in a range from 0.2:1 to 1:1.

### Claim 9 (depends on 1)

The method according to claim 1, wherein the reactor is continuous reactor selected from a fixed bed reactor, a moving bed reactor or a fluidized bed reactor.

### Claim 10 (depends on 1)

The method according to claim 1, wherein the atom ratio of Si to Al in the acidic molecular sieve Si/Al is in a range from 5 to 30.

### Claim 11 (depends on 3)

The method according to claim 3, wherein the mass fraction of the metal is in a range from 0.1% to 2%.

### Claim 12 (depends on 6)

The method according to claim 6, wherein the mass fraction of the forming agent is in a range from 10% to 30%.