Method for preparing acrylic acid and methyl acrylate

Patent metadata

Field	Value
Publication number	US-11111200-B2
Application number	US-201616463415-A
Country	US
Kind code	B2
Filing date	Nov 25, 2016
Priority date	Nov 25, 2016
Publication date	Sep 7, 2021
Grant date	Sep 7, 2021

Abstract

The present invention provides a method for preparing acrylic acid and methyl acrylate. The method comprises passing the feed gas containing dimethoxymethane and carbon monoxide through a solid acid catalyst to generate acrylic acid and methyl acrylate with a high conversion rate and selectivity at a reaction temperature in a range from 180 to 400 and a reaction pressure in a range from 0.1 MPa to 15.0 MPa, the mass space velocity of dimethoxymethane in the feed gas is in a range from 0.05 h−1 to 10.0 h−1, and the volume percentage of dimethoxymethane in the feed gas is in a range from 0.1% to 95%.

First claim

What is claimed is:

1. A method, for preparing acrylic acid and methyl acrylate, the method comprising passing a feed gas containing dimethoxymethane and carbon monoxide through a reactor loaded with a molecular sieve catalyst to carry out a reaction, to generate acrylic acid and methyl acrylate, methyl acetate and acetic acid;
wherein the esters produced by the method are further hydrolyzed to produce the corresponding carboxylic acids, including the hydrolysis of the methyl acrylate to produce the corresponding acrylic acid, and the hydrolysis of the methyl acetate to produce the corresponding acetic acid.

2. The method according to claim 1 , wherein the esters and carboxylic acids produced by the method are further hydrogenated to produce the corresponding alcohols, including the hydrogenation of the methyl acrylate and acrylic acid to produce the corresponding propanol, and the hydrogenation of the methyl acetate and acetic acid to produce the corresponding ethanol.

3. The method according to claim 1 , wherein the molecular sieve catalyst contains a binder, the binder is any one or more selected from the group consisting of alumina, silica and magnesia, and the binder content is in a range from 0 wt % to 70 wt % of the total weight of the catalyst.

4. The method according to claim 1 , wherein the feed gas includes hydrogen and an inactive gas in addition to dimethoxymethane and carbon monoxide, wherein the volume content of carbon monoxide is in a range from 50% to 95%, the volume content of hydrogen is in a range from 0% to 50%, and the volume content of the inactive gas is in a range from 0% to 50%; and the inactive gas includes any one or more selected from the group consisting of nitrogen, helium, argon, carbon dioxide, methane and ethane.

5. The method according to claim 1 , wherein the reactor is a fixed bed reactor, a fluidized bed reactor or a tank reactor.

6. The method according to claim 1 , wherein the reaction is carried out at a reaction temperature in a range from 180° C. to 400° C. and a reaction pressure in a range from 0.1 MPa to 15.0 MPa, the mass space velocity of dimethoxymethane in the feed gas is in a range from 0.05 h −1 to 10.0 h −1 , and the volume percentage of dimethoxymethane in the feed gas is in a range from 0.1% to 95%.

7. The method according to claim 1 , wherein the molecular sieve catalyst is any one or more selected from the group consisting of a ZSM-35 molecular sieve, a ZSM-5 molecular sieve, a MOR mordenite molecular sieve and a EMT molecular sieve.

8. The method according to claim 7 , wherein the atomic ratio of silicon to aluminum in the molecular sieve catalyst is Si/Al=3 to 100.

9. The method according to claim 7 , wherein
the atomic ratio of silicon to aluminum in the ZSM-35 molecular sieve is Si/Al=20 to 50;
the atomic ratio of silicon to aluminum in the ZSM-5 molecular sieve is Si/Al=20 to 60;
the atomic ratio of silicon to aluminum in the mordenite is Si/Al=10 to 30; and
the atomic ratio of silicon to aluminum in the EMT zeolite is Si/Al=5 to 20.

10. The method according to claim 7 , wherein the molecular sieve catalyst is obtained by heat treatment, hydrothermal treatment, inorganic acid treatment, organic acid treatment, F treatment, chelate treatment, or gas-solid phase dealuminization and silicon supplementation treatment.

11. The method according to claim 7 , wherein the molecular sieve catalyst comprises one or more selected from the group consisting of gallium, iron, copper and silver; introduction methods comprise in-situ synthesis, metal ion exchange or impregnation loading; and the metal content is in a range from 0.01 wt % to 10.0 wt % of the total weight of the catalyst, calculated by metal elementary substance.

12. The method according to claim 11 , wherein the metal content is in a range from 0.05 wt % to 1.0 wt % of the total weight of the catalyst.

13. The method according to claim 6 , wherein the reaction temperature is in a range from 220° C. to 300° C.

14. The method according to claim 6 , wherein the reaction pressure is in a range from 5 MPa to 10 MPa.

15. The method according to claim 6 , wherein the mass space velocity of dimethoxymethane in the feed gas is in a range from 0.3 h −1 to 2.0 h −1 .

16. The method according to claim 6 , wherein the volume percentage of dimethoxymethane in the feed gas is in a range from 0.5% to 30%.

17. The method according to claim 8 , wherein
the atomic ratio of silicon to aluminum in the ZSM-35 molecular sieve is Si/Al=20 to 50;
the atomic ratio of silicon to aluminum in the ZSM-5 molecular sieve is Si/Al=20 to 60;
the atomic ratio of silicon to aluminum in the mordenite is Si/Al=10 to 30; and
the atomic ratio of silicon to aluminum in the EMT zeolite is Si/Al=5 to 20.

Assignees

• Dalian Inst Chem & Physics Cas

Inventors

• Shi Lei
• Liu Zongmin
• In Youming
• Zhu Wenliang
• Liu Yong
• Liu Hongchao

Classifications

• C07C67/37

  by reaction of ethers with carbon monoxide · CPC title

• B01J37/0009 Primary

  Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst · CPC title

• B01J29/7638

  EMT-type, e.g. EMC-2, ECR-30, CSZ-1, ZSM-3 or ZSM-20 · CPC title

• B01J29/68

  Iron group metals or copper · CPC title

• B01J29/46

  Iron group metals or copper · CPC title