Process for dehydrating methanol to dimethyl ether

Patent metadata

Field	Value
Publication number	US-12084409-B2
Application number	US-201917433118-A
Country	US
Kind code	B2
Filing date	Feb 22, 2019
Priority date	Feb 22, 2019
Publication date	Sep 10, 2024
Grant date	Sep 10, 2024

Abstract

A process for dehydrating methanol to dimethyl ether product in the presence of a catalyst and a promoter, wherein the catalyst is at least one aluminosilicate zeolite, and the promoter is selected from one or more compounds of Formula I: (I) wherein each of X and any or all of the Y's may independently be selected from hydrogen, halide, a substituted or unsubstituted hydrocarbyl substituent, or a compound of the formula —CHO, —CO 2 R, —COR, or —OR, where R is hydrogen or a substituted or unsubstituted hydrocarbyl substituent, and wherein the molar ratio of promoter to methanol is maintained at less than 1.

First claim

The invention claimed is:

1. A process comprising dehydrating methanol to a dimethyl ether product in the presence of a catalyst and a promoter, wherein the catalyst is at least one aluminosilicate zeolite, and the promoter is selected from one or more compounds of Formula I:

wherein each of X and any or all of the Y's are independently hydrogen, halide, a substituted or unsubstituted hydrocarbyl substituent, or a group of the formula —CHO, —CO 2 R, —COR, or —OR, where R is hydrogen or a substituted or unsubstituted hydrocarbyl substituent, and
wherein the molar ratio of the promoter to the methanol is maintained at less than 1.

2. A process according to claim 1 , wherein the catalyst is at least one aluminosilicate zeolite which comprises at least one channel having a 10-membered ring.

3. A process according to claim 2 , wherein the catalyst is an aluminosilicate zeolite which comprises at least one channel having a 10-membered ring.

4. A process according to claim 1 , wherein the catalyst does not comprise any aluminosilicate zeolite which comprises at least one channel having a 12-membered ring.

5. A process according to claim 1 , wherein the aluminosilicate zeolite is a H-form zeolite.

6. A process according to claim 1 , wherein the aluminosilicate zeolite is selected from framework type CHA, TON, MTT, FER, MWW, MFI, MEL, MOR, BEA, and FAU.

7. A process according to claim 6 , wherein the aluminosilicate zeolite is selected from framework type FER, MWW, MFI, and MEL.

8. A process according to claim 7 , wherein the aluminosilicate zeolite is selected from ferrierite, PSH-3, ZSM-5, ZSM-11, ZSM-35, and MCM-22.

9. A process according to claim 1 , wherein the aluminosilicate zeolite is composited with a binder material.

10. A process according to claim 1 , wherein X and/or any of the Y's are independently selected from hydrogen, halide, and a substituted or unsubstituted hydrocarbyl substituent comprising from 1 to 11 carbon atoms.

11. A process according to claim 1 , wherein X and/or any of the Y's are independently selected from a substituted or unsubstituted hydrocarbyl substituent.

12. A process according to claim 11 , wherein X and/or any of the Y's are independently selected from an unsubstituted hydrocarbyl substituent comprising from 1 to 11 carbon atoms.

13. A process according to claim 11 , wherein X and/or any of the Y's are independently selected from a substituted hydrocarbyl substituent comprising from 1 to 11 carbon atoms.

14. A process according to claim 13 , wherein X and/or any of the Y's are independently a halide substituted hydrocarbyl.

15. A process according to claim 1 , wherein all of the Y's are hydrogen.

16. A process according to claim 1 , wherein the total amount of the promoter relative to the methanol is maintained in an amount of at least 1 ppm.

17. A process according to claim 1 , wherein the molar ratio of the promoter to the methanol is maintained in the range 0.00001:1 to 0.2:1.

18. A process according to claim 1 , wherein the process is carried out at a temperature of from 100° C. to 300° C.

19. A process according to claim 1 , wherein the process is carried out as a heterogeneous vapour phase process.

20. A process comprising dehydrating methanol to a dimethyl ether product in the presence of a catalyst, wherein the catalyst is at least one aluminosilicate zeolite, and wherein prior to using the catalyst in the dehydration process, the catalyst has been impregnated with a promoter selected from one or more compounds of Formula I:

wherein each of X and any or all of the Y's are independently hydrogen, halide, a substituted or unsubstituted hydrocarbyl substituent, or a group of the formula —CHO, —CO 2 R, —COR, or —OR, where R is hydrogen or a substituted or unsubstituted hydrocarbyl substituent.

21. A method of improving the productivity to dimethyl ether in a process for dehydrating methanol, the method comprising dehydrating methanol to dimethyl ether in the presence of a catalyst and a promoter, wherein the catalyst is at least one aluminosilicate zeolite, and the promoter is selected from one or more compounds of Formula I:

wherein each of X and any or all of the Y's are independently hydrogen, halide, a substituted or unsubstituted hydrocarbyl substituent, or a group of the formula —CHO, —CO 2 R, —COR, or —OR, where R is hydrogen or a substituted or unsubstituted hydrocarbyl substituent, and
wherein the molar ratio of the promoter to the methanol is maintained at less than 1.

Assignees

• Bp Plc
• Bp China Holdings Ltd

Inventors

• Dennis-Smither Benjamin James
• Sunley John Glenn
• Yang Zhiqiang

Classifications

• B01J29/85

  Silicoaluminophosphates [SAPO compounds] · CPC title

• B01J29/7046

  MTT-type, e.g. ZSM-23, KZ-1, ISI-4 or EU-13 · CPC title

• B01J29/7042

  TON-type, e.g. Theta-1, ISI-1, KZ-2, NU-10 or ZSM-22 · CPC title

• B01J29/7038

  MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25 · CPC title

• B01J29/7007

  Zeolite Beta · CPC title