Iridium catalysts for carbonylation

Patent metadata

Field	Value
Publication number	US-9421522-B2
Application number	US-201213716336-A
Country	US
Kind code	B2
Filing date	Dec 17, 2012
Priority date	Dec 28, 2011
Publication date	Aug 23, 2016
Grant date	Aug 23, 2016

Abstract

A solid catalyst comprising an effective amount of iridium and at least one second metal selected from gallium, zinc, indium and germanium associated with a solid support material is useful for vapor phase carbonylation to produce carboxylic acids and esters from alkyl alcohols, esters, ethers or ester-alcohol mixtures. The iridium and at least one second metal are deposited on a support material. In some embodiments of the invention, the catalyst is useful for vapor phase carbonylation.

First claim

We claim:

1. A method for producing at least one carboxylic acid, ester, or combination of carboxylic acid and ester mixtures from at least one reactant selected from alkyl alcohols, ethers, esters and combinations of two or more of the foregoing, the method comprising:
a) contacting a gaseous composition comprising the at least one reactant with carbon monoxide in a reaction zone under vapor-phase carbonylation reaction conditions in the presence of a catalyst comprising iridium and at least one second metal selected from gallium, zinc, indium and germanium, wherein the iridium and the at least one second metal are associated with a solid support material; and
b) recovering at least one carboxylic acid or ester from the reaction zone, wherein the solid support material comprises activated carbon.

2. The method of claim 1 wherein the reaction zone is maintained at a pressure of from about 0.1 to about 100 bar absolute and a temperature of from about 100° C. to about 350° C.

3. The method of claim 1 wherein the catalyst further comprises at least one vaporous component comprising a halogen promoting component selected from hydrogen halides, gaseous hydrogen iodide, alkyl and aryl halides having up to 12 carbon atoms, iodine, bromine or chlorine, and mixtures of two or more of the foregoing.

4. The method of claim 3 wherein the at least one vaporous halogen promoting component is selected from hydrogen iodide, methyl iodide, ethyl iodide, 1-iodopropane, 2-iodobutane, 1-iodobutane, hydrogen bromide, methyl bromide, ethyl bromide, benzyl iodide and combinations of two or more of the foregoing.

5. The method of claim 3 wherein the at least one vaporous halogen promoting component is selected from hydrogen iodide, methyl iodide, hydrogen bromide, methyl bromide and combinations of two or more of the foregoing.

6. The method of claim 3 wherein the at least one reactant is methanol and the at least one vaporous halogen promoting component is present in an amount that results in a molar ratio of about 1:1 to 10,000:1 of methanol or methanol equivalents to halide.

7. The method of claim 1 wherein the at least one reactant is selected from an alkyl alcohol having from 1 to 10 carbon atoms, alkane polyols having 2 to 6 carbon atoms, alkyl alkylene polyethers having 3 to 20 carbon atoms, alkoxyalkanols having from 3 to 10 carbon atoms and combinations of two or more of the foregoing.

8. The method of claim 1 wherein the catalyst includes from about 0.1 weight percent to about 3 weight percent of the total catalyst weight each of the iridium and the at least one second metal.

9. The method of claim 1 wherein the molar ratio in the catalyst of the at least one second metal to iridium is from about 0.1:1 to about 10:1.

10. The method of claim 1 wherein the molar ratio in the catalyst of the at least one second metal to iridium is from about 0.5:1 to about 5:1.

11. A method for producing at least one carboxylic acid, ester, or combination of carboxylic acid and ester mixtures from at least one selected from alkyl alcohols, ethers, esters and combinations of two or more of the foregoing, the method comprising:
a) contacting a gaseous composition comprising the at least one reactant with carbon monoxide in a reaction zone under vapor-phase carbonylation reaction conditions in the presence of a catalyst comprising from about 0.01 weight percent to about 10 weight percent of the total catalyst weight each of iridium and at least one second metal selected from gallium, zinc, indium and germanium, wherein the iridium and at least one second metal are associated with a solid support material; and
b) recovering at least one carboxylic acid or ester from the reaction zone wherein the solid support material comprises activated carbon.

12. The method of claim 11 wherein the reaction zone is maintained at a pressure of from about 0.1 to about 100 bar absolute and a temperature of from about 100° C. to about 350° C.

13. The method of claim 11 wherein the catalyst further comprises at least one vaporous component comprising a halogen promoting component selected from hydrogen halides, gaseous hydrogen iodide, alkyl and aryl halides having up to 12 carbon atoms, iodine, bromine or chlorine, and mixtures of two or more of the foregoing.

14. The method of claim 13 wherein the at least one vaporous halogen promoting component is selected from hydrogen iodide, methyl iodide, ethyl iodide, 1-iodopropane, 2-iodobutane, 1-iodobutane, hydrogen bromide, methyl bromide, ethyl bromide, benzyl iodide and combinations of two or more of the foregoing.

15. The method of claim 13 wherein the at least one vaporous halogen promoting component is selected from hydrogen iodide, methyl iodide, hydrogen bromide, methyl bromide and combinations of two or more of the foregoing.

16. The method of claim 13 wherein the at least one reactant is methanol and the at least one vaporous halogen promoting component is present in an amount that results in a molar ratio of about 1:1 to 10,000:1 of methanol or methanol equivalents to halide.

17. The method of claim 11 wherein the at least one reactant is selected from an alkyl alcohol having from 1 to 10 carbon atoms, alkane polyols having 2 to 6 carbon atoms, alkyl alkylene polyethers having 3 to 20 carbon atoms, alkoxyalkanols having from 3 to 10 carbon atoms and combinations of two or more of the foregoing.

18. The method of claim 11 wherein the catalyst includes from about 0.1 weight percent to about 3 weight percent of the total catalyst weight each of the iridium and the at least one second metal.

19. The method of claim 11 wherein the molar ratio in the catalyst of the at least one second metal to iridium is from about 0.5:1 to about 5:1.

Assignees

• Eastman Chem Co

Inventors

• Zhu Zhidong George
• Tustin Gerald Charles
• Zoeller Joseph Robert
• Moore Mary Kathleen
• Jenkins David Alan

Classifications

• B01J31/0231

  Halogen-containing compounds · CPC title

• B01J21/18

  Carbon · CPC title

• C07C67/36

  by reaction with carbon monoxide or formates (C07C67/02, C07C67/03, C07C67/10 take precedence) · CPC title

• B01J23/62 Primary

  with gallium, indium, thallium, germanium, tin or lead · CPC title

• B01J23/60

  with zinc, cadmium or mercury · CPC title