Oxidative esterification process

Patent metadata

Field	Value
Publication number	US-9969672-B2
Application number	US-201515521750-A
Country	US
Kind code	B2
Filing date	Oct 7, 2015
Priority date	Oct 31, 2014
Publication date	May 15, 2018
Grant date	May 15, 2018

Abstract

A process for the preparation of MMA via oxidative esterification in the presence of a catalyst comprising palladium, bismuth, and antimony.

First claim

What is claimed is:

1. A process for the preparation of methyl methacrylate (MMA) via oxidative esterification, the process comprising contacting methacrolein, methanol, and an oxygen-containing gas in a reaction zone in the presence of a catalyst comprising palladium, bismuth, and antimony under reaction conditions sufficient to produce MMA.

2. The process of claim 1 wherein the catalyst is a heterogeneous catalyst comprising a catalytic metal on a porous carrier or support, where the catalytic metal comprises palladium, bismuth, and antimony.

3. The process of any of claim 1 wherein the weight ratio of palladium to bismuth in the catalyst is from 20:1 to 1:10.

4. The process of claim 1 wherein the weight ratio of Sb to bismuth is from 100:1 to 1:10.

5. The process of claim 1 wherein the catalyst is a supported catalyst and the support comprises at least one of activated carbon, magnesium oxide, zinc oxide, titanium oxide, calcium carbonate, silica-alumina, alumina-silica, silica or alumina.

6. The process of claim 1 wherein the catalyst is a supported catalyst and the amount of the catalytic metal on the support is from 0.1 to 20% by weight, based on the weight of the support.

7. The process of claim 1 wherein the catalyst is a supported catalyst and the surface area of the catalyst is at least 50 m 2 /g.

8. The process of claim 1 wherein the catalyst is a supported catalyst and the median particle size of the supported catalyst is from 1 to 200 microns.

9. The process of claim 1 wherein the catalyst is a supported catalyst and the support comprises at least one of alumina and silica.

10. The process of claim 1 wherein the catalyst is a supported catalyst and the support comprises silica modified with magnesia.

11. The process of claim 1 wherein the catalyst is a supported catalyst and the support comprises primarily silica.

12. The process of claim 1 wherein the catalyst is a supported catalyst and the support is modified with alumina, magnesia, or a combination thereof.

13. The process of claim 1 wherein the weight ratio of palladium to bismuth in the catalyst is from 5:1 to 1:1, and the weight ratio of Sb to bismuth is from 1:1 to 1:4.

14. The process of claim 1 wherein the weight ratio of the catalyst in the reaction zone to methacrolein fed to the reaction zone is from 1:1000 to 20:1.

15. The process of claim 1 wherein the temperature in the reaction zone is from 0° C. to 120° C., and the pressure in the reaction zone is from 50 to 2000 kPa (7.3 to 290 psia).

Assignees

• Rohm & Haas

Inventors

• Limbach Kirk W
• Kraptchetov Dmitri A
• Frick Christopher D

Classifications

• C07C67/39 Primary

  by oxidation of groups which are precursors for the acid moiety of the ester · CPC title

• C07C67/44 Primary

  by oxidation-reduction of aldehydes, e.g. Tishchenko reaction · CPC title

• B01J21/08

  Silica · CPC title

• B01J23/6445

  Antimony · CPC title

• B01J21/10

  Magnesium; Oxides or hydroxides thereof · CPC title