Ethylene oxide catalyst and process

• US 5,801,259 A
• Filed: 04/30/1996
• Issued: 09/01/1998
• Est. Priority Date: 04/30/1996
• Status: Expired due to Term

• Current Assignee: Shell Oil Company (Shell Plc)
• Original Assignee: Shell Oil Company (Shell Plc)
• Inventors: Kowaleski, Ruth Mary
• Primary Examiner(s): Ivy, C. Warren
• Assistant Examiner(s): DAHLEN, GARTH
• Application Number:
  US08/643,158
• Time in Patent Office: 854 Days
• Field of Search: 549/536, 549/537, 502/348
• US Class Current: 549/536
• CPC Class Codes: B01J 23/66 Silver or gold
• CPC Class Codes: B01J 37/0009 Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
• CPC Class Codes: C07D 301/10 with catalysts containing silver or gold
• CPC Class Codes: Y02P 20/52 using catalysts, e.g. selective catalysts

Abstract

This invention relates to an ethylene oxide catalyst which contains silver and one or more alkali metal promoters supported on a carrier prepared by a process comprising the use of ceramic particle components with particle sizes chosen to ensure that a desired degree of porosity is obtained without the use of organic burnout materials.

Claims

1. A catalyst suitable for the vapor phase production of ethylene oxide from ethylene and oxygen comprising a catalytically effective amount of silver and a promoting amount of alkali metal(s) deposited on a carrier prepared by a process which comprises:

a) providing a mixture consisting essentially of;

i) ceramic components comprising at least about 80 percent by weight of alpha alumina, from about 0.01 percent by weight to about 10 percent by weight (measured as the oxide, MO) of an alkaline earth metal oxide, from about 0.01 percent by weight to about 10 percent by weight (measured as the silica) of a silicon oxide, and from about zero to about 15 percent by weight (measured as the dioxide) of zirconium in the form of an oxide;

ii) a liquid carrier medium in an amount to render the mixture shapable; and

iii) a total amount of from zero to about 15 percent by weight of ceramic bond, lubricant and/or forming aids;

b) shaping the mixture to form a carrier precursor;

c) drying the carrier precursor to remove the liquid from the carrier medium; and

d) firing the precursor to form a carrier with a porosity of from about 15 percent to about 60 percent, wherein the particle sizes of the ceramic components are chosen such that the packing density of the dried precursor is not greater than that of the fired carrier.

2. The catalyst of claim 1 wherein, in the carrier, the ceramic components of the mixture comprise at least about 85 percent by weight of alpha alumina, from about 0.01 percent by weight to about 6.0 percent by weight of an alkaline earth metal silicate selected from the group consisting of calcium and magnesium silicates and from about 0.01 percent by weight to about 10 percent by weight of zirconia.

3. The catalyst of claim 1 wherein, in the carrier, the alpha alumina component has a bimodal particle size distribution with a first mode having an average particle size of from about 15 microns to about 120 microns and a second mode having an average particle size that is less than one-half that of the first mode and is between about 1 and about 15 microns.

4. The catalyst of claim 1 wherein, in the carrier, the alpha alumina component selected comprises lightly sintered agglomerates with a median particle size of from about 15 microns to about 120 microns.

5. The catalyst of claim 4 wherein, in the carrier, the alpha alumina component selected comprises lightly sintered agglomerates with a median particle size of from about 30 microns to about 90 microns.

6. The catalyst of claim 1 wherein, in the carrier, the ceramic components further comprise a compound that forms titania when the carrier is fired in an amount sufficient to provide the equivalent of from about 0.01 percent by weight to about 5 percent by weight of titania.

7. The catalyst of claim 1 wherein the silver ranges from about 1 percent by weight to about 40 percent by weight of the total catalyst and the alkali metal ranges from about 10 parts per million to about 3000 parts per million, expressed as the metal, by weight of the total catalyst.

8. The catalyst of claim 7 wherein said alkali metal promoter is selected from the group consisting of potassium, rubidium, cesium, lithium and mixtures thereof.

9. The catalyst of claim 8 wherein said promoter is cesium.

10. The catalyst of claim 1 wherein said alkali metal promoter comprises cesium plus at least one additional alkali metal.

11. The catalyst of claim 1 wherein the catalyst additionally comprises a promoting amount of rhenium.

12. The catalyst of claim 11 wherein the catalyst additionally comprises a rhenium co-promoter selected from the group consisting of sulfur, molybdenum, tungsten, chromium, phosphorus, boron and mixtures thereof.

13. A catalyst suitable for the vapor phase production of ethylene oxide from ethylene and oxygen comprising a catalytically effective amount of silver and a promoting amount of alkali metal deposited on a carrier prepared by a process which comprises:

a) providing a mixture consisting essentially of;

i) ceramic components comprising at least about 90 percent by weight of alpha alumina, from about 0.01 percent by weight to about 10.0 percent by weight (measured as the oxide, MO) of an alkaline earth metal oxide, from about 0.01 percent by weight to about 10.0 percent by weight (measured as the silica) of a silicon oxide, and from about zero to about 15 percent by weight (measured as the dioxide) of zirconium in the form of an oxide;

ii) a liquid carrier medium in an amount to render the mixture shapable; and

iii) a total amount of from zero to about 15 percent by weight of ceramic bond, lubricant and/or forming aids;

b) shaping the mixture to form a carrier precursor;

c) drying the carrier precursor to remove the liquid from the carrier medium; and

d) firing the precursor to form a carrier with a porosity of from about 15 percent to about 60 percent,

wherein the particle sizes of the ceramic components are chosen such that the packing density of the dried precursor is not greater than that of the fired carrier.

14. The catalyst of claim 13 wherein, in the carrier, the ceramic components of the mixture comprise at least about 85 percent by weight of alpha alumina, from about 0.01 percent by weight to about 6.0 percent by weight of an alkaline earth metal silicate selected from the group consisting of calcium and magnesium silicates and from about 0.01 percent by weight to about 10 percent by weight of zirconia.

15. The catalyst of claim 13 wherein, in the carrier, the alpha alumina component has a bimodal particle size distribution with a first mode having an average particle size of from about 15 microns to about 120 microns and a second mode having an average particle size that is less than one-half that of the first mode and is between about 1 and about 15 microns.

16. The catalyst of claim 13 wherein, in the carrier, the alpha alumina component selected comprises lightly sintered agglomerates with a median particle size of from about 15 microns to about 120 microns.

17. The catalyst of claim 16 wherein, in the carrier, the alpha alumina component selected comprises lightly sintered agglomerates with a median particle size of from about 30 microns to about 90 microns.

18. The catalyst of claim 13 wherein, in the carrier, the ceramic components further comprise a compound that forms titania when the carrier is fired in an amount sufficient to provide the equivalent of from about 0.01 percent by weight to about 5 percent by weight of titania.

19. The catalyst of claim 13 wherein the silver ranges from about 1 percent by weight to about 40 percent by weight of the total catalyst and the alkali metal ranges from about 10 parts per million to about 3000 parts per million, expressed as the metal, by weight of the total catalyst.

20. The catalyst of claim 19 wherein said alkali metal promoter is selected from the group consisting of potassium, rubidium, cesium, lithium and mixtures thereof.

21. The catalyst of claim 20 wherein said promoter is cesium.

22. The catalyst of claim 13 wherein said alkali metal promoter comprises cesium plus at least one additional alkali metal.

23. The catalyst of claim 13 wherein the catalyst additionally comprises a promoting amount of rhenium.

24. The catalyst of claim 23 wherein the catalyst additionally comprises a rhenium co-promoter selected from the group consisting of sulfur, molybdenum, tungsten, chromium, phosphorus, boron and mixtures thereof.

25. A process for the production of ethylene oxide wherein ethylene is contacted in the vapor phase with an oxygen-containing gas at ethylene oxide forming conditions at a temperature in the range of from about 180°

C. to about 330°

C. in the presence of a catalyst comprising a catalytically effective amount of silver and a promoting amount of alkali metal deposited on a carrier prepared by a process which comprises;

a) providing a mixture consisting essentially of;

i) ceramic components comprising at least about 80 percent by weight of alpha alumina, from about 0.01 percent by weight to about 10 percent by weight (measured as the oxide, MO) of an alkaline earth metal oxide, from about 0.01 percent by weight to about 10 percent by weight (measured as the silica) of a silicon oxide, and from about zero to about 15 percent by weight (measured as the dioxide) of zirconium in the form of an oxide;

ii) a liquid carrier medium in an amount to render the mixture shapable; and

iii) a total amount of from zero to about 15 percent by weight of ceramic bond, lubricant and/or forming aids;

b) shaping the mixture to form a carrier precursor;

c) drying the carrier precursor to remove the liquid from the carrier medium; and

d) firing the precursor to form a carrier with a porosity of from about 15 percent to about 60 percent, wherein the particle sizes of the ceramic components are chosen such that the packing density of the dried precursor is not greater than that of the fired carrier.

26. A process for the epoxidation of olefins having no allylic hydrogens wherein an olefin having no allylic hydrogen is contacted in the vapor phase with an oxygen-containing gas at epoxide forming conditions at a temperature in the range of from about 75°

C. to about 325°

C. in the presence of an organic halide and a catalyst comprising a catalytically effective amount of silver and a promoting amount of alkali metal deposited on a carrier prepared by a process which comprises;

a) providing a mixture consisting essentially of;

i) ceramic components comprising at least about 80 percent by weight of alpha alumina, from about 0.01 percent by weight to about 10 percent by weight (measured as the oxide, MO) of an alkaline earth metal oxide, from about 0.01 percent by weight to about 10 percent by weight (measured as the silica) of a silicon oxide, and from about zero to about 15 percent by weight (measured as the dioxide) of zirconium in the form of an oxide;

ii) a liquid carrier medium in an amount to render the mixture shapable; and

iii) a total amount of from zero to about 15 percent by weight of ceramic bond, lubricant and/or forming aids;

b) shaping the mixture to form a carrier precursor;

c) drying the carrier precursor to remove the liquid from the carrier medium; and

d) firing the precursor to form a carrier with a porosity of from about 15 percent to about 60 percent, wherein the particle sizes of the ceramic components are chosen such that the packing density of the dried precursor is not greater than that of the fired carrier.