Preparation of ethylene oxide and catalyst

• US 5,929,259 A
• Filed: 11/25/1997
• Issued: 07/27/1999
• Est. Priority Date: 06/05/1996
• Status: Expired due to Fees

• Current Assignee: Shell Oil Company (Shell Plc)
• Original Assignee: Shell Oil Company (Shell Plc)
• Inventors: Lockemeyer, John Robert
• Primary Examiner(s): Yildirim, Bekir L.
• Application Number:
  US08/977,971
• Time in Patent Office: 609 Days
• Field of Search: 502/348, 502/351, 502/439, 549/534, 549/536
• US Class Current: 549/534
• CPC Class Codes: B01J 21/063 Titanium; Oxides or hydroxides thereof
• CPC Class Codes: B01J 23/66 Silver or gold
• CPC Class Codes: B01J 23/688 with manganese, technetium or rhenium
• 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 a process for preparing an ethylene oxide catalyst by depositing silver and one or more alkali metal promoters on an alpha alumina carrier in which a fired carrier body is impregnated with a source of titania in a liquid medium that upon heating yields titania and is then calcined to generate titania uniformly dispersed in the carrier in an amount of up to about 10 percent by weight, basis the total weight of the carrier, and subsequently drying the carrier having said silver and alkali metal supported thereon.

Claims

1. A process for the vapor phase production of ethylene oxide from ethylene and oxygen, said process comprising contacting ethylene 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, wherein said catalyst is prepared by a process comprising;

a) forming a mixture comprising at least one alumina component, ceramic bond, and a liquid medium;

b) shaping the mixture into carrier bodies;

c) drying and firing the bodies at a temperature of from 1200°

C. to about 1500°

C. to form porous carrier bodies;

d) impregnating the porous carrier bodies with a titania generator in a liquid medium;

e) calcining the impregnated bodies at a temperature sufficient to remove volatiles and generate titania;

f) drying the carrier; and

g) depositing a catalytically effective amount of silver and a promoting amount of alkali metal on said carrier.

2. The process of claim 1 wherein, in the carrier, the dried, fired carrier bodies are impregnated using a titania generator selected from the group consisting of a titania sol and a solution of a titanium compound containing ligands which form volatile products.

3. The process of claim 1 wherein, in the carrier, at least about 80 percent by weight of the ceramic components is provided by alpha alumina.

4. The process of claim 1 wherein, in the carrier, the titania generator is added by impregnation in a volume amount equal to the pore volume of the carrier and sufficient to provide from about 0.05 percent by weight to about 10 percent by weight of titania, basis the weight of the finished carrier.

5. The process of claim 1 wherein, in the carrier, the impregnated carrier is calcined a temperature between about 400°

C. and about 1400°

C.

6. The process of claim 1 wherein, in the carrier, a ceramic bond material comprising silica, alumina and an alkali metal is added to the extrudable mixture in an amount in the range of from about 1 percent by weight to about 3 percent by weight of the alumina components, expressed as alpha alumina, in the mixture.

7. The process of claim 1 wherein the amount of 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 process of claim 1 wherein said alkali metal promoter is selected from the group consisting of potassium, rubidium, cesium, lithium and mixtures thereof.

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

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

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

12. The process 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 process for the vapor phase production of ethylene oxide from ethylene and oxygen, said process comprising contacting ethylene 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, wherein said catalyst is prepared by a process comprising;

a) forming a mixture comprising;

i) an alpha alumina having a first component with a median particle size of from about 2 to about 4 microns and a second component with a median particle size of about 4 to about 8 microns;

ii) a seeded, hydrated precursor of alpha alumina in an amount sufficient to provide from about 5 percent by weight to about 60 percent by weight, basis the total weight of alpha alumina, in the catalyst carrier product;

iii) from about 0 to about 40 percent by weight, based on the weight of the alpha alumina, of a burnout material;

iv) from about 1 percent by weight to about 3 percent by weight, based on the weight of alumina in the composition, expressed as alpha alumina, of a ceramic bond material comprising silica alumina and an alkali metal; and

v) water in sufficient quantity to shape the mixture;

b) forming the mixture into the desired shape;

c) firing to convert the seeded precursor of alpha alumina to alpha alumina and form a porous carrier product in which alpha alumina particles with a median particle size of from about 3 microns to about 8 microns are dispersed in a matrix of alpha alumina derived from the seeded precursor material;

d) adding to the porous fired carrier a titania generator selected from the group consisting of an aqueous titania sol and a solution of a titanium compound containing ligands that form volatile products in an amount equivalent to an added titania content in the final carrier formulation of from about 0.05 percent to about 5 percent of the weight of the carrier;

e) calcining the impregnated carrier to remove the solvent and generate the titania;

f) drying the carrier; and

g) depositing a catalytically effective amount of silver and a promoting amount of alkali metal on said carrier.

14. The process of claim 13 wherein, in the carrier, the precursor of alpha alumina is seeded with a sub-micron sized particles of alpha alumina in an amount that is from about 0.2 percent by weight to about 5 percent by weight, basis the total alumina weight, measured as alpha alumina, in the catalyst carrier.

15. The process of claim 13 wherein, in the carrier, the impregnated carrier is calcined at a temperature of from 400°

C. to about 1400°

C.

16. The process of claim 13 wherein the amount of 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.

17. The process of claim 13 wherein said alkali metal promoter is selected from the group consisting of potassium, rubidium, cesium, lithium and mixtures thereof.

18. The process of claim 17 wherein said promoter is cesium.

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

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

21. The process of claim 20 wherein the catalyst additionally comprises a rhenium co-promoter selected from the group consisting of sulfur, molybdenum, tungsten, chromium, phosphorus, boron and mixtures thereof.

22. 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 prepared by depositing a catalytically effective amount of silver and a promoting amount of alkali metal on a carrier prepared by a process comprising;

a) forming a mixture comprising at least one alumina component, ceramic bond, and a liquid medium;

b) shaping the mixture into carrier bodies;

c) drying and firing the bodies at a temperature of from 1200°

C. to about 1500°

C. to form porous carrier bodies;

d) impregnating the porous carrier bodies with a titania generator in a liquid medium; and

then

e) calcining the impregnated bodies at a temperature sufficient to remove volatiles and generate titania,

and subsequently drying the carrier having said silver and alkali metal supported thereon.

23. A process for the epoxidation of one or more olefins wherein said olefin 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 prepared by the process comprising;

a) forming a mixture comprising at least one alumina component, ceramic bond, and a liquid medium;

b) shaping the mixture into carrier bodies;

c) drying and firing the bodies at a temperature of from 1200°

C. to about 1500°

C. to form porous carrier bodies;

d) impregnating the porous carrier bodies with titania generator in a liquid medium;

e) calcining the impregnated bodies at a temperature sufficient to remove volatiles and generate titania;

f) depositing a catalytically effective amount of silver and a promoting amount of alkali metal on said carrier, and

g) drying the carrier having said silver and alkali metal supported thereon.