Method for improving the selectivity of a catalyst and a process for the epoxidation of an olefin

• US 7,485,597 B2
• Filed: 06/26/2003
• Issued: 02/03/2009
• Est. Priority Date: 06/28/2002
• Status: Active Grant

• Current Assignee: Shell USA Incorporated (Shell Plc)
• Original Assignee: Shell Oil Company (Shell Plc)
• Inventors: Reinalda, Donald, Yeates, Randall Clayton, Lockemeyer, John Robert
• Primary Examiner(s): Hailey; Patricia L
• Application Number:
  US10/606,440
• Publication Number:
  US 20040049061A1
• Time in Patent Office: 2,049 Days
• Field of Search: 502/344, 502/347, 502/348, 502/202, 502305-324, 502/219, 502208-216
• US Class Current: 502/216
• CPC Class Codes: B01J 23/50 Silver
• CPC Class Codes: B01J 23/688 with manganese, technetium or rhenium
• CPC Class Codes: B01J 37/0213 Preparation of the impregnating solution
• CPC Class Codes: B01J 37/14 with gases containing free oxygen
• CPC Class Codes: C07D 301/10 with catalysts containing silver or gold

Abstract

A method for improving the selectivity of a supported highly selective epoxidation catalyst comprising silver in a quantity of at most 0.17 g per m² surface area of the support, which method comprises

• • contacting the catalyst, or a precursor of the catalyst comprising the silver in cationic form, with a feed comprising oxygen at a catalyst temperature above 250° C. for a duration of up to 150 hours, and
  • subsequently decreasing the catalyst temperature to a value of at most 250° C.; and
    a process for the epoxidation of an olefin, which process comprises
  • contacting a supported highly selective epoxidation catalyst comprising silver in a quantity of at most 0.17 g per m² surface area of the support, or a precursor of the catalyst comprising the silver in cationic form, with a feed comprising oxygen at a catalyst temperature above 250° C. for a duration of up to 150 hours, and
  • subsequently decreasing the catalyst temperature to a value of at most 250° C. and contacting the catalyst with the feed comprising the olefin and oxygen.

Claims

1. A method for improving the selectivity of a supported highly selective epoxidation catalyst comprising silver in a quantity of at most 0.17 g per m² surface area of the support and further comprising rhenium or compound thereof, which method comprises

contacting the catalyst, or a precursor of the catalyst comprising the silver in cationic form, with a feed comprising oxygen at a catalyst temperature above 250°

C. for a duration of at least 1 hour and up to 150 hours, and

subsequently decreasing the catalyst temperature to a value of at most 250 °

C.

2. A method as claimed in claim 1, wherein the catalyst, or the precursor of the catalyst, comprises an α

-alumina support having a surface area of at least 1 m²/g, and a pore size distribution such that pores with diameters in the range of from 0.2 to 10 μ

m represent at least 70 % of the total pore volume and such pores together provide a pore volume of at least 0.25 ml/g, relative to the weight of the support.

3. A method as claimed in claim 1, wherein the catalyst, or the precursor of the catalyst, comprises, in addition to silver, a Group IA metal.

4. A method as claimed in claim 1, wherein the catalyst, or the precursor of the catalyst, further comprises or compound thereof, selected from the group of Group IA metals, Group IIA metals, molybdenum, tungsten, chromium, titanium, hafnium, zirconium, vanadium, thallium, thorium, tantalum, niobium, gallium and germanium and mixtures thereof, and optionally a rhenium co-promoter which may be selected from one or more of sulfur, phosphorus, boron, and compounds thereof, on the support material.

5. A method as claimed in claim 1, wherein the catalyst, or the precursor of the catalyst, comprises silver in a quantity of from 50 to 250 g/kg, on the total catalyst,and the support has a surface area of from 1 to 5 m²/g.

6. A method as claimed in claim 1, wherein the feed comprises oxygen in a quantity of from 1 to 30% v, relative to the total feed.

7. A method as claimed in claim 6, wherein the feed comprises oxygen in a quantity of from 2 to 25% v, relative to the total feed.

8. A method as claimed in claim 1, wherein the catalyst, or the precursor of the catalyst, is contacted with a feed comprising oxygen at a temperature in the range of from 250 to 320°

C.

9. A method as claimed in claim 8, wherein the temperature in the range of from 255 to 300°

C.

10. A method as claimed in claim 1, wherein the duration is in the range of from 1 to 50 hours.

11. A method as claimed in claim1, wherein the duration is in the range of from 2 to 40 hours.

12. A method as claimed in claim 1, wherein the feed comprises an olefin, in addition to oxygen.

13. A method as claimed in claim 12, wherein the feed comprises the olefin in a concentration of from 0.5 to 70 mole-%;

oxygen in a concentration of from 1 to 15 mole-%; and

, in addition, a saturated hydrocarbon, if any, in a concentration of from 0 to 80 mole-%, relative to the total feed.

14. A method as claimed in claim 13, wherein the feed comprises the olefin in a concentration of from 1 to 60 mole-%;

oxygen in a concentration of from 2 to 10 mole-%; and

a saturated hydrocarbon in a concentration of from 30 to 75 mole-%, relative to the total feed.

15. A method as claimed in claim 1, wherein the quantity of silver relative to the surface area of the support is in the range of from 0.01 to 0.15 g/m².

16. A method as claimed in claim 15, wherein the quantity of silver relative to the surface area of the support is in the range of from 0.02 to 0.12 g/m².

17. A method as claimed in claim 15, wherein the catalyst, or the precursor of the catalyst, comprises silver in a quantity of from 50 to 250 g/kg, on the total catalyst, and the catalyst comprises an α

-alumina support having a surface area of from 1 to 5 m²/g, and a pore size distribution such that pores with diameters in the range of from 0.2 to 10 μ

m represent at least 70% of the total pore volume and such pores together provide a pore volume of at least 0.25 ml/g, relative to the weight of the support.

18. A method as claimed in claim 15, wherein the catalyst, or the prcursor of the catalyst, comprises, in addition to silver, a Group IA metal.

19. A method as claimed in claim 18, wherein the catalyst, or the precursor of the catalyst, further comprises, a further metal or compound thereof selected from the group of Group IA metals, Group IIA metals, molybdenum, tungsten, chromium, titanium, hafnium, zirconium, vanadium, thallium, thorium, tantalum, niobium, gallium and germanium and mixtures thereof, and optionally a rhenium co-promoter which may be selected from one or more of sulfur, phosphorus boron, and compounds thereof, on the support material.

20. A method as claimed in claim 15, wherein the catalyst, or the precursor of the catalyst, is contacted with a feed comprising oxygen at a temperature in the range of from 250 to 320°

C.

21. A method as claimed in claim 20, wherein the catalyst, or the precursor of the catalyst, is contacted with a feed comprising oxygen at a temperature in the range of from 255 to 300°

C.

22. A method as claimed in claim 15, wherein the duration is in the range of from 1 to 50 hours.

23. A method as claimed in claim 22, wherein the duration is in the range of from 2 to 40 hours.

24. A method as claimed in claim 23, wherein the feed comprises the olefin in a concentration of from 0.5 to 70 mole-%;

oxygen in a concentration of from 1 to 15 mole-%; and

, in addition, a saturated hydrocarbon, if any, in a concentration of from 0 to 80 mole-%, relative to the total feed.