Claims
- 1. A process for the preparation of a catalyst useful for conversion of synthesis gas to a product containing liquid hydrocarbons, said process comprising:
- (A) depositing cobalt or nickel precursor on a refractory metal oxide support by impregnation or
- precipitation to distribute cobalt or nickel as crystallites on said support to form a supported catalyst, and
- (B) activating said supported catalyst by subjecting said supported catalyst to the steps, in sequence, of
- (i) reduction in hydrogen gas, (ii) oxidation in an oxygen-containing gas and (iii) reduction in hydrogen gas, steps (i), (ii) and (iii) being conducted at a temperature of from about 100.degree. to about 450.degree. C. to form an, activated, supported catalyst more active for conversion of synthesis gas after said step (iii) than after step (i).
- 2. The process of claim 1 wherein said catalyst is prepared by subjecting cobalt on a refractory metal oxide support to said activation procedure.
- 3. The process of claim 1 wherein said catalyst is prepared by subjecting nickel on a refractory metal oxide support to said activation procedure.
- 4. The process of claim 1 wherein said support is alumina or silica.
- 5. The process of claim 4 wherein said support is alumina.
- 6. The process of claim 1 wherein said first reduction step (i) is conducted at a temperature in the range of from about 200.degree. to about 450.degree. C.
- 7. The process of claim 6 wherein said oxidation step (ii) is conducted at a temperature in the range of between about 250.degree. and about 400.degree. C.
- 8. The process of claim 7 wherein said second reduction step (iii) is conducted at a temperature in the range of from about 200.degree. to about 450.degree. C.
- 9. The process of claim 1 wherein said activation steps are conducted while heating at a rate of from about 0.1.degree. to about 2.degree. C. per minute.
- 10. The process of claim 1 wherein said catalyst contains from about 5 to about 15 weight percent cobalt.
- 11. The process of claim 1 wherein said catalyst is prepared by impregnating said support with a non-aqueous, organic impregnating solution of a cobalt salt prior to said activation procedure.
- 12. The process of claim 11 wherein said non-aqueous, organic impregnation solution additionally contains a ruthenium salt.
- 13. The process of claim 1 wherein said activation is conducted at a temperature in the range of between about 250.degree. and about 400.degree. C.
- 14. The process of claim 1 wherein said catalyst additionally contains between about 0.05 and about 0.50 weight percent ruthenium.
- 15. The process of claim 1 wherein said catalyst consists essentially of cobalt on alumina.
- 16. The process of claim 1 wherein said catalyst additionally contains a lanthanum or manganese promoter.
- 17. The process of claim 1 wherein step (i) is conducted in the presence of substantially pure hydrogen.
- 18. The process of claim 1 wherein step (i) is conducted in the presence of a hydrogen-nitrogen mixture.
- 19. A catalyst for the conversion of synthesis gas to a product containing liquid hydrocarbons said catalyst prepared by a process comprising:
- (A) depositing cobalt or nickel precursor on a refractory metal oxide support by impregnation or precipitation to distribute cobalt or nickel as crystallites on said support to form a supported catalyst, and
- (B) activating said supported catalyst by subjecting said supported catalyst to the steps, in sequence, of (i) reduction in hydrogen gas, (ii) oxidation in an oxygen-containing gas and (iii) reduction in hydrogen gas, steps (i), (ii) and (iii) being conducted at a temperature of from about 100.degree. to about 450.degree. C. to form an, activated, supported catalyst more active for conversion of synthesis gas after said step (iii) than after step (i).
- 20. The catalyst of claim 19 wherein said catalyst is prepared by subjecting cobalt on a refractory metal oxide support to said activation procedure.
- 21. The catalyst of claim 19 wherein said catalyst is prepared by subjecting nickel on a refractory metal oxide support to said activation procedure.
- 22. The catalyst of claim 19 wherein said support is alumina or silica.
- 23. The catalyst of claim 22 wherein said support is alumina.
- 24. The catalyst of claim 19 wherein said first reduction step (i) is conducted at a temperature in the range of from about 200.degree. to about 450.degree. C.
- 25. The catalyst of claim 24 wherein said oxidation step (ii) is conducted at a temperature in the range of between about 250.degree. and about 400.degree. C.
- 26. The catalyst of claim 19 wherein said second reduction step (iii) is conducted at a temperature in the range of from about 200.degree. to about 450.degree. C.
- 27. The catalyst of claim 19 wherein said activation steps are conducted while heating at a rate of from about 0.1.degree. to about 2.degree. C. per minute.
- 28. The catalyst of claim 19 wherein said catalyst contains from about 5 to about 15 weight percent cobalt.
- 29. The catalyst of claim 19 wherein said catalyst is prepared by impregnating said support with a non-aqueous, organic impregnating solution of a cobalt salt prior to said activation procedure.
- 30. The catalyst of claim 29 wherein said non-aqueous, organic impregnation solution additionally contains a ruthenium salt.
- 31. The catalyst of claim 29 wherein said non-aqueous solvent is acetone.
- 32. The catalyst of claim 29 wherein said activation is conducted at a temperature in the range of between about 250.degree. and 400.degree. C.
- 33. The catalyst of claim 19 said catalyst additionally contains between about 0.05 and about 0.50 weight percent ruthenium.
- 34. The catalyst of claim 19 wherein said catalyst consists essentially of cobalt on alumina.
- 35. The catalyst of claim 19 wherein said support is silica.
- 36. The catalyst of claim 35 wherein said catalyst additionally contains a lanthanum or manganese promoter.
- 37. The catalyst of claim 19 wherein step (i) is conducted in the presence of substantially pure hydrogen.
- 38. The catalyst of claim 19 wherein step (i) is conducted in the presence of a hydrogen-nitrogen mixture.
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of U.S. Ser. No. 635,911 filed July 30, 1984, now U.S. Pat. No. 4,585,798 which, in turn, is a continuation-in-part of U.S. Ser. No. 310,969 filed Oct. 13, 1981 now abandoned and U.S. Ser. No. 540,662 filed Oct. 11, 1983, now U.S. Pat. No. 493,905 which, in turn, is a divisional of U.S. Ser. No. 310,977 filed Oct. 13, 1981, now U.S. Pat. No. 4,413,064, all in the name of H. Beuther et al.
US Referenced Citations (7)
Number |
Name |
Date |
Kind |
4002658 |
Della Betta et al. |
Jun 1977 |
|
4026823 |
Van Hook et al. |
May 1977 |
|
4090980 |
Carter et al. |
May 1978 |
|
4413064 |
Beuther et al. |
Nov 1983 |
|
4493905 |
Beuther et al. |
Jan 1985 |
|
4585798 |
Beuther et al. |
Apr 1986 |
|
4605676 |
Kobylinski et al. |
Aug 1986 |
|
Foreign Referenced Citations (1)
Number |
Date |
Country |
796921 |
Jun 1958 |
GBX |
Divisions (2)
|
Number |
Date |
Country |
Parent |
734189 |
May 1985 |
|
Parent |
310977 |
Oct 1981 |
|
Continuation in Parts (2)
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Number |
Date |
Country |
Parent |
635911 |
Jul 1984 |
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Parent |
310969 |
Oct 1981 |
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