Patent EA-005120-B1 (EA)
Title: Cobalt catalyst activation process
Inventor: CLARKSON JAY SIMON
IPC: B01J37/08
Filed: 2002-04-05
Abstract: 1. A process for activating a cobalt-containing catalyst by contacting the catalyst with hydrogen in a reactor system suitable for use in a Fischer-Tropsch synthesis wherein a first gaseous stream comprising 0.25 to 5% by volume of hydrogen and 95 to 99.75% by volume of inert gas is continuously introduced into the reactor system and a second gaseous stream is continuously withdrawn from the reactor system wherein the activation procedure comprises the steps of: (A) heating the contents of the reactor system to a temperature which is in a range of 25 to 5 degree C below a critical activation temperature; (B) thereafter increasing the temperature at a rate of up to 20 degree C per hour to a first hold temperature which is in a range of from the critical activation temperature to a temperature which is at most 20 degree C above the critical activation temperature; and (C) maintaining the contents of the reactor system at the first hold temperature until the hydrogen content of the second gaseous stream approaches the hydrogen content of the first gaseous stream. 2. A process as claimed in Claim 1 wherein the critical activation temperature of the catalyst is in the range 210 to 260 degree C, preferably 220 to 250 degree C. 3. A process as claimed in Claims 1 or 2 wherein the hydrogen content of the second gaseous stream is determined either continuously or intermittently and is compared with the hydrogen content of the first gaseous stream. 4. A process as claimed in Claim 3 wherein the critical activation temperature is the temperature at which the hydrogen content of the second gaseous stream falls to less than 90%, preferably less than 80% of the hydrogen content of the first gaseous stream. 5. A process as claimed in Claims 3 or 4 wherein the reduction of the catalyst is continued at the first hold temperature until the hydrogen content of the second gaseous stream is at least 95%, preferably at least 98% of the hydrogen content of the first gaseous stream. 6. A process as claimed in any one of the preceding claims wherein the contents of the reactor system are heated in step (A) to a temperature which is in the range of 25 to 5 degree C below, preferably 15 to 7.5 degree C below the critical activation temperature of the catalyst. 7. A process as claimed in any one of the preceding claims wherein air is purged from the reactor system prior to step (A) by continuously feeding into the reactor system an inert gaseous stream comprising an inert gas selected from the group consisting of nitrogen, helium and argon containing less than 0.2% by volume of oxygen and continuously withdrawing from the reactor system a purge stream until the oxygen content of the purge stream is less than 0.5 % by volume. 8. A process as claimed in any one of the preceding claims wherein the contents of the reactor system are heated in step (A) at a rate of up to4 C/minute, preferably up to2 C/minute, until the temperature is in a range of from 25 to5 C below the critical activation temperature. 9. A process as claimed in any one of the preceding claims wherein step (C) is carried out at a hold temperature which is at most 20 degree C above, preferably at most 10 degree C above the critical activation temperature. 10. A process as claimed in any one of the preceding claims wherein, in step (B), the temperature is ramped to the first hold temperature at a rate of up to10 C per hour, more preferably at a rate of up to 3 degree C per hour. 11. A process as claimed in any one of the preceding claims wherein the catalyst is maintained at the first hold temperature of step (C) for 12 to 120 hours, preferably 24 to 72 hours. 12. A process as claimed in any one of the preceding claims wherein in a further step (D), the contents of the reactor system are heated at a rate of up to 20 degree C per hour from the first hold temperature to a second hold temperature which is up to the maximum operating temperature of the reactor system. 13. A process as claimed in Claim 12 wherein the temperature is ramped to the second hold temperature at a rate of up to 10 degree C per hour, more preferably a rate of up to up to 3 degree C per hour. 14. A process as claimed in Claims 12 or 13 wherein the second hold temperature of step (D) is a temperature of up to 260 degree C, preferably a temperature of up to 240 degree C. 15. A process as claimed in any one of Claims 12 to 14 wherein the contents of the reactor system are maintained at the second hold temperature until the hydrogen content of the first gaseous stream is substantially the same as the hydrogen content of the second gaseous stream. 16. A process as claimed in Claim 15 wherein the catalyst is maintained at the second hold temperature for a period of 0.5 to 48 hours, preferably 4 to 8 hours. 17. A process as claimed in any one of the preceding claims wherein the first gaseous stream comprises 0.5 to 1.5 % by volume of hydrogen and 98.5 to 99.5 % by volume of inert gas, preferably 1 % by volume of hydrogen and 99 % by volume of inert gas. 18. A process as claimed in any one of the preceding claims wherein the first gaseous stream comprises an inert gas selected from the group consisting of nitrogen, helium and argon. 19. A process as claimed in any one of Claims 3 to 18 wherein the hydrogen content of the second gaseous stream is monitored intermittently with a time interval between the analyses of less than 15 minutes, preferably less than 10 minutes. 20. A process as claimed in any one of the preceding claims wherein the hydrogen content of the second gaseous stream is analyzed by gas chromatography or mass spectrometry. 21. A process as claimed in any one of the preceding claims wherein the first gaseous stream is introduced into the reactor system at a flow rate such that the gas hourly space velocity is in the range 200 to 800, preferably 300 to 500 at normal temperature and pressure. 22. A process as claimed in any one of the preceding claims wherein at least a portion of the second gaseous stream is recycled to the reactor system to form at least part of the first gaseous stream and make-up hydrogen is introduced to the gaseous recycle stream so as to maintain the hydrogen content of the first gaseous stream at a substantially constant value. 23. A process as claimed in Claim 22 wherein the gaseous recycle stream is cooled to below its dew point before being recycled to the reactor system, and condensed water is removed from the gaseous recycle stream by means of a gas liquid separator. 24. A process as claimed in any one of the preceding claims wherein the process is carried out at a pressure of less than 20 bar absolute, preferably at a pressure in the range 2 to 5 bar absolute. 25. A process as claimed in any one of the preceding claims wherein the cobalt-containing catalyst comprises cobalt on a support selected from the group consisting of elemental carbon, silica, alumina, titania, ceria, zirconia and zinc oxide. 26. A process as claimed in Claim 25 wherein the catalyst contains from 2 to 35% w, especially from 5 to 25% w of cobalt. 27. A process as claimed in Claims 25 or 26 wherein the catalyst comprises a promoter selected from the group consisting of zirconium, titanium, ruthenium, and chromium. 28. A process as claimed in any one of the preceding claims wherein the cobalt-containing catalyst is pre-treated at elevated temperature with a gas comprising an inert gas and molecular oxygen, before being introduced to the reactor system. 29. A process as claimed in any one of the preceding claims wherein the catalyst is used in the form of a fluidized bed and the first gaseous stream is introduced into the reactor system at a flow rate which sustains fluidization of the bed without entrainment of the catalyst out of the bed. 30. A process as claimed in any one of Claims 1 to28 wherein the catalyst is suspended in a liquid medium and the first gaseous stream is introduced into the reactor system at a flow rate which is sufficiently high to maintain the catalyst in suspension in the liquid medium.