[특허]Fischer-Tropsch synthesis

GTL.FI AG

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Fischer-Tropsch synthesis

특허상세정보
국가/구분	United States(US) Patent 등록
국제특허분류(IPC7판)	B01J-023/78 B01J-023/80 B01J-023/83 B01J-023/889 B01J-023/89 C07C-001/04 B01J-021/04 B01J-023/00 B01J-023/75 B01J-035/00 B01J-035/10 B01J-037/02 B01J-037/08 B01J-037/18 C10G-002/00
출원번호	US-0510867 (2010-11-16)
등록번호	US-10040054 (2018-08-07)
우선권정보	GB-0920226.8 (2009-11-18)
국제출원번호	PCT/GB2010/002111 (2010-11-16)
§371/§102 date	20120924 (20120924)
국제공개번호	WO2011/061484 (2011-05-26)
발명자 / 주소	Rytter, Erling Borg, Øyvind Eri, Sigrid Sperle, Thomas
출원인 / 주소	GTL.FI AG
대리인 / 주소	Stender, Brian L.
인용정보	피인용 횟수 : 0 인용 특허 : 122

초록

A process for the preparation of an F-T catalyst in which the presence of alkaline earth metals is minimized in the support itself and in the processing conditions, in order to provide a catalyst with an alkaline earth metal content of less than 2000 ppm.

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1. A catalyst for a Fischer-Tropsch synthesis reaction made by taking an initial alumina porous support material having an alkaline earth metal content of less than 1000 ppm, wherein the initial alumina support material is modified by treatment with a divalent metal which is capable of forming a spinel and is calcined at a temperature in the range of 900 to 1400° C. such that the modified support comprises a spinel compound, wherein the modified support material is impregnated with a source of cobalt in the form of a cobalt precursor, which contributes an additional alkaline earth metal content of less than 1000 ppm in the final catalyst, wherein the impregnated support material is heat treated at a temperature of at least 200° C. to yield a cobalt oxide catalyst, and wherein the catalyst comprises: a porous support material, an active cobalt content of 5 to 60 wt % expressed in terms of weight of the catalyst as a whole, assuming complete reduction of the cobalt precursor to cobalt metal, and an alkaline earth metal content of less than 2000 ppm. 2. The catalyst for a Fischer-Tropsch synthesis reaction of claim 1, wherein the support material is γ-alumina, any transition alumina, α-alumina, boehmite, aluminium hydroxide or mixtures thereof. 3. The catalyst for a Fischer-Tropsch synthesis reaction of claim 1, wherein the support material is alumina and is prepared by the precipitation method or the alkoxide route. 4. The catalyst for a Fischer-Tropsch synthesis reaction of claim 1, wherein the support material is γ-alumina, and is prepared by heating to a temperature in the range 400 to 800° C. 5. The catalyst for a Fischer-Tropsch synthesis reaction of claim 1, wherein the initial support material has an alkaline earth metal content of less than 500 ppm. 6. The catalyst for a Fischer-Tropsch synthesis reaction of claim 1, wherein the initial support material has an alkaline earth metal content of between 5 and 1000 ppm. 7. The catalyst for a Fischer-Tropsch synthesis reaction of claim 1, wherein the alkaline earth metal is calcium or magnesium. 8. The catalyst for a Fischer-Tropsch synthesis reaction of claim 1, further comprising a stabilizer incorporated into the porous support material. 9. The catalyst for a Fischer-Tropsch synthesis reaction of claim 8, wherein the stabilizer is lanthanum. 10. The catalyst for a Fischer-Tropsch synthesis reaction of claim 1, wherein the cobalt is selected from cobalt nitrate (Co(NO3)2), cobalt carbonate(s), cobalt (hexa) amine salt(s) and organic cobalt compounds. 11. The catalyst for a Fischer-Tropsch synthesis reaction of claim 1, wherein the support material comprises a promoter. 12. The catalyst for a Fischer-Tropsch synthesis reaction of claim 11, wherein the promoter comprises platinum or rhenium. 13. The catalyst for a Fischer-Tropsch synthesis reaction of claim 12, wherein the promoter is platinum and represents between 0.001 and 0.5 wt %. 14. The catalyst for a Fischer-Tropsch synthesis reaction of claim 12, wherein the promoter is rhenium and represents between 0.01 and 5 wt %. 15. The catalyst for a Fischer-Tropsch synthesis reaction of claim 12, wherein the promoter is rhenium and the source of rhenium is selected from perrhenic acid (HReO4), ammonium perrhenate, rhenium halide and rhenium carbonyl(s). 16. The catalyst for a Fischer-Tropsch synthesis reaction of claim 1, wherein the divalent metal is nickel or zinc or mixtures thereof. 17. The catalyst for a Fischer-Tropsch synthesis reaction of claim 16, wherein the source of nickel is nickel nitrate, and/or the source of zinc is zinc nitrate. 18. The catalyst for a Fischer-Tropsch synthesis reaction of claim 1, wherein the divalent metal is deployed in one or more impregnation steps using a solvent, yielding from the impregnation step an alkaline earth metal content of less than 500 ppm in the cobalt oxide catalyst. 19. The catalyst for a Fischer-Tropsch synthesis reaction of claim 1, wherein the divalent metal is deployed in one or more impregnation steps using a solvent, yielding from the impregnation step an alkaline earth metal content between 5 and 500 ppm. 20. The catalyst for a Fischer-Tropsch synthesis reaction of claim 1, wherein the support material has a specific surface area below 80 m2/g. 21. The catalyst for a Fischer-Tropsch synthesis reaction of claim 1, wherein the support material has a pore volume below 0.5 ml/g. 22. A Fischer-Tropsch catalyst comprising: a cobalt source impregnated on a porous support material;wherein the porous support material comprises alumina and a divalent metal spinel; said porous support material being prepared by modifying an initial alumina support material by treatment with a source of a divalent metal which is capable of forming a spinel and calcining the treated support material at a temperature in the range of 900 to 1400° C. to yield the divalent metal spinel andwherein said catalyst has an alkaline earth metal content of less than 2000 ppm. 23. The Fischer-Tropsch catalyst of claim 22, wherein the support material is alumina and is prepared by the precipitation method or the alkoxide route. 24. The Fischer-Tropsch catalyst of claim 22, wherein the support material is gamma-alumina, any transition alumina, alpha-alumina, boehmite, aluminium hydroxide or mixtures thereof. 25. The Fischer-Tropsch catalyst of claim 24, wherein the support material is gamma-alumina, the gamma-alumina prepared by heating to a temperature in the range of 400° C. to 800° C. 26. The Fischer-Tropsch catalyst of claim 22, wherein the divalent metal comprises cobalt, nickel, magnesium or zinc. 27. The Fischer-Tropsch catalyst of claim 22, wherein the divalent metal is nickel or zinc or mixtures thereof. 28. The Fischer-Tropsch catalyst of claim 27, wherein the divalent metal is nickel from a source of nickel nitrate. 29. The Fischer-Tropsch catalyst of claim 27, wherein the divalent metal is zinc from a source of zinc nitrate. 30. The Fischer-Tropsch catalyst of claim 22, wherein the porous support material has an alkaline earth metal content of less than 500 ppm. 31. The Fischer-Tropsch catalyst of claim 22, wherein the porous support material has an alkaline earth metal content of between 5 and 1000 ppm. 32. The Fischer-Tropsch catalyst of claim 22, wherein the alkaline earth metal is calcium or magnesium. 33. The Fischer-Tropsch catalyst of claim 22, further comprising a stabilizer incorporated into the porous support material. 34. The Fischer-Tropsch catalyst of claim 33, wherein the stabilizer is lanthanum. 35. The Fischer-Tropsch catalyst of claim 22, further comprising a promoter. 36. The Fischer-Tropsch catalyst of claim 35, wherein the promoter comprises platinum or rhenium. 37. The Fischer-Tropsch catalyst of claim 36, wherein the promoter is platinum and represents between 0.001 and 0.5 wt %. 38. The Fischer-Tropsch catalyst of claim 36, wherein the promoter is rhenium and represents between 0.01 and 5 wt %. 39. The Fischer-Tropsch catalyst of claim 36, wherein the promoter is rhenium and the source of rhenium is selected from perrhenic acid (HReO4), ammonium perrhenate, rhenium halide and rhenium carbonyl(s). 40. The Fischer-Tropsch catalyst of claim 22, wherein the cobalt source is in an oxidated state. 41. The Fischer-Tropsch catalyst of claim 22, wherein the cobalt is an activated cobalt. 42. The Fischer-Tropsch catalyst of claim 22, wherein the source of cobalt is selected from cobalt nitrate (Co(NO3)2), cobalt carbonate(s), cobalt (hexa) amine salt(s) and organic cobalt compounds. 43. The Fischer-Tropsch catalyst of claim 22, wherein the porous support material comprises a divalent metal yielding an alkaline earth metal content of less than 500 ppm. 44. The Fischer-Tropsch catalyst of claim 22, wherein the porous support material comprises a divalent metal yielding an alkaline earth metal content between 5 and 500 ppm. 45. The Fischer-Tropsch catalyst of claim 22, wherein the porous support material has a specific surface area below 80 m2/g. 46. The Fischer-Tropsch catalyst of claim 22, wherein the porous support material has a pore volume below 0.5 ml/g.

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