Slurry bed Fischer-Tropsch catalysts with silica/alumina structural promoters
View Patent ↗A structurally promoted, precipitated, Fischer-Tropsch catalyst that exhibits an RCAI-10 of 0-2.8 and/or produces less than 6 wt % fines after 5 hours ASTM Air Jet Attrition testing, due to formation via: preparing a nitrate solution by forming at least one metal slurry and combining the at least one metal slurry with a nitric acid solution; combining the nitrate solution with a basic solution to form a precipitate; structurally promoting the precipitate with at least one source of silicon to form a promoted mixture, wherein promoting comprises combining the precipitate with (a) silicic acid and one or more component selected from the group consisting of non-crystalline silicas, crystalline silicas, and sources of kaolin or (b) a component selected from the group consisting of non-crystalline silicas and sources of kaolin, in the absence of silicic acid; and spray drying the promoted mixture to produce catalyst having a desired particle size.
1. A structurally promoted, precipitated, Fischer-Tropsch catalyst that exhibits an RCAI-10 in the range of from about 0 to about 2.8, produced by a method comprising:
preparing a nitrate solution, wherein preparing comprises forming at least one metal slurry and combining the at least one metal slurry with a nitric acid solution;
combining the nitrate solution with a basic solution to form a precipitate;
structurally promoting the precipitate with at least one source of silicon to form a promoted mixture, wherein promoting comprises combining the precipitate with (a) silicic acid and one or more component selected from the group consisting of non-crystalline silicas, crystalline silicas, and sources of kaolin or (b) at least one component selected from the group consisting of non-crystalline silicas and sources of kaolin, in the absence of silicic acid; and
spray drying the promoted mixture to produce a spray-dried catalyst having a particle size.
2. The Fischer-Tropsch catalyst of claim 1 exhibiting an RCAI-20 in the range of from about 0 to about 4.3.
3. The Fischer-Tropsch catalyst of claim 1 comprising iron, obtained by preparation of the nitrate solution with an iron slurry, and having a weight ratio of Fe:SiO 2 in the range of from about 100:5 to 100:25.
4. The Fischer-Tropsch catalyst of claim 3 further comprising potassium, obtained by incorporation thereof via double promotion of the precipitate, including chemical promotion with a source of potassium and structural promotion via (a) or (b), and having a weight ratio of Fe:K in the range of from about 100:2 to 100:5.
5. The Fischer-Tropsch catalyst of claim 4 wherein the source of potassium is selected from the group consisting of KOH, K 2 O, and combinations thereof.
6. The Fischer-Tropsch of claim 3 wherein promoting comprises combining the precipitate with (a) silicic acid and one or more component selected from the group consisting of non-crystalline silicas, crystalline silicas, and sources of kaolin, and wherein the source of silicon comprises up to or equal to about 5 weight percent silicic acid.
7. The Fischer-Tropsch catalyst of claim 6 wherein promoting comprises combining the precipitate with silicic acid and at least one non-crystalline silica.
8. The Fischer-Tropsch catalyst of claim 7 wherein the at least one non-crystalline silica is selected from the group consisting of fumed silicas.
9. The Fischer-Tropsch catalyst of claim 7 wherein promoting comprises combining the precipitate with silicic acid, at least one non-crystalline silica, and at least one source of kaolin.
10. The Fischer-Tropsch catalyst of claim 6 wherein promoting comprises combining the precipitate with silicic acid and at least one crystalline silica.
11. The Fischer-Tropsch catalyst of claim 10 wherein promoting comprises combining the precipitate with silicic acid, at least one crystalline silica, and at least one source of kaolin.
12. The Fischer-Tropsch catalyst of claim 6 wherein promoting comprises combining the precipitate with silicic acid, at least one crystalline silica, at least one non-crystalline silica, and at least one source of kaolin.
13. The Fischer-Tropsch catalyst of claim 1 comprising iron and copper, obtained by preparation of the nitrate solution with a metal slurry comprising iron and copper, a metal slurry comprising iron and a metal slurry comprising copper, or both, and having a weight ratio of Fe:SiO 2 in the range of from about 100:5 to 100:25, and a weight ratio of Fe:Cu in the range of from about 100:2 to about 100:5.
14. The Fischer-Tropsch catalyst of claim 1 wherein promoting comprises combining the precipitate with (b) at least one component selected from the group consisting of non-crystalline silicas and sources of kaolin, in the absence of silicic acid.
15. The Fischer-Tropsch catalyst of claim 14 wherein promoting comprises combining the precipitate with at least one non-crystalline silica, in the absence of silicic acid.
16. The Fischer-Tropsch catalyst of claim 15 wherein the non-crystalline silica is selected from fumed silicas.
17. The Fischer-Tropsch catalyst of claim 14 wherein promoting comprises combining the precipitate with at least one source of kaolin, in the absence of silicic acid.
18. The Fischer-Tropsch catalyst of claim 14 wherein promoting comprises combining the precipitate with at least one non-crystalline silica and at least one source of kaolin, in the absence of silicic acid.
19. The Fischer-Tropsch catalyst of claim 1 wherein the basic solution comprises at least one selected from the group consisting of sodium carbonate and ammonium hydroxide.
20. The Fischer-Tropsch catalyst of claim 1 wherein the spray-dried catalyst is substantially spherical, and wherein the particle size is in the range of from about 40 to about 100 micrometers.
21. The Fischer-Tropsch catalyst of claim 1 , wherein the method further comprises:
filtering to remove liquids from the precipitate and form a filter residue, reslurrying the filter residue, and combining the reslurried residue with (a) or (b), wherein the reslurried residue has a pH of greater than or equal to about 10, enabling superior dissolution of the structural promoters of (a) or (b).
22. The Fischer-Tropsch catalyst of 1 wherein, upon calcination, the calcined catalyst has a surface area of at least 70 m 2 /g, a pore volume in the range of from about 0.2 and 0.3, an average pore size in the range of from 50 and 78 Å, or a combination thereof.
23. The Fischer-Tropsch catalyst of claim 1 comprising a substantially homogeneous distribution of structural promoter, provided via structural promotion of (a) or (b) at a pH of greater than or equal to about 10.
24. The Fischer-Tropsch catalyst of claim 1 further comprising platinum, obtained by incorporation thereof during structural promotion, wherein the weight ratio of Fe:Pt in the Fischer-Tropsch catalyst is in the range of from about 100:1 to about 100:2.
25. The Fischer-Tropsch catalyst of claim 1 that produces less than about 6 weight percent fines after 5 hours ASTM Air Jet Attrition testing.
26. A structurally promoted, precipitated, Fischer-Tropsch catalyst that produces less than 6 weight percent fines after 5 hours ASTM Air Jet Attrition testing, due to formation via:
preparing a nitrate solution, wherein preparing comprises forming at least one metal slurry and combining the at least one metal slurry with a nitric acid solution;
combining the nitrate solution with a basic solution to form a precipitate;
structurally promoting the precipitate with at least one source of silicon to form a promoted mixture, wherein promoting comprises combining the precipitate with (a) silicic acid and one or more component selected from the group consisting of non-crystalline silicas, crystalline silicas, and sources of kaolin or (b) at least one component selected from the group consisting of non-crystalline silicas and sources of kaolin, in the absence of silicic acid; and
spray drying the promoted mixture to produce a spray-dried catalyst having a particle size.
27. The Fischer-Tropsch catalyst of claim 26 , that produces less than 4, 3.4, 3, 2, or 1.3 weight percent fines after 5 hours ASTM Air Jet Attrition testing.
28. The Fischer-Tropsch catalyst of claim 26 wherein promoting comprises combining the precipitate with (a) silicic acid and one or more component selected from the group consisting of non-crystalline silicas, crystalline silicas, and sources of kaolin, and wherein the source of silicon comprises up to or equal to about 5 weight percent silicic acid.
29. The Fischer-Tropsch catalyst of claim 28 wherein enhanced physical attrition resistance thereof is provided by a multi-step structural promotion, wherein the silicic acid is added to the precipitate separately from any other source of silicon, relative to a Fischer-Tropsch catalyst in which the silicic acid is added in the same step as any other source of silicon.
30. The Fischer-Tropsch catalyst of claim 28 having a main reduction peak temperature in the range of from about 204° C. and 259° C.
31. The Fischer-Tropsch catalyst of claim 26 comprising iron, obtained by preparation of the nitrate solution with an iron slurry, and having a weight ratio of Fe:SiO 2 in the range of from about 100:6 to 100:24.
32. The Fischer-Tropsch catalyst of claim 31 having a BET surface area in the range of from about 144 m 2 /g to about 237 m 2 /g.
33. The Fischer-Tropsch catalyst of claim 32 having a pore volume in the range of from about 0.2 to about 0.3.
34. The Fischer-Tropsch catalyst of claim 33 having an average pore size in the range of from 50 and 78 Å.
35. The Fischer-Tropsch catalyst of claim 26 comprising a substantially homogeneous distribution of structural promoter, provided by structural promotion of (a) or (b) at a pH of greater than or equal to about 10.
36. The Fischer-Tropsch catalyst of claim 26 formed by precipitation with basic solution comprising sodium carbonate.
37. A structurally promoted, precipitated Fischer-Tropsch catalyst comprising a weight ratio of Fe:SiO 2 in the range of from about 100:5 to about 100:25, a weight ratio of Fe:K in the range of from about 100:2 to about 100:5, and a weight ratio of Fe:Cu in the range of from about 100:2 to about 100:5, wherein silicon is incorporated into the catalyst by structural promotion of an iron-based catalyst precipitate with up to 5 weight percent silicic acid, with any balance of the silicon in the catalyst being incorporated by structural promotion with another silicon source selected from the group consisting of non-crystalline silicas, crystalline silicas, and sources of kaolin.
38. The Fischer-Tropsch catalyst of claim 37 wherein the balance of the silicon in the catalyst is provided by one or more non-crystalline silicon source.
39. The Fischer-Tropsch catalyst of claim 37 comprising a substantially homogeneous distribution of silicon structural promoter, provided by structural promotion at a pH of greater than or equal to about 10.
40. The Fischer-Tropsch catalyst of claim 37 wherein enhanced physical attrition resistance thereof is provided by a multi-step structural promotion, wherein the silicic acid is added to the iron catalyst precipitate separately from any other source of silicon, relative to a Fischer-Tropsch catalyst in which the silicic acid is added in the same step as any other source of silicon.
41. The Fischer-Tropsch catalyst of claim 37 having a main reduction peak temperature in the range of from about 204° C. and 259° C.
42. The Fischer-Tropsch catalyst of claim 37 that produces less than about 6 weight percent fines after 5 hours ASTM Air Jet Attrition testing.