Combination of amorphous materials for hydrocracking catalysts
An amorphous support, methods for making the same and methods of using, particularly in hydrocracking. A method of making may comprise mixing a first amorphous material and a second amorphous material of different acidities to form a mixture, and treating by either separately treating the first and second amorphous materials before mixing or treating the mixture, so as to form an amorphous catalyst support. Treating preferably includes calcining. The acidity of the amorphous support may be modified by the different acidities of the precursor amorphous materials, their proportions in the mixture, and/or the order of the mixing and treating steps. A method of use may comprise reacting a hydrocarbon fraction with hydrogen over a hydrocracking catalyst comprising the amorphous catalyst support to form a hydrocracked product. Further embodiments include the first and second amorphous materials comprising silica-alumina, and/or differing in Brönsted acidity, Lewis acidity, or acidity index.
1. A hydrocracking catalyst, comprising:
a catalytic metal comprising a Group 6 metal, a Group 8 metal, a Group 9 metal, a Group 10 metal, or combinations thereof; and
an amorphous catalyst support comprising a mixture of a first amorphous material and a second amorphous material, wherein the first amorphous material comprises a Brönsted acidity measured at 150° C. between about 0.1 μmol pyridine/g and about 4 μmol pyridine/g; and the second amorphous material comprising a Brönsted acidity that differs by at least 1 μmol pyridine/g from that of the first amorphous material.
2. The catalyst of claim 1 , wherein the first amorphous material comprises silica-alumina, silica-titania, silica-magnesia, or alumina-titania; and wherein the second amorphous material comprises silica-alumina, silica-titania, silica-magnesia, or alumina-titania.
3. The catalyst claim 1 , wherein the first amorphous material and the second amorphous material comprise silica-alumina.
4. The catalyst of claim 1 , wherein the amorphous catalyst support has a Brönsted acidity between about 2.5 μmol pyridine/g and about 7 μmol pyridine/g.
5. The catalyst of claim 1 , wherein the Brönsted acidity of the first amorphous material is between about 1 μmol pyridine/g and about 3 μmol pyridine/g.
6. The catalyst of claim 1 , wherein the Brönsted acidity of the second amorphous material is between about 4 μmol pyridine/g and about 7 μmol pyridine/g.
7. The catalyst of claim 1 , wherein the mixture comprises a weight ratio of the first amorphous material to the second amorphous material between about 5:95 and about 95:5.
8. The catalyst of claim 1 , wherein the mixture comprises a weight ratio of the first amorphous material to the second amorphous material between about 1:3 and about 3:1.
9. The catalyst of claim 1 , wherein the catalytic metal comprises a noble metal selected from the group consisting of palladium, platinum, and combinations thereof.
10. The catalyst of claim 1 , wherein the catalytic metal comprises a non-noble metal selected from the group consisting of Ni, Co, W, Mo, and any combinations of two or more thereof.
11. A method for making a hydrocracking catalyst comprising an amorphous catalyst support and a catalytic metal selected from the group consisting of a Group 6 metal, a Group 8 metal, a Group 9 metal, a Group 10 metal, and combinations thereof, said method comprising the following steps:
(A) providing a first amorphous material and a second amorphous material, wherein the first amorphous material comprises a Brönsted acidity between 0 μmol pyridine/g and about 4 μmol pyridine/g, and wherein the second amorphous material comprises a Brönsted acidity that differs by at least 1 μmol pyridine/g from that of the first amorphous material;
(B) mixing the first amorphous material and the second amorphous material to form a mixture;
(C) either treating the mixture or separately treating the first and second amorphous materials before the mixing step so as to form the amorphous catalyst support; and
performing one of the following deposition steps selected from the group consisting of:
depositing the catalytic metal on the amorphous catalyst support;
separately depositing the catalytic metal to the first amorphous material and the second amorphous material in step (A); and
depositing the catalytic metal to the first amorphous material and the second amorphous material during step (B).
12. The method of claim 11 , wherein the amorphous catalyst support has a Brönsted acidity between about 2.5 μmol pyridine/g and about 7 μmol pyridine/g.
13. The method of claim 11 wherein the first amorphous material comprises silica-alumina, silica-titania, silica-magnesia, or alumina-titania; and wherein the second amorphous material comprises silica-alumina, silica-titania, silica-magnesia, or alumina-titania.
14. The method of claim 11 wherein the first amorphous material and the second amorphous material comprise silica-alumina.
15. The method of claim 11 wherein the Brönsted acidity of the first amorphous material is between about 1 μmol pyridine/g and about 3 μmol pyridine/g.
16. The method of claim 11 wherein the Brönsted acidity of the second amorphous material is between about 4 μmol pyridine/g and about 7 μmol pyridine/g.
17. The method of claim 11 wherein step (A) further comprises preparing a first gel comprising the first amorphous material and a second gel comprising the second amorphous material.
18. The method of claim 17 , wherein mixing the first amorphous material and the second amorphous material of step (B) comprises mixing the first gel and the second gel to form a gel mixture, and wherein the mixture comprises the gel mixture, and further wherein the treating step (C) comprises calcining the gel mixture.
19. The method of claim 11 wherein the mixture comprises a weight ratio of the first amorphous material to the second amorphous material between about 5:95 and about 95:5.
20. The method of claim 11 wherein the mixture comprises a weight ratio of the first amorphous material to the second amorphous material between about 1:10 and about 10:1.
21. The method of claim 11 wherein the mixture comprises a weight ratio of the first amorphous material to the second amorphous material between about 1:3 and about 3:1.
22. A method for hydrocracking a hydrocarbon fraction, comprising:
(A) providing a hydrocracking catalyst, wherein the hydrocracking catalyst comprises
(1) a catalytic metal comprising a Group 6 metal, a Group 8 metal, a Group 9 metal, a Group 10 metal, or combinations thereof and
(2) an amorphous support, wherein the amorphous support comprises a mixture of a first amorphous material comprising a Brönsted acidity between 0 μmol pyridine/g and about 4 μmol pyridine/g and a second amorphous material comprising a Brönsted acidity that differs by at least 1 μmol pyridine/g from that of the first amorphous material; and
(B) reacting the hydrocarbon fraction with hydrogen over the hydrocracking catalyst to form a hydrocracked product.
23. The method of claim 22 , wherein the catalytic metal comprises a Group 6 metal.
24. The method of claim 22 , wherein the catalytic metal comprises a noble metal.
25. The method of claim 22 , wherein the catalytic metal comprises platinum, palladium, or combinations thereof.
26. The method of claim 22 , wherein the first amorphous material comprises silica-alumina, silica-titania, silica-magnesia, or alumina-titania; and wherein the second amorphous material comprises silica-alumina, silica-titania, silica-magnesia, or alumina-titania.
27. The method of claim 22 , wherein the first amorphous material and the second amorphous material comprise silica-alumina.
28. The method of claim 22 , wherein the amorphous support comprises a Brönsted acidity between about 2.5 μmol pyridine/g and about 7 μmol pyridine/g.
29. The method of claim 22 , wherein the Brönsted acidity of the first amorphous material is between about 1 μmol pyridine/g and about 3 μmol pyridine/g.
30. The method of claim 22 , wherein the Brönsted acidity of the second amorphous material is between about 4 μmol pyridine/g and about 7 μmol pyridine/g.
31. The method of claim 22 , wherein the mixture comprises a weight ratio of the first amorphous material to the second amorphous material between about 5:95 and about 95:5.
32. The method of claim 22 , wherein the mixture comprises a weight ratio of the first amorphous material to the second amorphous material between about 1:3 and about 3:1.
33. The method of claim 22 , wherein the hydrocarbon fraction comprises a hydrocarbon product of a hydrocarbon synthesis process.
34. A hydrocracking catalyst, comprising:
a catalytic metal comprising a Group 6 metal, a Group 8 metal, a Group 9 metal, a Group 10 metal, or any combination thereof and
a catalyst support comprising:
a mixture of a first amorphous silica-alumina material and a second amorphous silica-alumina material, wherein the first amorphous silica-alumina material and the second amorphous silica-alumina differ in at least one property selected from the group consisting of acid strength, Brönsted acidity, Lewis acidity, acidity index, and silica-to-alumina molar ratio.
35. The catalyst of claim 34 , wherein each of the first and second silica-alumina materials comprises a Brönsted acidity, and wherein the Brönsted acidity of the second amorphous silica-alumina material differs by least 1 μmol pyridine/g from that of the first amorphous silica-alumina material.
36. The catalyst of claim 34 , wherein the first and second amorphous silica-alumina materials are derived from two synthesized silica-alumina gels.
37. The catalyst of claim 36 , wherein the two synthesized silica-alumina gels have the same silica-to-alumina molar ratio.
38. The catalyst of claim 36 , wherein the two synthesized silica-alumina gels are synthesized by using different silicon precursor compounds and different aluminum precursor compounds to effect a difference in acidity.
39. The catalyst of claim 36 , wherein the catalyst support is made by one of the following methods:
separately calcining said synthesized silica-alumina gels to form two calcined amorphous silica-aluminas and then mixing said calcined amorphous silica-aluminas; or
mixing said synthesized silica-alumina gels to form a gel mixture, and then calcining the gel mixture.
40. The catalyst of claim 39 , wherein the calcining step in either method is carried out at a temperature between about 400° C. and about 600° C.
41. The catalyst of claim 34 , wherein the catalyst support is essentially free of zeolitic material.
42. The catalyst of claim 34 , wherein the catalyst support has a Brönsted acidity between about 2.5 μmol pyridine/g and about 7 μmol pyridine/g.
43. The catalyst of claim 34 , wherein the catalyst support has a BET surface area between about 300 m 2 /g and about 800 m 2 /g.
44. The catalyst of claim 34 , wherein the catalyst support has a total pore volume between about 0.5 ml/g and about 1.2 ml/g.
45. The catalyst of claim 34 , wherein the catalyst support has an average pore size between about 2 nm and about 12 nm.
46. The catalyst of claim 34 , wherein the catalyst support has a Brönsted acidity between about 4 μmol pyridine/g and about 13 μmol pyridine/g.
47. The catalyst of claim 34 , wherein the catalytic metal comprises a noble metal selected from the group consisting of palladium, platinum, and combinations thereof.
48. The catalyst of claim 47 , wherein the hydrocracking catalyst comprises said noble metal in an amount from about 0.05 percent by weight to about 2 percent by weight per total weight of the hydrocracking catalyst.
49. The catalyst of claim 34 , wherein the catalytic metal comprises a non-noble metal selected from the group consisting of Ni, Co, W, Mo, and any combinations of two or more thereof.