Sulfur tolerant noble metal containing aromatics hydrogenation catalyst and a method of making and using such catalyst
View Patent ↗An aromatics hydrogenation catalyst composition which comprises a noble metal component and a support comprising zirconia, silica, and, optionally, alumina. The catalyst composition is manufactured by co-mulling silica, a zirconium compound, and, optionally, alumina to form a mixture that is formed into a shape, such as by extrusion to form an extrudate, with the shape being calcined and noble metal being incorporated into the shape. The catalyst composition may be used in the saturation of aromatic compounds.
1. A method of preparing a sulfur tolerant aromatics hydrogenation catalyst composition, wherein said method comprises:
co-mulling from 1 to 30 wt. % of a zirconium compound and from 60 to 99 wt % of an inorganic oxide selected from the group consisting of silica, alumina and silica-alumina to form a mixture;
forming an agglomerate particle comprising said mixture; and
calcining said agglomerate particle to thereby provide a calcined particle suitable for use as a catalyst support;
incorporating into said catalyst support from 0.01 to 5 wt % of a platinum component and from 0.01 to 5 wt % of a palladium component in a weight ratio of elemental palladium-to-platinum of 1:10 to 10:1, to provide an intermediate catalyst composition; and
calcining said intermediate catalyst composition to thereby provide a final sulfur tolerant aromatics hydrogenation catalyst composition.
2. A method as recited in claim 1 , wherein said mixture contains an amount of said zirconium compound such that said calcined particle has a zirconium content in the range of from 0.5 to 20 wt. % zirconium based on the total weight of said calcined particle.
3. A method as recited in claim 2 , wherein said zirconium compound is selected from the group consisting of oxides, nitrates, sulfates, silicates, carbonates, acetates, chlorides, hydroxides, and hydrates of zirconium.
4. A method as recited in claim 3 , wherein said mixture contains an amount of said inorganic oxide material such that said calcined particle has an inorganic oxide content in the range of from 70 to 99 wt. % inorganic oxide.
5. A method as recited in claim 4 , wherein said platinum component and said palladium component are present in a weight ratio of elemental palladium-to-platinum in the range of from 1:2 to 5:1.
6. A method as recited in claim 5 ,
wherein said intermediate catalyst composition is calcined at a temperature from 250° C. to 550° C. to thereby provide said final sulfur tolerant aromatics hydrogenation catalyst composition.
7. A sulfur tolerant aromatics hydrogenation catalyst, comprising:
from 0.01 to 5 wt % of a platinum component and from 0.01 to 5 wt % of a palladium component in a weight ratio of elemental palladium-to-platinum in the range of 1:10 to 10:1, and a calcined mixture as a catalyst support, wherein said mixture of said calcined mixture, before calcination, comprises a zirconium compound that has been co-mulled with an inorganic oxide selected from the group consisting of silica, alumina and silica-alumina, and wherein the zirconium content of said calcined mixture is in the range from 1 to 30 wt % and the inorganic oxide content of said calcined mixture is in the range from 70 to 90 wt %.
8. A sulfur tolerant aromatics hydrogenation catalyst as recited in claim 7 , wherein said calcined mixture comprises silica and alumina in relative amounts such that the molar ratio of silica-to-alumina is in the range of from 1:10 to 10:1.
9. A sulfur tolerant aromatics hydrogenation catalyst as recited in claim 8 , wherein said zirconium compound is present in said calcined mixture in an amount in the range of from 0.5 to 20 wt. % with the weight percent being based on the total weight of the aromatics hydrogenation catalyst and calculated as elemental metal.
10. A sulfur tolerant aromatics hydrogenation catalyst as recited in claim 9 , wherein said platinum component and said palladium component are present in a weight ratio of elemental palladium-to-platinum in the range of 1:2 to 5:1.
11. A sulfur tolerant aromatics hydrogenation catalyst as recited in claim 10 , wherein said platinum component and said palladium component are present in a weight ratio of elemental palladium-to-platinum in the range of 1:1 to 3:1.
12. A sulfur tolerant aromatics hydrogenation catalyst as recited in claim 11 , wherein said aromatics hydrogenation catalyst has a surface area in the range of from 300 m 2 /gm to 600 m 2 /gm.
13. A sulfur tolerant aromatics hydrogenation catalyst as recited in claim 12 , wherein said aromatics hydrogenation catalyst has a pore volume in the range of from 0.7 ml/gm to 1.3 ml/m and a median pore diameter in the range of from 50 angstroms to 250 angstroms.
14. A sulfur tolerant aromatics hydrogenation catalyst as recite in claim 7 , wherein said calcined mixture has a silica-to-alumina molar ratio of greater than 10:1.
15. A sulfur tolerant aromatics hydrogenation catalyst as recited in claim 14 , wherein said zirconium compound is present in said calcined mixture in an amount in the range of from 3 to 30 wt. % with the weight percent being based on the total weight of the aromatics hydrogenation catalyst and calculated as elemental metal.
16. A sulfur tolerant aromatics hydrogenation catalyst as recited in claim 15 , wherein said platinum component and said palladium component are present in a weight ratio of elemental palladium-to-platinum in the range of 1:2 to 5:1.
17. A sulfur tolerant aromatics hydrogenation catalyst as recited in claim 16 , wherein said platinum component and said palladium component are present in a weight ratio of elemental palladium-to-platinum in the range of 1:1 to 3:1.
18. A sulfur tolerant aromatics hydrogenation catalyst as recited in claim 17 , wherein said aromatics hydrogenation catalyst has a surface area in the range of from 200 m 2 /gm to 500 m 2 /gm.
19. A sulfur tolerant aromatics hydrogenation catalyst as recited in claim 18 , wherein said aromatics hydrogenation catalyst has a pore volume in the range of from 0.7 ml/gm to 1.3 ml/gm and a median pore diameter in the range of from 50 angstroms to 250 angstroms.
20. A sulfur tolerant aromatics hydrogenation catalyst, comprising: from 1 to 30 wt % zirconia, from 0.01 to 5 wt % of a platinum component and from 0.01 to 5 wt % of a palladium component in a weight ratio of elemental palladium-to-platinum in the range of 1:10 to 10:1, and from 60 to 99% inorganic oxide selected from the group consisting of silica, alumina and silica-alumina, wherein said amount of zirconia is incorporated into said sulfur tolerant hydrogenation catalyst by co-mulling with said inorganic oxide.
21. A sulfur tolerant aromatics hydrogenation catalyst composition made by any one of the methods of claims 1 through 6 .
22. A sulfur tolerant aromatics hydrogenation catalyst composition suitable for treating hydrocarbon feedstocks having a sulfur concentration in the range from 10 to 1,000 ppm, comprising: from 1 to 30 wt % zirconia, from 0.01 to 5 wt % of a platinum component and from 0.01 to 5 wt % of a palladium component in a weight ratio of elemental palladium to platinum of 1:2 to 5:1, and from 70 to 99% inorganic oxide selected from the group consisting of silica, alumina and silica-alumina, wherein said amount of zirconia is incorporated into said sulfur tolerant hydrogenation catalyst by co-mulling with said inorganic oxide, and wherein the surface area of said sulfur tolerant aromatics hydrogenation catalyst is in the range of from 200 m 2 /gm to 500 m 2 /gm, the pore volume is in the range of from 0.7 ml/gm to 1.3 ml/gm and a median pore diameter is in the range of from 50 angstroms to 250 angstroms.
23. A sulfur tolerant aromatics hydrogenation catalyst composition as recited in claim 22 , wherein the weight ratio of the elemental palladium to platinum is 1:1 to 3:1.
24. A sulfur tolerant aromatics hydrogenation catalyst composition as recited in claim 23 , wherein said inorganic oxide is silica and the amount of co-mulled zirconia is from 5 to 25 wt %.
25. The method of claim 5 , wherein said palladium and platinum are incorporated into said catalyst support in a weight ratio of elemental palladium to platinum of 1:1 to 3:1 using an impregnating solution containing tetraamine platinum (II) nitrate and tetraamine palladium (II) nitrate.