Catalysts for the conversion of methane to synthesis gas
View Patent ↗The present invention relates to improved catalyst compositions, as well as methods of making and using such compositions to prepare synthesis gas and ultimately C 5+ hydrocarbons. In particular, preferred embodiments of the present invention comprise catalyst systems comprising a core and an outer region disposed on said core, wherein a substantial amount of the catalytic metal is located in the outer region of the catalyst support matrix. In addition, the catalyst systems are able to maintain high conversion and selectivity values with very low catalytically active metal loadings. The catalyst systems are appropriate for improved syngas, oxidative dehydrogenation and other partial oxidation reactions, including improved reaction schemes for the conversion of hydrocarbon gas to C 5+ hydrocarbons.
1. A process for producing synthesis gas comprising:
passing a hydrocarbon containing gas and an oxygen containing gas over a partial oxidation catalyst, under conditions effective to produce a gas stream comprising hydrogen and carbon monoxide,
wherein the partial oxidation catalyst comprises a catalytic metal and a support material;
wherein the partial oxidation catalyst includes a plurality of discrete structures, each comprising a core containing said support material and an outer region disposed on said core;
wherein the plurality of discrete structures has an average size greater than 0.5 mm;
wherein the outer region has an thickness of not more than 200 microns, and further
wherein more than 60% of the catalytically active metal loaded on the discrete structure is located in the outer region
further wherein the catalyst comprises a substantially blocked-micropore layer disposed between the outer region and the center of the core, said substantially blocked-micropore layer being either at the periphery of the core or extended substantially throughout the core.
2. The process according to claim 1 wherein the catalytic metal comprises a Group VIII metal or noble metal.
3. The process according to claim 1 wherein the catalytic metal comprises rhodium.
4. The process according to claim 3 wherein the catalytic metal comprises about 1 wt % or less of the total catalyst weight.
5. The process according to claim 3 wherein the catalytic metal comprises about 0.75 wt % or less of the total catalyst weight.
6. The process according to claim 1 wherein 80% of the catalytic metal is located within the outer region.
7. The process according to claim 1 wherein the outer region thickness is no greater than 100 microns.
8. The process according to claim 1 wherein the support material comprises alumina.
9. The process according to claim 1 wherein the partial oxidation catalyst exhibits a methane conversion of greater than or equal to 80 mole %.
10. The process according to claim 1 wherein the partial oxidation catalyst exhibits a hydrogen selectivity of greater than or equal to 80 mole %.
11. The process according to claim 1 wherein the partial oxidation catalyst exhibits a carbon monoxide selectivity of greater than or equal to 80 mole %.
12. The process according to claim 1 wherein the hydrocarbon containing gas and an oxygen containing gas over the catalyst is done at a GHSV greater then 100,000 hr −1 .
13. The process according to claim 1 wherein the hydrocarbon containing gas comprises methane.
14. The process according to claim 1 wherein 80% of the catalytic metal is located within the outer region.
15. The process according to claim 1 wherein the catalytically active metal is iridium, rhenium, or rhodium.
16. The process according to claim 15 wherein the catalytically active metal comprises about 1 wt % or less of the total catalyst weight.
17. The process according to claim 15 wherein the catalytically active metal comprises about 0.75 wt % or less of the total catalyst weight.
18. The process according to claim 15 wherein the catalytically active metal comprises about 0.5 wt % or less of the total catalyst weight.
19. The process according to claim 3 wherein the catalyst further comprises a promoter selected from the group consisting of lanthanide metals, rhenium, zirconium, and combinations thereof.
20. The process according to claim 3 wherein the catalyst further comprises a promoter selected from the group consisting of rhenium, zirconium, and combinations thereof.
21. The process according to claim 3 wherein the catalytic metal comprises about 0.5 wt % or less of the total catalyst weight.
22. The process according to claim 1 wherein the outer region is delimited by the exterior surface of the catalyst structure; the core comprises the center of the structure; and wherein the catalyst comprises a gradient in catalytically active metal concentration with the highest concentration near said exterior surface and essentially zero near said center.
23. The process according to claim 1 wherein the outer region comprises rhodium and a promoter selected from the group consisting of samarium, rhenium, zirconium, and combinations thereof.
24. The process according to claim 1 wherein the catalyst further comprises a promoter, and more than 60% of the promoter loaded on the discrete structure is located in the outer region.
25. The process according to claim 1 wherein more than 80% of the catalytic metal is located within the outer region.
26. The process according to claim 1 wherein the outer region is a catalytic outer layer greater than 0.5 micron thick.
27. The process according to claim 1 wherein said substantially blocked-micropore layer is disposed at the periphery of the core.
28. The process according to claim 1 wherein the substantially blocked-micropore layer is created before the loading of the catalytically active metal by a method comprising applying silicic acid or sodium carbonate to the support material and then calcining.
29. The process according to claim 1 wherein the discrete structures are particles with a trilobe configuration.
30. The process according to claim 1 wherein the discrete structures are particles with a spherical configuration.
31. The process according to claim 1 wherein the discrete structures are particles having a size greater than about 1 mm.
32. The process according to claim 1 wherein the support material comprises a refractory material selected from the group consisting of alumina, titania, zirconia, gallium oxide (Ga 2 O 3 ), silica and mixtures thereof.
33. The process according to claim 1 wherein the oxygen containing gas comprises air, oxygen-enriched air, oxygen blended with a diluent gas, or substantially pure oxygen.
34. The process according to claim 1 wherein the hydrocarbon containing gas comprises natural gas.
35. The process according to claim 1 wherein the partial oxidation catalyst exhibits a hydrogen selectivity of greater than or equal to 85 mole %.
36. The process according to claim 1 wherein the partial oxidation catalyst exhibits a carbon monoxide selectivity of greater than or equal to 85 mole %.
37. The process according to claim 1 wherein the partial oxidation catalyst exhibits a methane conversion of greater than or equal to 85 mole %.
38. The process according to claim 1 wherein the gas stream comprising hydrogen and carbon monoxide is further reacted in a hydrocarbon synthesis reactor under conditions effective to produce liquid hydrocarbons.
39. A process for producing synthesis gas comprising:
passing a hydrocarbon containing gas and an oxygen containing gas over a partial oxidation catalyst, under conditions effective to produce a gas stream comprising hydrogen and carbon monoxide,
wherein the partial oxidation catalyst comprises a catalytic metal and a support material;
wherein the partial oxidation catalyst includes a plurality of discrete structures, each comprising a core containing said support material and an outer region disposed on said core;
wherein the plurality of discrete structures has an average size greater than 0.5 mm;
wherein the outer region has an thickness of not more than 200 microns,
wherein more than 60% of the catalytically active metal loaded on the discrete structure is located in the outer region, and further
wherein the core is nonmicroporous.
40. The process according to claim 39 wherein the nonmicroporous core is created before the loading of the catalytically active metal by applying a pore blocking material to the support material and then calcining, said pore blocking material being selected from the group consisting of silicic acid and sodium carbonate.