Supported rhodium-spinel catalysts and process for producing synthesis gas
View Patent ↗Rhodium-spinel catalysts with activity for efficiently catalyzing the net partial oxidation of methane at high selectivities for CO and H 2 products are disclosed, along with their method of making. A syngas production process employing such catalysts for the net catalytic partial oxidation of a C 1 -C 5 hydrocarbon (e.g., natural gas or methane) to a product gas mixture comprising CO and H 2 is also disclosed. Preferred reaction conditions include maintaining the catalyst at a temperature of about 400-1,200° C., superatmospheric pressure, and flow rate sufficient to pass the reactant gas mixture over the catalyst at space velocities of at least about 100,000-25,000,000 hr −1 .
1. A method of producing synthesis gas comprising:
contacting a reactant gas mixture comprising C 1 -C 5 hydrocarbon-containing gas and O 2 -containing gas with a catalytically effective amount of a catalyst comprising a catalytic composition
comprising Rh deposited on a spinel having the general formula MAl 2 O 4 , wherein M is at least one metal having a +2 oxidation state, said catalytic composition being carried on a refractory support; and
maintaining net partial oxidation reaction promoting conditions and superatmospheric pressure such that a product gas mixture comprising H 2 and CO is produced.
2. The method of claim 1 wherein said M in the spinel general formula MAl 2 O 4 , is chosen from the group consisting of Co, Al, Li, Ti, Ni, Mn, Cd, Zn, Cu, Mg, Ca, Fe, Mo and La, and mixtures thereof.
3. The method of claim 2 wherein said M is chosen from the group consisting of Mg, Co and Ni, and mixtures thereof.
4. The method of claim 1 comprising combining a hydrocarbon-containing feedstock and an oxygen-containing feedstock to provide a reactant gas mixture having a carbon:oxygen ratio of about 1.5:1 to about 3.3:1.
5. The method of claim 4 wherein the carbon:oxygen ratio is about 1.7:1 to about 2.1:1.
6. The method of claim 5 wherein the carbon:oxygen ratio is about 2:1.
7. The method of claim 1 wherein the C 1 -C 5 hydrocarbon comprises at least about 80% methane by volume.
8. The method of claim 1 further comprising preheating the hydrocarbon before contacting the catalyst.
9. The method of claim 8 wherein the preheating comprises heating the hydrocarbon to a temperature in the range of about 30° C. to about 750° C.
10. The method of claim 1 comprising passing a stream of the reactant gas mixture over the catalyst at a gas hourly space velocity in the range of 20,000 to 100,000,000 hr −1 .
11. The method of claim 10 wherein the gas hourly space velocity is in the range of 100,000 to 25,000,000 hr −1 .
12. The method of claim 1 comprising maintaining a catalyst temperature in the range of about 350° C.-1,500° C. during the contacting.
13. The method of claim 12 wherein the temperature is in the range of 400-1,200° C.
14. The method of claim 1 comprising maintaining a reactant gas mixture pressure of 200 to 32,000 kPa during the contacting.
15. The method of claim 14 wherein the pressure is in the range of about 200-10,000 kPa.
16. The method of claim 1 wherein the reactant gas mixture comprises steam and/or CO 2 .
17. The method of claim 1 wherein said product gas mixture comprises a H 2 to CO molar ratio of about 2:1.
18. The method of claim 1 wherein the contacting comprises a residence time of each portion of reactant gas mixture in contact with the catalyst of no more than about 200 milliseconds.
19. The method of claim 18 wherein the contacting comprises a residence time of each portion of reactant gas mixture in contact with the catalyst less than 50 milliseconds.
20. The method of claim 19 wherein the contacting comprises a residence time of each portion of reactant gas mixture in contact with the catalyst less than 20 milliseconds.
21. The method of claim 20 wherein the contacting comprises a residence time of each portion of reactant gas mixture in contact with the catalyst less than 10 milliseconds.
22. The method of claim 1 wherein the catalyst comprises 0.1-10 wt. % rhodium (based on total catalyst weight).
23. The method of claim 22 wherein the catalyst comprises about 4-5 wt % Rh.
24. The method of claim 1 wherein the support comprises a material selected from the group consisting of zirconia, magnesium stabilized zirconia (PSZ), alpha-alumina, cordierite, zirconia-tetra-alumina, oxide-bonded silicon carbide, mullite, lithium aluminum silicate, sialon, a titanate, fused silica, magnesia, yttrium aluminum garnet and boron nitride.
25. The method of claim 24 wherein the support comprises zirconia, alpha-alumina or PSZ.
26. The method of claim 1 wherein the support comprises a foam monolith having about 30-150 pores per inch (12-60 pores per cm).
27. The method of claim 1 wherein the catalyst comprises Rh deposited on a CoAl 2 O 4 spinel-coated refractory support.
28. The method of claim 1 wherein the catalyst comprises Rh deposited on a NiAl 2 O 4 spinel-coated refractory support.
29. The method of claim 1 wherein the catalyst comprises Rh deposited on a MgAl 2 O 4 spinel-coated refractory support.
30. The method of claim 1 wherein the catalyst comprises a plurality of divided units.
31. The method of claim 30 wherein said divided units comprise particles, granules, beads, pills, pellets, cylinders, trilobes, extrudates or spheres.
32. The method of claim 30 wherein each said divided unit is less than 10 millimeters in its longest dimension.
33. The method of claim 32 wherein each said divided unit is ≦6 millimeters in its longest dimension.
34. A catalyst active for catalyzing the net partial oxidation of methane to synthesis gas comprising H 2 and CO, said catalyst comprising about 0.1-10 wt % Rb in the form of at least one spinel compound having the general formula MRh 2 O 4 or MM′RhO 4 wherein M and M′ are at least one metal chosen from the group consisting of Co, Mg, Al, B, V, La, Li, Ti, Ca, Cu, Zn, Cd, Mn, Ga, Ni, Fe, Ag, Mo, Na, Pt, and Cr, said spinel being disposed on a support, and said catalyst being mechanically stable at gas pressures greater than 2 atmospheres.
35. The catalyst of claim 34 wherein the support comprises a refractory material.
36. The catalyst of claint 35 wherein said support comprises a monolith.
37. The catalyst of claim 35 wherein said support comprises a plurality of divided units.
38. The catalyst of claim 37 wherein said divided units comprise particles, granules, beads, pills, pellets, cylinders, trilobes, extrudates or spheres.
39. The catalyst of claim 37 wherein each said divided unit is less than 10 millimeters in its longest dimension.
40. The catalyst of claim 39 wherein each said divided unit is ≦6 millimeters in its longest dimension.
41. The catalyst of claim 34 wherein said support comprises a material selected from the group consisting of zirconia, magnesium stabilized zirconia (PSZ), alpha-alumina, cordierite, zirconia-tetra-alumina, oxide-bonded silicon carbide, mullite, lithium aluminum silicate, sialon, a titanate, fused silica, magnesia, yttrium aluminum garnet and boron nitride.
42. The catalyst of claim 34 wherein said spinel is chosen from the group consisting of CoRh 2 O 4 , MgRh 2 O 4 , CoRhAlO 4 , RhLiTiO 4 , CaRh 2 O 4 , CuRh 2 O 4 , ZnRh 2 O 4 , and CdRh 2 O 4 .
43. A method of producing synthesis gas comprising:
contacting a reactant gas mixture comprising C 1 -C 5 hydrocarbon-containing gas and O 2 -containing gas with a catalytically effective amount of a catalyst comprising a spinel having the general formula MRh 2 O 4 or MM′RhO 4 wherein M and M′ are at least one metal chosen from the group consisting of Co, Mg, Al, Li, Ti, Ca, Cu, Zn, Cd, Mn, Ga and Cr; and
maintaining net partial oxidation reaction promoting conditions and superatmospheric pressure such that a product gas mixture comprising H 2 and CO is produced.
44. The method of claim 43 wherein the catalyst comprises CoRh 2 O 4 spinel on a refractory support.
45. The method of claim 43 wherein the catalyst comprises MgRh 2 O 4 spinel an a refractory support.
46. The method of claim 43 wherein the catalyst comprises CoRhAlO 4 spinel on a refractory support.
47. The method of claim 43 wherein the catalyst comprises CoRh 2 O 4 spinel on a refractory support.
48. The method of claim 43 wherein the catalyst comprises RhLiTiO 4 spinel on a refractory support.
49. The method of claim 43 wherein the catalyst comprises CaRh 2 O 4 spinel on a refractory support.
50. The method of claim 43 wherein the catalyst comprises CuRh 2 O 4 spinel on a refractory support.
51. The method of claim 43 wherein the catalyst comprises ZnRh 2 O 4 spinel on a refractory support.
52. The method of claim 43 wherein the catalyst comprises CdRh 2 O 4 spinel on a refractory support.
53. The method of claim 43 wherein the catalyst further comprises a refractory support structure selected from the group consisting of zirconia, magnesium stabilized zirconia (PSZ), alpha-alumina, cordierite, zirconia-tetra-alumina, oxide-bonded silicon carbide, mullite, lithium aluminum silicate, sialon, a titanate, fused silica, magnesia, yttrium aluminum garnet and boron nitride.
54. The method of claim 43 wherein the catalyst comprises a spinel disposed on a refractory support, said spinel being chosen from the group consisting of CoRh 2 O 4 , MgRh 2 O 4 , CoRhAlO 4 , RhLiTiO 4 , CaRh 2 O 4 , CuRh 2 O 4 , ZnRh 2 O 4 , and CdRh 2 O 4 .
55. The method of claim 43 wherein maintaining net partial oxidation reaction promoting conditions comprises a gas hourly space velocity in the range of 100,000 hr −1 to 25,000,000 hr −1 .
56. The method of claim 43 wherein the superatmospheric pressure comprises a pressure in the range of about 200-32,000 kPa.