초록

The present invention provides catalysts, reactors, and methods of steam reforming alcohols over a catalyst. Surprisingly superior results and properties obtained in methods and catalysts of the present invention are also described.

대표청구항 ▼

1. A method of methanol steam reforming comprising:contacting methanol and water vapor with a catalyst; wherein the catalyst comprises a palladium on zinc oxide catalyst wherein said catalyst has a pore volume and at least 20% of the catalyst's pore volume is composed of pores in the size range of 0

1. A method of methanol steam reforming comprising:contacting methanol and water vapor with a catalyst; wherein the catalyst comprises a palladium on zinc oxide catalyst wherein said catalyst has a pore volume and at least 20% of the catalyst's pore volume is composed of pores in the size range of 0.1 to 300 microns; and forming hydrogen from the reaction of said methanol and water vapor at a rate of at least 1.5 mole methanol per gram catalyst per hour (1.5 mole methanol/(g catalyst)(hr)). 2. The method of claim 1 wherein the catalyst comprises 2 to 10 weight percent Pd.3. The method of claim 1 wherein the ZnO forms a layer having a thickness of less than 40 μm on a large pore support.4. The method of claim 1 wherein the catalyst comprises a large pore support wherein the support comprises a metal foam or metal felt.5. The method of claim 1 wherein the catalyst has a pore volume of 30 to 95%.6. The method of claim 5 wherein at least 50% of the catalyst's pore volume is composed of pores in the size range of 0.1 to 300 microns.7. The method of claim 1 wherein at least 50% of the catalyst's pore volume is composed of pores in the size range of 0.3 to 200 microns.8. The method of claim 1 wherein at least 20% of the catalyst's pore volume is composed of pores in the size range of 1 to 100 microns.9. The method of claim 1 wherein the catalyst comprises a large pore support that has a corrugated shape.10. The method of claim 1 wherein the contact time is less than 1 sec.11. The method of claim 10 wherein the step of contacting methanol and water vapor with a catalyst is conducted at a temperature of 200 to 500° C.12. The method of claim 11 wherein methanol conversion is at least 50%.13. The method of claim 1 wherein the contact time is in the range of 10 to 500 msec.14. The method of claim 13 wherein the step of contacting methanol and water vapor with a catalyst is conducted at a temperature of 200 to 500° C.15. The method of claim 14 wherein the step of contacting methanol and water vapor with a catalyst is conducted at a temperature of greater than 350° C.16. The method of claim 1 wherein the catalyst is disposed in a reaction chamber in a flow-by configuration.17. The method of claim 16 wherein the catalyst is disposed in a reaction chamber that has a width less than 2 mm; and further wherein the reaction chamber is in thermal contact with a heat exchange chamber.18. The method of claim 17 wherein the catalyst comprises a porous support having a thickness of between 0.1 and 1 mm.19. The method of claim 17 wherein the step of contacting methanol and water vapor with a catalyst is conducted at a temperature of greater than 350° C.20. The method of claim 16 wherein the step of contacting methanol and water vapor with a catalyst is conducted at a temperature of greater than 350° C; andwherein the pressure drop through the reaction chamber is 20 psig or less. 21. The method of claim 16 wherein the catalyst comprises two pieces separated by a gap.22. The method of claim 21 wherein the reaction chamber that has a width less than 2 mm.23. The method of claim 1 wherein the catalyst is disposed in a reaction chamber that has a width less than 2 mm; and further wherein the reaction chamber is in thermal contact with a heat exchange chamber.24. The method of claim 23 wherein the reaction chamber and heat exchange chamber are adjacent and in an interleaved chamber orientation.25. The method of claim 24 wherein the heat exchange chamber has a width of less than 2 mm.26. The method of claim 1 wherein the step of contacting methanol and water vapor with a catalyst is conducted at a temperature of greater than 350° C.27. The method of claim 26 wherein the catalyst is disposed in a reaction chamber in a flow though configuration.28. A method of alcohol steam reforming comprising:contacting methanol and water vapor with a catalyst with a contact time of less than 1s in a reaction chamber having a width less than 2 mm; wherein the catalyst comprises palladium or ruthenium on cerium-promoted zirconia or alumina; and forming hydrogen from the reaction of said methanol and water vapor; wherein the methanol conversion is at least 80% and the H2 selectivity is at least 50%. 29. The method of claim 28 wherein the CO selectivity is below about 80%.30. The method of claim 29 wherein the method is conducted at a temperature of 200 to 500° C.31. The method of claim 28 wherein the CO selectivity is below about 20%.32. The method of claim 31 wherein the method is conducted at a temperature of 240 to 400° C.33. The method of claim 31 wherein the methanol conversion is at least 90% and the H2 selectivity is at least 85%.34. The method of claim 28 wherein the methanol conversion is at least 90% and the H2 selectivity is at least 85%.35. The method of claim 34 wherein the catalyst contains 2 to 10 weight % Pd.36. The method of claim 35 wherein the catalyst has a pore volume of 5 to 98% and at least 50% of the catalyst's pore volume is composed of pores in the size range of 0.1 to 300 microns.37. The method of claim 28 wherein the cerium-promoted zirconia or alumina is a layer of less than 1 mm on a large pore support that has a volumetric average pore size of 0.1 μm or greater.38. The method of claim 37 wherein the large pore support has a porosity of 30 to 99% and a volumetric average pore size of between 1 and 500 μm.39. The method of claim 38 wherein the large pore support has a thickness of between 0.1 and 1 mm and the layer of cerium-promoted zirconia or alumina has a thickness of less than 40 μm.40. The method of claim 28 wherein the catalyst has a pore volume and at least 20% of the catalysts pore volume is composed of pores in the size range of 0.1 to 300 microns.41. A method of alcohol steam reforming comprising:contacting methanol and water vapor with a catalyst with a contact time of less than 1s; wherein the catalyst comprises a palladium-ruthenium alloy on zirconia or alumina; wherein the catalyst comprises a higher weight percent of palladium than of ruthenium; and forming hydrogen from the reaction of said methanol and water vapor; wherein the methanol conversion is at least 80% and the H2 selectivity is at least 60%. 42. The method of claim 41 wherein the CO selectivity is below about 80%.43. The method of claim 42 wherein the catalyst is disposed in a reaction chamber having a width less than 2 mm and wherein the method is conducted at a temperature of 200 to 500° C.44. The method of claim 41 wherein the CO selectivity is below about 20%.45. The method of claim 44 wherein the catalyst is disposed in a reaction chamber having a width less than 2 mm and wherein the method is conducted at a temperature of 240 to 400° C.46. The method of claim 45 wherein the methanol conversion is at least 90% and the H2 selectivity is at least 85%.47. The method of claim 46 wherein the catalyst has a pore volume of 5 to 98% and at least 50% of the catalyst's pore volume is composed of pores in the size range of 0.1 to 300 microns.48. The method of claim 45 wherein the catalyst contains 2 to 10 weight % Pd and 0.2 to 5 weight % Ru.49. The method of claim 48 where in the large pore support has a porosity of 30 to 99% and a volumetric average pore size of between 1 and 500 μm.50. The method of claim 48 wherein the large pore support has a thickness of between 0.1 and 1 mm and the layer of cerium-promoted zirconia or alumina has a thickness of less than 40 μm.51. The method of claim 41 wherein the methanol conversion is at least 90% and the H2 selectivity is at least 85%.52. The method of claim 41 wherein the cerium-promoted zirconia or alumina is a layer of less than 1 mm on a large pore support that has a volumetric average pore size of 0.1 μm or greater.53. The method of claim 41 wherein the catalyst has a pore volume and at least 20% of the catalyst's pore volume is composed of pores in the size range of 0.1 to 300 microns.