Steam reforming methods and catalysts
The present invention provides catalysts, reactors, and methods of steam reforming over a catalyst. Surprisingly superior results and properties obtained in methods and catalysts of the present invention are also described. For example, a coated catalyst was demonstrated to be highly stable under steam reforming conditions (high temperature and high pressure of steam). Methods of making steam reforming catalysts are also described.
1. A method of methane steam reforming, comprising:
conducting a reaction in which methane and steam contact a catalyst at a temperature of at least 800° C. for at least 2000 hours without regenerating the catalyst;
wherein the catalyst comprises a stabilized alumina support and a catalytically active material; and wherein the method is further characterized by a contact time of 5 ms or less while the conversion of methane is at least 85% of the equilibrium conversion, and where the conversion has diminished by less than 3% over the 2000 hours without regenerating the catalyst;
and further wherein N is greater than 1.0;
wherein N is the gram moles of methane fed per minute per gram of catalytically active material.
2. The method of claim 1 wherein the temperature during the at least 2000 hours, the temperature is at least 850° C. and the partial pressure of H 2 O is at least 5 atm.
3. The method of claim 2 wherein the steam to carbon ratio is 3 or less.
4. The method of claim 2 wherein averaged over the at least 2000 hours
the method has a ΔT approach in the range
1° C.× N<ΔT approach <25° C.× N
wherein ΔT approach is the difference between the peak catalyst bed temperature and the apparent equilibrium conversion temperature; wherein the peak catalyst bed temperature is the highest temperature in the catalyst.
5. The method of claim 4 wherein a stream containing the methane and steam is passed into a reaction microchannel containing the catalyst.
6. The method of claim 1 wherein the catalyst temperature is 1000° C. or less.
7. The method of claim 4 wherein, averaged over the at least 2000 hours the method has a ΔT approach in the range
1.5° C.× N<ΔT approach <15° C.× N.
8. The method of claim 3 wherein heat is transferred into the catalyst from a microchannel heat exchanger that is adjacent to the reaction microchannel.
9. A method of methane steam reforming, comprising:
passing a stream comprising methane and water in a steam to carbon ratio of 3 or less, contacting said stream with a catalyst at a contact time of 5 ms or less and maintaining the same conditions for at least 1000 hours, wherein there is a continuous period of at least 595 hours in which the methane conversion changes by 3% or less; wherein the conversion of methane is at least 85% of the equilibrium conversion; and wherein at least 2 mol of methane are converted per gram catalytically-active material each minute.
10. The method of claim 9 wherein the catalyst comprises Rh and at least 2 mol of methane are converted per gram Rh each minute.
11. The method of claim 9 wherein the stream is passed into a reaction microchannel containing the catalyst.
12. The method of claim 11 wherein heat is transferred into the catalyst from a microchannel heat exchanger that is adjacent to the reaction microchannel.
13. The method of claim 10 wherein 1° C.×N<ΔT approach <25° C.×N over the at least 595 hours, and the conversion of methane is at least 90% of the equilibrium conversion;
wherein N is the gram moles of methane fed per minute per gram of catalytically active material; and wherein ΔT approach is the difference between the peak catalyst bed temperature and the apparent equilibrium conversion temperature; wherein the peak catalyst bed temperature is the highest temperature in the catalyst.
14. The method of claim 10 wherein 1° C.×N<ΔT approach <5° C.×N over the at least 595 hours;
wherein N is the gram moles of methane fed per minute per gram of catalytically active material; and wherein ΔT approach is the difference between the peak catalyst bed temperature and the apparent equilibrium conversion temperature; wherein the peak catalyst bed temperature is the highest temperature in the catalyst.
15. The method of claim 5 wherein 1° C.×N<ΔT approach <5° C.×N over the at least 2000 hours;
wherein N is the gram moles of methane fed per minute per gram of catalytically active material; and wherein Δ approach is the difference between the peak catalyst bed temperature and the apparent equilibrium conversion temperature; wherein the peak catalyst bed temperature is the highest temperature in the catalyst.
16. The method of claim 2 wherein the catalyst comprises Rh and at least 2 mol of methane are converted per gram Rh each minute.
17. The method of claim 1 wherein the methane and steam flow into contact with the catalyst in a steam to carbon ratio of 3:1 to 1:1.
18. The method of claim 17 wherein the stabilized alumina support is stabilized with Mg.
19. A method of methane steam reforming, comprising:
conducting a reaction in which methane and steam contact a catalyst at a temperature of at least 800° C. for at least 1000 hours without regenerating the catalyst;
wherein the catalyst comprises a stabilized alumina support and a catalytically active material; and wherein the method is further characterized by a contact time of 5 ms or less while achieving an average approach to equilibrium conversion of greater than 90% and further wherein the conversion has diminished by less than 3% over the 1000 hours without regenerating the catalyst; and further wherein N is greater than 1.0;
wherein the average approach to equilibrium conversion is the ratio of measurable hydrocarbon conversion to equilibrium hydrocarbon conversion; wherein N is the gram moles of methane fed per minute per gram of catalytically active material.
20. The method of claim 19 wherein the catalyst comprises Rh.
21. The method of claim 18 wherein the catalyst comprises 1 to 3 wt % Rh.
22. The method of claim 1 wherein the methane and steam contact the catalyst at a temperature of less than 900° C.
23. The method of claim 1 characterized by a contact time of 5 ms or less while achieving an average approach to equilibrium conversion of greater than 90%.
24. The method of claim 23 wherein the catalyst comprises Rh.
25. The method of claim 1 wherein the partial pressure of steam is at least 2 atm.
26. The method of claim 9 wherein after the 595 hours of continuous operation, the CO selectivity is essentially unchanged.
27. The method of claim 1 wherein the method is conducted at a pressure of from 10 atm to 30 atm.
28. The method of claim 1 wherein a stream containing the methane and steam is passed into a reaction microchannel containing the catalyst.