Copper CHA zeolite catalysts
View Patent ↗Zeolite catalysts and systems and methods for preparing and using zeolite catalysts having the CHA crystal structure are disclosed. The catalysts can be used to remove nitrogen oxides from a gaseous medium across a broad temperature range and exhibit hydrothermal stable at high reaction temperatures. The zeolite catalysts include a zeolite carrier having a silica to alumina ratio from about 15:1 to about 256:1 and a copper to alumina ratio from about 0.25:1 to about 1:1.
1. A catalyst comprising:
a zeolite having the CHA crystal structure and a mole ratio of silica to alumina greater than about 15 and an atomic ratio of copper to aluminum exceeding about 0.25.
2. The catalyst of claim 1 , wherein the mole ratio of silica to alumina is from about 15 to about 256 and the atomic ratio of copper to aluminum is from about 0.25 to about 0.50.
3. The catalyst of claim 2 , wherein the mole ratio of silica to alumina is from about 25 to about 40.
4. The catalyst of claim 2 , wherein the mole ratio of silica to alumina is about 30.
5. The catalyst of claim 2 , wherein the atomic ratio of copper to aluminum is from about 0.30 to about 0.50.
6. The catalyst of claim 2 , wherein the atomic ratio of copper to aluminum is about 0.40.
7. The catalyst of claim 2 , wherein the mole ratio of silica to alumina is from about 25 to about 40 and the atomic ratio of copper to aluminum is from about 0.30 to about 0.50.
8. The catalyst of claim 2 , wherein the mole ratio of silica to alumina is about 30 and the atomic ratio of copper to alumina is about 0.40.
9. The catalyst of claim 2 , wherein the catalyst contains ion-exchanged copper and an amount of non-exchanged copper sufficient to maintain NOx conversion performance of the catalyst in an exhaust gas stream containing nitrogen oxides after hydrothermal aging of the catalyst.
10. The catalyst of claim 9 , wherein the NOx conversion performance of the catalyst at about 200° C. after aging is at least 90% of the NOx conversion performance of the catalyst at about 200° C. prior to aging.
11. The catalyst of claim 9 , wherein the catalyst contains at least about 2.00 weight percent copper oxide.
12. The catalyst of claim 2 , wherein the catalyst is deposited on a honeycomb substrate.
13. The catalyst of claim 12 , wherein the honeycomb substrate comprises a wall flow filter substrate.
14. The catalyst of claim 12 , wherein the honeycomb substrate comprises a flow through substrate.
15. The catalyst of claim 14 , wherein at least a portion of the flow through substrate is coated with CuCHA adapted to reduce oxides of nitrogen contained in a gas stream flowing through the substrate.
16. The catalyst of claim 15 , wherein at least a portion of the flow through substrate is coated with Pt and CuCHA adapted to oxidize ammonia in the exhaust gas stream.
17. The catalyst of claim 14 , wherein at least a portion of the flow through substrate is coated with Pt and CuCHA adapted to oxidize ammonia in the exhaust gas stream.
18. The catalyst of claim 13 , wherein at least a portion of the wall flow substrate is coated with CuCHA adapted to reduce oxides of nitrogen contained in a gas stream flowing through the substrate.
19. The catalyst of claim 18 , wherein at least a portion of the wall flow substrate is coated with Pt and CuCHA adapted to oxidize ammonia in the exhaust gas stream.
20. The catalyst of claim 13 , wherein at least a portion of the wall flow substrate is coated with Pt and CuCHA adapted to oxidize ammonia in the exhaust gas stream.
21. An exhaust gas treatment system comprising the catalyst of claim 15 disposed downstream from a diesel engine and an injector that adds a reductant to an exhaust gas stream from the engine.
22. An exhaust gas treatment system comprising the catalyst of claim 17 disposed downstream from a diesel engine and an injector to add a reductant to an exhaust gas stream from the engine.
23. An exhaust gas treatment system comprising the catalyst of claim 18 disposed downstream from a diesel engine and an injector to add a reductant to an exhaust gas stream from the engine.
24. An exhaust gas treatment system comprising the catalyst of claim 20 disposed downstream from a diesel engine and an injector to add a reductant to an exhaust gas stream from the engine.
25. A catalyst article comprising a honeycomb substrate having a zeolite having the CHA crystal structure deposited on the substrate, the zeolite having a mole ratio of silica to alumina greater than about 15 and an atomic ratio of copper to aluminum exceeding about 0.25 and containing an amount of free copper exceeding ion-exchanged copper.
26. The catalyst of claim 25 , wherein the free copper is present in an amount sufficient to prevent hydrothermal degradation of the nitrogen oxide conversion of the catalyst.
27. The catalyst of claim 26 , wherein the free copper prevents hydrothermal degradation of the nitrogen oxide conversion of the catalyst upon exposure to temperatures in excess of about 800° C. and in the presence of about 10% water vapor.
28. The catalyst of claim 25 , further comprising a binder.
29. The catalyst of claim 25 , wherein the ion-exchanged copper is exchanged using copper acetate.
30. An exhaust gas treatment system comprising an exhaust gas stream containing NOx, and a catalyst in accordance with claim 2 effective for selective catalytic reduction of at least one component of NOx in the exhaust gas stream.
31. An exhaust gas treatment system comprising an exhaust gas stream containing ammonia and a catalyst in accordance with claim 2 effective for destroying at least a portion of the ammonia in the exhaust gas stream.
32. The catalyst of claim 2 , wherein the substrate comprises a high efficiency open cell foam filter.
33. An exhaust gas treatment system comprising the catalyst of claim 2 and further comprising a catalyzed soot filter.
34. The exhaust gas treatment system of claim 33 , wherein said catalyzed soot filter is upstream of said catalyst.
35. The exhaust gas treatment system of claim 33 , wherein said catalyzed soot filter is downstream of said catalyst.
36. The exhaust gas treatment system of claim 33 , further comprising a diesel oxidation catalyst.
37. The exhaust gas treatment system of claim 36 , wherein said diesel oxidation catalyst is upstream of said catalyst comprising a zeolite having the CHA crystal structure.
38. The exhaust gas treatment system of claim 36 , wherein said diesel oxidation catalyst and catalyzed soot filter are upstream from said catalyst comprising a zeolite having the CHA crystal structure.