Zeolite catalyst with improved NOx reduction in SCR
The present invention is directed to a novel metal-promoted zeolite catalyst, a method of producing the catalyst and a method of using the catalyst for the selective catalytic reduction of NOx with improved hydrothermal durability. The novel metal-promoted zeolite is formed from a low sodium zeolite and is hydrothermally treated after metal ion-exchange.
1. A method of preparing a metal-promoted zeolite catalyst for selective catalytic reduction of NOx, said catalyst synthesis comprising the step of:
a. ion-exchanging said metal into a zeolite having the faujasite (FAU) structure and having a sodium content of less than 3.0 wt. % as Na 2 O following metal ion-exchange, the metals selected from the group consisting of metal ions of iron, cobalt, and copper,
b. subsequently treating said metal exchanged zeolite with a hydrothermal treatment, and
c. wherein said catalyst has improved NOx reduction activity in selective catalytic reduction compared to metal-exchanged zeolite catalysts not treated by step b.
2. The method of claim 1 , wherein said zeolite is treated prior to said ion-exchange by acid dealumination, steam dealumination or extraction of extra-framework aluminum with a complexing agent.
3. The method of claim 1 , wherein said zeolite is selected from the group consisting of zeolite Y, faujasites, ultra-stable Y, ZSM-3, ZSM-20, CSZ-1, ECR-30, and LZ-210.
4. The method of claim 3 , wherein said zeolite is zeolite Y and said metal is copper.
5. The method of claim 1 , wherein said metal ion-exchange is in an aqueous exchange solution having a pH of less than about 5.0.
6. The method of claim 1 , wherein said metal ion-exchange is in an aqueous exchange solution having a pH of from about 2.5 to about 3.5.
7. The method of claim 1 , wherein more than one ion-exchange step is used and wherein an intermediate calcination step is used between said more than one ion-exchange steps.
8. The method of claim 1 , wherein said metal exchanged zeolite is hydrothermally treated at a temperature from about 540° C. to about 1000° C., with a steam concentration of from about 5 to about 100%, for about 5 minutes to about 250 hours.
9. The method of claim 1 , wherein said metal exchanged zeolite is calcined prior to hydrothermal treatment.
10. The method of claim 1 , wherein the zeolite has a pore diameter of at least about 7.4 angstroms.
11. The method of claim 1 , wherein said zeolite has a sodium content of less than 0.4 wt. % as Na 2 O following metal ion-exchange.
12. A copper containing aluminosilicate zeolite catalyst formed by the method of claim 1 .
13. A hydrothermally stable zeolite catalyst for the selective reduction of nitrogen oxides, said catalyst comprising: a metal-promoted zeolite having the faujasite (FAU) structure and a sodium content of less than 3.0 wt. % as Na 2 O following metal ion-exchange which has been hydrothermally treated after metal ion-exchange to form extra-framework aluminum and wherein a major portion of said extra-framework aluminum is removed from zeolitic pores and said catalyst has improved NOx reduction activity in selective catalytic reduction compared to a metal-exchanged zeolite catalyst that has not been hydrothermally treated after ion exchange, wherein the metal is selected from the group consisting of copper, cobalt and iron.
14. The zeolite catalyst of claim 13 , wherein less than 65 wt. % of the total aluminum resides in the zeolitic pores.
15. The metal-promoted zeolite catalyst of claim 13 , wherein said zeolite is zeolite Y and said metal is copper.
16. The metal-promoted zeolite catalyst of claim 13 , wherein the zeolite contains mesopores having a diameter of 2 to 50 nm and said mesopores have a pore volume of at least 0.07 cm 3 /g.
17. The hydrothermally stable zeolite catalyst of claim 13 , wherein said zeolite contains a metal loading at the external surface of the zeolite from about 1 wt. % to about 10.0 wt. %, based on the weight of the cation-exchanged zeolite.
18. The metal-promoted zeolite catalyst of claim 13 , wherein said metal-promoted zeolite catalyst is coated onto a substrate.
19. The zeolite catalyst of claim 13 , wherein a major portion of the extra-framework aluminum has migrated to the external surface of the metal-promoted zeolite.
20. The zeolite catalyst of claim 13 , wherein the zeolite has a pore diameter of at least about 7.4 angstroms.
21. The zeolite catalyst of claim 13 , wherein said zeolite has a sodium content of less than 0.4 wt. % as Na 2 O following metal ion-exchange.
22. The zeolite catalyst of claim 13 , wherein the catalyst further comprises a metal selected from the group consisting of vanadium, chromium, manganese, nickel and cerium.
23. A method of reducing NOx in an exhaust gas or flue gas stream with ammonia and oxygen by selective catalytic reduction said method comprising contacting said exhaust gas or flue gas stream with the metal-promoted zeolite catalyst of claim 12 .
24. A method of reducing NOx in an exhaust gas or flue gas stream with ammonia and oxygen by selective catalytic reduction said method comprising contacting said exhaust gas or flue gas stream with the metal-promoted zeolite catalyst of claim 18 .