Metal doped zeolite and process for its preparation
View Patent ↗A metal-doped or metal-exchanged zeolite is disclosed, wherein the doping metal is present in the zeolite in the form of individual atoms i.e. as monomeric and/or dimeric species. Further, a process for the preparation of such a metal-doped or metal-exchanged zeolite is disclosed. The metal-doped zeolites are useful, in particular, as catalysts for the reduction of nitrogen oxides.
1. A process for the preparation of a metal-exchanged zeolite comprising providing an aqueous suspension of a zeolite having a zeolite skeleton in a sealable reaction vessel and then:
a) increasing the pH of the suspension to a value in the range from 8 to 10 using NH 4 OH, and setting the oxygen level of the reaction vessel to a value of <10%,
b) reducing the pH to a value in the range from 1.5 to 6,
c) adding a metal salt including a replacement metal and reacting the suspension over a period of 1 to 15 hours to prepare a metal-exchanged zeolite, and
d) filtering off and washing the metal-exchanged zeolite.
2. The process according to claim 1 , wherein the suspension of step a) contains 5 to 25 wt.-% zeolite.
3. The process according to claim 1 , wherein a molar ratio of ammonia to zeolite at the end of step a) has a value of 0.01 to 0.1.
4. The process according to claim 1 , wherein the pH is reduced in step b) by adding a mineral acid.
5. The process according to claim 4 , wherein the pH in step b) is set to a value in the range from 1.5 to 3.
6. The process according to claim 4 , wherein, after reducing the pH in step b), the suspension is heated to a temperature in the range from 80 to 100° C.
7. The process according to claim 6 , wherein, during the exchange reaction in step c), the oxygen level in the reaction vessel is less than 5%.
8. The process according to claim 7 , wherein the zeolite obtained after step d) is dried at a temperature of greater than 100° C.
9. The process according to claim 7 , wherein the process is carried out several times.
10. The process according to claim 8 , wherein the dried zeolite is calcined at a temperature of 400 to 600° C.
11. The process according to claim 10 , wherein the calcination takes place under inert gas.
12. The process according to claim 1 , wherein the zeolite is selected from the group consisting of AEL, BEA, CHA, EUO, FAO, FER, KFI, LTA, LTL, MAZ, MOR, MEL, MTW, LEV, OFF, TON, ERI, and MFI.
13. The process according to claim 12 , wherein the zeolite is selected from the group consisting of BEA, MFI, FER, MOR, MTW, and ERI.
14. The process according to claim 1 , wherein a pore size of the zeolites is from 0.4 to 1.5 nm.
15. The process according to claim 14 , wherein the replacement metal is catalytically active.
16. The process according to claim 15 , wherein the replacement metal is selected from the group consisting of Fe, Co, Ni, Ag, Cu, V, Rh, Pd, Pt, and Ir.
17. The process according to claim 16 , wherein the replacement metal is selected from the group consisting of Fe, Co, Ni, and Cu.
18. The process according to claim 16 , wherein the replacement metal is provided in step c) in a quantity of 1 to 5 wt.-% calculated as metal oxide relative to the total weight of the zeolite.
19. The process according to claim 18 , wherein 70% to 90% of the exchangeable sites of the zeolite obtained in step d) are occupied by the replacement metal.
20. A process for the preparation of a metal-exchanged zeolite comprising providing an aqueous suspension of a zeolite having a zeolite skeleton in a sealable reaction vessel and then:
a) increasing the pH of the suspension to a value in the range from 8 to 10 using a base, and setting the oxygen level of the reaction vessel to a value of <10%,
b) reducing the pH to a value in the range from 1.5 to 6,
c) adding a metal salt including a replacement metal and reacting the suspension over a period of 1 to 15 hours to prepare a metal-exchanged zeolite, and
d) filtering off and washing the metal-exchanged zeolite.