Method for producing metal exchanged microporous materials by solid-state ion exchange

Patent metadata

Field	Value
Publication number	US-9895660-B2
Application number	US-201415125502-A
Country	US
Kind code	B2
Filing date	Oct 15, 2014
Priority date	Apr 7, 2014
Publication date	Feb 20, 2018
Grant date	Feb 20, 2018

Abstract

A method is disclosed for the preparation of a metal exchanged microporous materials, e.g. metal exchanged silicoaluminophosphates or metal exchanged zeolites, or mixtures of metal exchanged microporous materials, comprising the steps of providing a dry mixture of a) one or more microporous materials that exhibit ion exchange capacity and b) one or more metal compounds; heating the mixture in a gaseous atmosphere containing ammonia and one or more oxides of nitrogen to a temperature and for a time sufficient to initiate and perform a solid state ion exchange of ions of the metal compound and ions of the microporous material; and obtaining the metal-exchanged microporous material.

First claim

The invention claimed is:

1. Method for the preparation of a metal exchanged crystalline microporous material or mixtures of metal exchanged crystalline microporous materials comprising the steps of providing a dry mixture containing a) one or more crystalline microporous materials that exhibit ion exchange capacity and b) one or more metal compounds; heating the mixture in a gaseous atmosphere containing ammonia and one or more oxides of nitrogen to a temperature and for a time sufficient to initiate and perform a solid state ion exchange of ions of the metal compound and ions of the crystalline microporous material; and obtaining the crystalline metal-exchanged microporous material.

2. Method according to claim 1 , wherein the crystalline microporous material is selected from the group consisting of zeolite or zeotype materials.

3. Method according to claim 2 , where the zeolite or zeotype materials have the framework code of AEI, AFX, CHA, KFI, LTA, IMF, ITH, MEL, MFI, SZR, TUN, *BEA, BEC, FAU, FER, MOR, LEV.

4. Method according to claim 2 , wherein the zeolite or zeotype materials are selected from the group consisting of ZSM-5, zeolite Y, beta zeolite, SSZ-13, SSZ-39, SSZ-62, Chabazite, and SAPO-34, SAPO-44, Ferrierite, TNU-9.

5. Method according to claim 1 , wherein the crystalline microporous material or mixtures of crystalline microporous materials are in the H or NH 4 form.

6. Method according to claim 1 , wherein the crystalline microporous material or mixtures of crystalline microporous material contains an organic structure directing agent.

7. Method according to claim 1 , wherein the metal compound is selected from the group of metal oxides, metal nitrates and phosphates, sulfates, oxalates, acetates or a combination thereof.

8. Method according to claim 1 , wherein the metals in the metal compounds are selected from the group of Fe, Co, Cu.

9. Method according to claim 1 , wherein the metal compounds comprise one or more oxides of Cu.

10. Method according to claim 1 , wherein the oxide of nitrogen is selected from nitrogen monoxide, and nitrogen dioxide and mixtures thereof.

11. Method according to claim 1 , wherein the content of ammonia in the atmosphere is between 1 and 5000 vol. ppm.

12. Method according to claim 1 , wherein the content of the one or more nitrogen oxides in the gaseous atmosphere is between 1 and 5000 vol. ppm.

13. Method according to claim 1 , wherein the molar ratio of ammonia to nitrogen oxides is larger than 0.01, preferably between 0.2 and 1.

14. Method according to claim 1 , wherein the oxygen content in the atmosphere is 1% or lower.

15. Method according to claim 1 , wherein the gaseous atmosphere contains 5% water or less.

16. A method according to claim 1 , wherein the mixture is heated in the gaseous atmosphere containing ammonia and one or more oxides of nitrogen to a temperature lower than 300° C.

17. A method according to claim 1 , wherein the mixture is heated in the gaseous atmosphere containing ammonia and one or more oxides of nitrogen to a temperature in a range from 100° C. and to below 300° C.

18. A method according to claim 1 , wherein the mixture is heated in the gaseous atmosphere containing ammonia and one or more oxides of nitrogen to a temperature in a range between 150° C. and 250° C.

19. A method for the removal of nitrogen oxides from exhaust gas by selective catalytic reduction with a reductant, comprising:
preparing a catalyst comprising a metal exchanged crystalline microporous material or mixtures of metal exchanged crystalline microporous materials by: providing a dry mixture containing (a) one or more crystalline microporous materials that exhibit ion exchange capacity and (b) one or more metal compounds; heating the mixture in a gaseous atmosphere containing ammonia and one or more oxides of nitrogen to a temperature and for a time sufficient to initiate and perform a solid state ion exchange of ions of the metal compound and ions of the crystalline microporous material; and obtaining the catalyst comprising crystalline metal-exchanged microporous material; and
containing the exhaust gas with the catalyst comprising metal exchanged crystalline microporous material or mixtures of metal exchanged crystalline microporous materials.

20. A method according to claim 19 , wherein the reductant is ammonia or a precursor thereof.

21. A method according to claim 19 , wherein the reductant is hydrocarbons.

Assignees

• Haldor Topsoe As
• Haldor Topsoe As

Inventors

• Janssens Ton V W
• Vennestrøm Peter N R

Classifications

• B01D2255/50

  Zeolites · CPC title

• B01J37/0238

  via the gaseous phase-sublimation · CPC title

• B01J29/763

  CHA-type, e.g. Chabazite, LZ-218 · CPC title

• B01J29/7607

  A-type · CPC title

• B01J37/08

  Heat treatment {(B01J37/0009, B01J37/0018 take precedence)} · CPC title