A PROCESS FOR PREPARING A ZEOLITIC MATERIAL COMPRISING A METAL M AND HAVING FRAMEWORK TYPE AEI

Abstract

A process for preparing a zeolitic material comprising a metal M, having framework type AEI, and having a framework in structure which comprises a tetravalent element Y, a trivalent element X, and oxygen, said process comprising (i) providing a zeolitic of material comprising the metal M, having a framework type other than AEI, and having a framework structure comprising the trivalent element X, and oxygen; (ii) preparing a synthesis mixture comprising the zeolitic material provided in (i), water, a source of the tetravalent element Y, and an AEI framework structure directing agent; (iii) subjecting the synthesis mixture prepared in (ii) to hydrothermal synthesis conditions comprising heating the synthesis mixture to a temperature in the range of from 100 to 200 C. and keeping the synthesis mixture at a temperature in this range under autogenous pressure, obtaining the zeolitic material having framework type AEI; wherein Y is one or more of Si, Ge, Sn, Ti, Zr; wherein X is one or more of Al, B, Ga, In; wherein M is a transition metal of groups 7 to 12 of the periodic table of elements.

Claims

1. A process for preparing a zeolitic material comprising a metal M, having framework type AEI, and having a framework structure which comprises a tetravalent element Y, a trivalent element X, and oxygen, said process comprising: (i) providing a zeolitic material comprising the metal M, having a framework type other than AEI, and having a framework structure comprising the trivalent element X, and oxygen; (ii) preparing a synthesis mixture comprising the zeolitic material provided in (i), water, a source of the tetravalent element Y, and an AEI framework structure directing agent; (iii) subjecting the synthesis mixture prepared in (ii) to hydrothermal synthesis conditions comprising heating the synthesis mixture to a hydrothermal synthesis temperature in a range of from 100 to 200 C., to obtain a heated synthesis mixture, and keeping the heated synthesis mixture at a temperature in said range under autogenous pressure, to obtain a mixture comprising zeolitic material having framework type AEI; wherein Y is one or more of Si, Ge, Sn, Ti, and Zr; X is one or more of Al, B, Ga, and In; and M is a transition metal of groups 7 to 12 of the periodic table of elements.

2. The process of claim 1, wherein M is one or more of Fe, Co, Ni, Cu, and Zn.

3. The process of claim 1, wherein the zeolitic material provided in (i) comprises M in an amount in a range of from 0.1 to 5 weight-%, calculated as elemental M and based on a total weight of the zeolitic material.

4. The process of claim 1, wherein the zeolitic material provided in (i) has a framework structure which additionally comprises the tetravalent element Y.

5. The process of claim 1, wherein X is Al and Y is Si.

6. The process of claim 1, wherein the zeolitic material provided in (i) has framework type CHA, FAU, LTA, MOR, MFI, or BEA.

7. The process of claim 1, wherein (i) comprises: (i.1) providing a zeolitic material which does not comprise the metal M, which has the framework type other than AEI, and which has the framework structure comprising the trivalent element X and oxygen; and (i.2) supporting the metal Mon the zeolitic material provided in (i.1).

8. The process of claim 1, wherein Y is Si and the source of the tetravalent element Y according to (ii) comprises one or more of a wet-process silica, a dry-process silica, and a colloidal silica; and the AEI framework structure directing agent comprises one or more quaternary phosphonium cation containing compounds and/or one or more quaternary ammonium cation containing compounds; wherein the one or more quaternary phosphonium cation containing compounds comprise one or more R.sup.1R.sup.2R.sup.3R.sup.4P-containing compounds, wherein R.sup.1, R.sup.2, R.sup.3, and R.sup.4 independently from one another represent optionally substituted and/or optionally branched (C.sub.1-C.sub.6)alkyl; the one or more quaternary ammonium cation containing compounds comprise one or more N,N-dialkyl-dialkylpiperidinium cation containing compounds; and the one or more quaternary phosphonium cation containing compounds and/or the one or more quaternary ammonium cation containing compounds are salts.

9. The process of claim 1, wherein in the synthesis mixture prepared in (ii) which is subjected to (iii), aweight ratio of the zeolitic material relative to the source of the tetravalent element Y, calculated as YO.sub.2, is in a the range of from 1.0:1 to 3.0:1; a weight ratio of the zeolitic material relative to the water is in a range of from 0.005:1 to 0.030:1; and a weight ratio of the zeolitic material relative to the AEI framework structure directing agent is in a range of from 0.1:1 to 3:1.

10. The process of claim 1, wherein the synthesis mixture prepared in (ii) which is subjected to (iii) additionally comprises a source of a base.

11. The process of claim 1, wherein the hydrothermal synthesis temperature is in a range of from 110 to 175 C.

12. The process of claim 1, further comprising: (iv) cooling the mixture obtained from (iii), to obtain a cooled mixture; (v) separating the zeolitic material comprising the metal M from the mixture obtained from (iii) or from the cooled mixture obtained from (iv), to obtain a separated zeolitic material comprising the metal M; and (vi) calcining the separated zeolitic material comprising the metal M obtained from (v).

13. A zeolitic material, comprising a metal M, having framework type AEI, and having a framework structure which comprises a tetravalent element Y, a trivalent element X, and oxygen, wherein the zeolitic material is obtainable or obtained by the process of claim 1, and comprises M in an amount in a range of from 0.1 to 5 weight-%, calculated as elemental M and based on a total weight of the zeolitic material.

14. The zeolitic material of claim 13, having a total amount of acid sites in a range of from 1.0 to 2.0 mmol/g, wherein the total amount of acid sites is defined as a total molar amount of desorbed ammonia per mass of the zeolitic material determined according to a temperature programmed desorption of ammonia; wherein the zeolitic material has an amount of medium acid sites in a range of from 0.1 to 0.8 mmol/g, wherein the amount of medium acid sites is defined as an amount of desorbed ammonia per mass of the zeolitic material determined according to the temperature programmed desorption of ammonia in a temperature range of from 250 to 500 C.

15. An article, wherein the article is a catalytically active material, catalyst, or catalyst component comprising the zeolitic material of claim 13.

Description

BRIEF DESCRIPTION OF THE FIGURES

[0320] FIG. 1: shows the XRD pattern of the Cu containing zeolitic material according to Example 1.

[0321] FIG. 2: shows the SEM picture of the Cu containing zeolitic material according to Example 1.

[0322] FIG. 3: shows the XRD pattern of the Cu containing zeolitic material according to Example 2.

[0323] FIG. 4: shows a result of the testing according to Example 3, in particular the result of the respective materials aged at 650 C. (simulating heavy duty diesel application). The x axis shows the conversion of NOx for the respective material at a conversion temperature of 200 N, the y axis shows the conversion of NOx for the respective material at a conversion temperature of 200 C. The empty triangle symbol stands for the reference material, the template-free CHA zeolite, the black square stands for the zeolitic material according to Example 1, the black circle stands for the zeolitic material according to Example 2.

[0324] FIG. 5: shows a result of the testing according to Example 3, in particular the result of the respective materials aged at 800 C. (simulating light duty diesel application). The x axis shows the conversion of NOx for the respective material at a conversion temperature of 200 N, the y axis shows the conversion of NOx for the respective material at a conversion temperature of 200 C. The empty triangle symbol stands for the reference material, the template-free CHA zeolite, the black square stands for the zeolitic material according to Example 1, the black circle stands for the zeolitic material according to Example 2.

CITED LITERATURE

[0325] WO 2013/068976 A [0326] Madsen, I. C., Scarlett , N. V. Y. (2008) Quantitative phase analysis in: Dinnebier, R. E., Billinge S. J. L. (eds) Powder diffraction: theory and practice, The Royal Society of Chemistry, Cambridge, pp. 298-331 [0327] WO 2013/182974 A