Method for preparing the silicoaluminate form of the AEI zeolite structure with high yields, and its application in catalysis

Patent metadata

Field	Value
Publication number	US-10526208-B2
Application number	US-201615566302-A
Country	US
Kind code	B2
Filing date	Apr 14, 2016
Priority date	Apr 16, 2015
Publication date	Jan 7, 2020
Grant date	Jan 7, 2020

Abstract

A synthesis process for a crystalline material with the AEI zeolite structure, comprising (i) preparation of a mixture containing, at least, water, one zeolite with the FAU crystal structure as the only source of silicon and aluminum, a cyclic ammonium cation with alkyl substituents as the OSDA, and a source of alkaline or alkaline-earth cations (A), wherein the synthesis mixture has the following molar composition: SiO 2 :a Al 2 O 3 :b OSDA:c A:d H 2 O where a ranges between 0.001 and 0.2; where b ranges between 0.01 and 2; where c ranges between 0 and 2; where d ranges between 1 and 200; and wherein the mixture is free from phosphorous and fluorinated species, (ii) crystallisation of the mixture and, (iii) recovery of the crystalline material. Also, preparation of catalysts based on the AEI zeolite and application as a catalysts in processes including the selective catalytic reduction of NO x .

First claim

The invention claimed is:

1. Synthesis process for a crystalline material with the AEI zeolite structure, comprising, at least, the following steps:
(i) preparation of a mixture containing, at least, water, one zeolite with the FAU crystal structure as the only source of silicon and aluminum, a cyclic ammonium cation with alkyl substituents as the OSDA, and a source of alkaline or alkaline-earth cations (A), wherein the synthesis mixture has the following molar composition:
SiO 2 :a Al 2 O 3 :b OSDA: c A:d H 2 O
where a ranges between 0.001 and 0.2;
where b ranges between 0.01 and 2;
where c ranges between 0 and 2;
where d ranges between 1 and 200; and
wherein the mixture is free from phosphorous and fluorinated species;

(ii) crystallisation of the mixture obtained in (i) in a reactor; and
(iii) recovery of the crystalline material obtained in (ii).

2. Process according to claim 1 , wherein the cyclic ammonium cation used as the OSDA is a quaternary ammonium selected from N,N-dimethyl-3,5-dimethylpiperidinium (DMDMP), N,N-diethyl-2,6-dimethylpiperidinium (DEDMP), N,N-dimethyl-2,6-dimethylpiperidinium, N-ethyl-N-methyl-2,6-dimethylpiperidinium, and combinations thereof.

3. Process according to claim 2 , wherein the OSDA is N,N-dimethyl-3,5-dimethylpiperidinium.

4. Process according to claim 1 , further comprising another co-operative OSDA present in step (i), which is any organic molecule.

5. Process according to claim 4 , wherein the co-operative OSDA is an ammonium cation.

6. Process according to claim 5 , wherein the co-operative OSDA is a cyclic ammonium cation.

7. Process according to claim 4 , wherein the co-operative OSDA is an amine.

8. Process according to claim 1 , wherein the crystallisation process described in (ii) is performed in autoclaves, under static or dynamic conditions.

9. Process according to claim 1 , wherein the crystallisation process described in (ii) is performed at a temperature ranging between 100° C. and 200° C.

10. Process according to claim 1 , wherein the crystallisation time of the process described in (ii) ranges between 6 hours and 50 days.

11. Process according to claim 1 , further comprising the addition of AEI crystals, designed to act as seeds, to the synthesis mixture in a quantity of up to 25% by weight with respect to the total quantity of oxides.

12. Process according to claim 11 , wherein the AEI crystals are added before the crystallisation process or during the crystallisation process.

13. Process according to claim 1 , wherein the recovery step (iii) is performed using a separation technique selected from decantation, filtration, ultrafiltration, centrifugation and combinations thereof.

14. Process according to claim 1 , further comprising the elimination of the organic content retained inside the material by means of an extraction process.

15. Process according to claim 1 , further comprising the elimination of the organic content retained inside the material by means of a heat treatment at temperatures ranging between 100° C. and 1000° C. for a period of time ranging between 2 minutes and 25hours.

16. Process according to claim 1 , wherein the material obtained is pelletised.

17. Process according to claim 1 , wherein any cation present in the material may be exchanged with other cations by means of ion exchange using conventional techniques.

18. Process according to claim 17 , wherein the exchange cation is selected from metals, protons, proton precursors and mixtures thereof.

19. Process according to claim 18 , wherein the exchange cation is a metal selected from rare earth elements, metals of groups IIA, IIIA, IVA, VA, IB, IIB, IIIB, IVB, VB, VIB, VIIB and VIII, and combinations thereof.

20. Process according to claim 19 , wherein the metal is copper.

21. Synthesis process for a crystalline material with the AEI zeolite structure, comprising, at least, the following steps:
(i) preparation of a mixture containing, at least: water; one zeolite with the FAU crystal structure as the only source of silicon and aluminum; an OSDA selected from the group consisting of N,N-dimethyl-3,5-dimethylpiperidinium (DMDMP), N,N-diethyl-2,6-dimethylpiperidinium (DEDMP), N,N-dimethyl-2,6-dimethylpiperidinium, N-ethyl-N-methyl-2,6-dimethylpiperidinium, and combinations thereof; and a source of alkaline or alkaline-earth cations (A), wherein the synthesis mixture has the following molar composition:
SiO 2 :a Al 2 O 3 :b OSDA:c A:d H 2 O
where a ranges between 0.001 and 0.2;
where b ranges between 0.01 and 2;
where c ranges between 0 and 2;
where d ranges between 1 and 200; and
wherein the mixture is free from phosphorous and fluorinated species;

(ii) crystallisation of the mixture obtained in (i) in a reactor; and
(iii) recovery of the crystalline material obtained in (ii).

22. The synthesis process according to claim 21 , wherein the zeolite with the FAU crystal structure has a SiO 2 :Al 2 O 3 molar ratio of 21.

Assignees

• Consejo Superior Investigacion
• Univ Valencia Politecnica
• Consejo Superior Investigacion
• Univ Politencia De Valencia

Inventors

• Corma Canós Avelino
• Moliner Marín Manuel
• Martín García Nuria

Classifications

• B01D9/0036

  Crystallisation on to a bed of product crystals; Seeding · CPC title

• C01B39/24

  Type Y {(C01B39/205 takes precedence)} · CPC title

• C01B39/023

  Preparation of physical mixtures or intergrowth products of zeolites chosen from group C01B39/04 or two or more of groups C01B39/14 - C01B39/48 · CPC title

• C01B39/48 Primary

  using at least one organic template directing agent · CPC title

• C07C2529/072

  Iron group metals or copper · CPC title