Method for the direct synthesis of Cu-containing silicoaluminate material with the AEI zeolite structure, and the catalytic applications thereof

Patent metadata

Field	Value
Publication number	US-10646826-B2
Application number	US-201615566585-A
Country	US
Kind code	B2
Filing date	Apr 14, 2016
Priority date	Apr 16, 2015
Publication date	May 12, 2020
Grant date	May 12, 2020

Abstract

The present invention provides a new method for preparing the copper-containing silicoaluminate form of the AEI zeolite structure by means of a direct synthesis methodology. This new process involves combining a organometallic copper-complex with an additional organic molecule capable of directing the crystallization of the silicoaluminate form of the AEI zeolite structure as organic structure-directing agents (OSDAs).

First claim

The invention claimed is:

1. Process for the direct synthesis of a material with the copper-containing silicoaluminate form of the AEI zeolite structure, which comprises, at least, the following steps:
(i) preparation of a mixture containing, at least,
one source of water,
one source of copper,
one polyamine,
one source of tetravalent element Y, one source of trivalent element X,
one cyclic ammonium cation with alkyl substituents as the OSDA and
one source of alkaline or alkaline-earth cations (A), where the synthesis mixture has the following molar composition:
YO 2 :a X 2 O 3 :b OSDA: c A: d H 2 O: e Cu: f Polyamine

where
a ranges between 0.001 and 0.2;
b ranges between 0.01 and 2;
c ranges between 0 and 2;
d ranges between 1 and 200;
e ranges between 0.001 and 1; and
f ranges between 0.001 and 1;

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

2. Process for the direct synthesis of a material according to claim 1 , wherein c ranges between 0.001 and 1.

3. Process for the direct synthesis of a material according to claim 1 , wherein Y is a tetravalent element selected from Si, Sn, Ti, Ge, and combinations thereof.

4. Process for the direct synthesis of a material according to claim 3 , wherein Y is Si and originates from a source selected from silicon oxide, silicon halide, colloidal silica, fumed silica, tetraalkyl orthosilicate, silicate, silicic acid, a previously synthesised crystalline material, a previously synthesised amorphous material, and combinations thereof.

5. Process for the direct synthesis of a material according to claim 4 , wherein the source of Y is a previously synthesised crystalline material.

6. Process for the direct synthesis of a material according to claim 1 , wherein X is selected from Al, B, Fe, In, Ga, and combinations thereof.

7. Process for the direct synthesis of a material according to claim 6 , wherein X is Al and originates from a source selected from aluminum salt, any hydrated aluminum oxide, any aluminum alkoxide, a previously synthesised crystalline material, a previously synthesised amorphous material and combinations thereof.

8. Process for the direct synthesis of a material according to claim 7 , wherein the source of X is a previously synthesised crystalline material.

9. Process for the direct synthesis of a material according to claim 1 , wherein a zeolite with the FAU structure is the only source of Y and X.

10. Process for the direct synthesis of a material according to claim 1 , wherein any source of copper may be used in step (i).

11. Process for the direct synthesis of a material according to claim 10 , wherein the source of copper is selected from nitrate, sulfate and oxalate salts, and combinations thereof.

12. Process for the direct synthesis of a material 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.

13. Process for the direct synthesis of a material according to claim 12 , wherein the OSDA selected is N,N-dimethyl-3,5-dimethylpiperidinium.

14. Process for the direct synthesis of a material according to claim 1 , wherein the polyamine of step (i) comprises primary amines, secondary amines, tertiary amines, or mixtures thereof.

15. Process for the direct synthesis of a material according to claim 14 , wherein the polyamine required in step (i) is selected from tetraethylenepentamine, triethylenetetramine, 1,4,8,11-tetraazacyclotetradecane, 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane, or mixtures thereof.

16. Process for the direct synthesis of a material according to claim 15 , wherein the polyamine used in step (i) is tetraethylenepentamine.

17. Process for the direct synthesis of a material according to claim 1 , wherein the crystallisation process described in (ii) is performed in autoclaves, under static or dynamic conditions.

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

19. Process for the direct synthesis of a material according to claim 1 , wherein the crystallisation time for the process described in (ii) ranges between 6 hours and 50 days.

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

21. Process for the direct synthesis of a material according to claim 1 , wherein the recovery step (iii) is performed by means of a separation technique selected from decantation, filtration, ultrafiltration, centrifugation, and combinations thereof.

22. Process for the direct synthesis of a material according to claim 1 , further comprising the elimination of the organic content retained inside the material by an extraction process.

23. Process for the direct synthesis of a material 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 25 hours.

24. Process for the direct synthesis of a material according to claim 1 , wherein the material obtained is pelletised.

25. Process for the direct synthesis of a material according to claim 1 , further comprising the introduction of at least one precious metal.

26. Process for the direct synthesis of a material according to claim 25 , wherein the precious metal is selected from Pd, Pt, and combinations thereof.

27. Process for the direct synthesis of a material with the copper-containing silicoaluminate form of the AEI zeolite structure, which comprises, at least, the following steps:
(i) Preparation of a mixture containing, at least,
one source of water,
one source of copper,
one polyamine, selected from tetraethylenepentamine, triethylenetetramine, 1,4,8,11-tetraazacyclotetradecane, 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane, or mixtures thereof,
one source of tetravalent element Y, which is Si, and one source of trivalent element X, which is Al, wherein a zeolite with the FAU structure is the only source of Y and X,
one cyclic ammonium cation with alkyl substituents as the OSDA, 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 and
one source of alkaline or alkaline-earth cations (A), selected from a source of Na, K, and combinations thereof, where the synthesis mixture has the following molar composition:
YO 2 :a X 2 O 3 :b OSDA: c A: d H 2 O: e Cu: f Polyamine

where
a ranges between 0.001 and 0.2;
b ranges between 0.01 and 2;
c ranges between 0.01 and 0.8;
d ranges between 1 and 200;
e ranges between 0.001 and 1;
f ranges between 0.001 and 1;
and wherein the molar ratio of A:YO 2 is at least 0.1,

wherein the mixture formed in (i) is free from any source of ph

Assignees

• Consejo Superior Investigacion
• Univ Valencia Politecnica

Inventors

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

Classifications

• B01J37/009

  Preparation by separation, e.g. by filtration, decantation, screening · CPC title

• B01D2255/50

  Zeolites · CPC title

• B01D53/9418 Primary

  for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas · CPC title

• B01J37/10

  in the presence of water, e.g. steam · CPC title

• C01B39/48 Primary

  using at least one organic template directing agent · CPC title