Direct synthesis of Cu-CHA by means of combining a Cu complex and tetraethylammonium and applications in catalysis

Patent metadata

Field	Value
Publication number	US-10676367-B2
Application number	US-201615569700-A
Country	US
Kind code	B2
Filing date	May 3, 2016
Priority date	May 5, 2015
Publication date	Jun 9, 2020
Grant date	Jun 9, 2020

Abstract

The present invention relates to a process for the direct synthesis of a material with a CHA zeolite structure in the silicoaluminate form thereof containing copper atoms, which comprises at least the following steps:
(i) Preparation of a mixture which contains at least one water source, one copper source, one polyamine, one source of Y tetravalent element, one source of X trivalent element, the tetraethylammonium cation as the only OSDA and one source of alkaline or alkaline earth (A) cations, and wherein the synthesis mixture has the following molar composition:

YO 2 :aX 2 O 3 :bOSDA:cA:dH 2 O:eCu:fpolyamine
(ii) Crystallization of the mixture obtained in (i) in a reactor; (iii) Recovery of the crystalline material obtained in (ii).

First claim

The invention claimed is:

1. A process for the direct synthesis of a material with a CHA zeolite structure in the silicoaluminate form thereof containing copper atoms, which comprises at least the following steps:
(i) Preparation of a mixture which contains at least
one water source,
one copper source,
one polyamine, selected from tetraethylenepentamine, triethylenetetramine, 1,4,8,11-tetraazacyclotetradecane, 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane, and combinations thereof,
one source of Y tetravalent element, which is Si, and one source of X trivalent element, which is Al, wherein a zeolite with an FAU structure is the only source of Y and X,
tetraethylammonium cations as the only OSDA, and
one source of alkaline or alkaline earth (A) cations, selected from a source of Na, K, and combinations thereof, and wherein the synthesis mixture has the following molar composition:
YO 2 :aX 2 O 3 :bOSDA:cA:dH 2 O:eCu:fpolyamine

wherein
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;

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

2. The process for the direct synthesis of a material according to claim 1 , wherein any copper source can be used in step (i).

3. The process for the direct synthesis of a material according to claim 2 , wherein the copper source is selected from nitrate, sulfate and oxalate salts, or mixtures thereof.

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

5. The process for the direct synthesis of a material according to claim 4 , wherein the polyamine used in step (i) is tetraethylenepentamine.

6. The process for the direct synthesis of a material according to claim 1 , wherein the crystallization process described in (ii) is carried out in autoclaves, in static or dynamic conditions.

7. The process for the direct synthesis of a material according to claim 1 , wherein the crystallization process described in (ii) is carried out at a temperature between 100 and 200° C.

8. The process for the direct synthesis of a material according to claim 1 , wherein the crystallization time of the process described in (ii) is between 6 hours and 50 days.

9. The process for the direct synthesis of a material according to claim 1 , further comprising adding CHA crystals as seeds to the synthesis mixture in a quantity up to 25% by weight with respect to the total quantity of oxides.

10. The process for the direct synthesis of a material according to claim 1 , wherein the recovery step (iii) is carried out using a separation technique selected from among decantation, filtration, ultrafiltration, centrifugation, and combinations thereof.

11. The process for the direct synthesis of a material according to claim 1 , further comprising extracting the organic content confined in the interior of the material.

12. The process for the direct synthesis of a material according to claim 1 , further comprising removing the organic content confined in the interior of the material by means of heat treatment at temperatures of between 100 and 1000° C. for a period of time of between 2 minutes and 25 hours.

13. The process for the direct synthesis of a material according to claim 1 , further comprising pelletizing the recovered crystalline material.

14. The process for the direct synthesis of a material according to claim 1 , further comprising introducing at least one precious metal.

15. The process for the direct synthesis of a material according to claim 14 , wherein the precious metal is selected from Pd, Pt, and combinations thereof.

16. A zeolite material with a CHA structure obtained according to the process according to claim 1 , comprising the following molar composition after being calcined:
YO 2 :oX 2 O 3 :pA:rCu
wherein o ranges between 0.001 and 0.2;
wherein p ranges between 0 and 2;
wherein r ranges between 0.001 and 1.

17. The zeolite material with a CHA structure obtained according to claim 16 , wherein Y is Si and X is Al and the zeolite material comprises following molar composition:
SiO 2 :oAl 2 O 3 :pA:rCu
wherein o ranges between 0.001 and 0.2;
wherein p ranges between 0 and 2;
wherein r ranges between 0.001 and 1.

18. The zeolite material with a CHA structure obtained according to claim 16 wherein the material is Cu-SSZ-13.

19. The zeolite material with a CHA structure obtained according to claim 16 , further comprising a precious metal.

20. The zeolite material with a CHA structure obtained according to claim 19 , wherein the precious metal is selected from Pd, Pt, and combinations thereof.

21. A method of removing a component from a supply current, which comprises using the zeolite material according to claim 16 as molecular sieve by contacting the zeolite material with the supply current.

22. A method of performing selective catalytic reduction (SCR) of nitrogen oxides (NO x ) in a gaseous current, which comprises contacting the gaseous current with the zeolite material according to claim 16 .

23. The the method according to claim 22 , which comprises adding a reducing agent, selected from ammonia, urea, hydrocarbons and combinations thereof to the gaseous current.

24. A method of converting methane into methanol, which comprises contacting the methane with the zeolite material according to claim 16 .

25. A method for selective oxidation of ammonia to nitrogen, which comprises contacting the ammonia with the zeolite material according to claim 16 .

Assignees

• Consejo Superior Investigacion
• Univ Valencia Politecnica

Inventors

• Corma Canós Avelino
• Moliner Marín Manuel
• Martin Garcia Nuria

Classifications

• B01D53/9418

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

• B01J35/002

  Operations & Transport · mapped topic

• C01B39/48 Primary

  using at least one organic template directing agent · CPC title

• C01B39/026 Primary

  After-treatment · CPC title

• B01D2255/50

  Zeolites · CPC title