Process for the direct synthesis of Cu-SAPO-34

Patent metadata

Field	Value
Publication number	US-9561498-B2
Application number	US-201214395872-A
Country	US
Kind code	B2
Filing date	Apr 27, 2012
Priority date	Apr 27, 2012
Publication date	Feb 7, 2017
Grant date	Feb 7, 2017

Abstract

A process for the direct synthesis of Cu-SAPO-34 comprising at least the steps: preparation of a mixture of water, at least one silicon source, at least one Al source, at least one P source, at least one Cu source, at least one 0SDA1 (any polyamine), and at least one OSDA2 source (where OSDA2 is any organic molecule capable of directing the synthesis of SAPO 34); and where the final synthesis mixture has the molar composition: a Si:0.5 Al:c Cu:d OSDA1:e OSDA2:f H2O wherein a is in the range from 0.01 to 0.3; b is in the range from 0.2 to 0.49; c is in the range from 0.001 to 0.6; d is in the range from 0.001 to 0.6; e is in the range from 0.001 to 2; f is in the range 1 to 200; hydrothermal treatment of the mixture at 80−200° C. until formation of the crystalline material, and recovery of the crystalline material.

First claim

The invention claimed is:

1. Process for the direct synthesis of Cu-SAPO-34 comprising the steps of:
(i) preparing a synthesis mixture containing water, at least one silicon source, at least one Al source, at least one P source, at least one Cu source, at least one OSDA1 wherein the OSDA1 is a polyamine selected from the group of tetraethylenepentamine, triethylenetetramine, 1,4,8,11-tetraazacyclotetradecane or 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane, and at least one OSDA2, wherein the OSDA2 is an organic compound different from polyamine and capable of directing the synthesis of the SAPO-34 and a final synthesis mixture having a molar composition of:
a Si:0.5 Al:b P:c Cu:d OSDA1:e OSDA2:fH2O
where a is in the range from 0.01 to 0.3;
where b is in the range from 0.2 to 0.49;
where c is in the range from 0.001 to 0.6;
where d is in the range from 0.001 to 0.6;
where e is in the range from 0.001 to 2;
where f is in the range from 1 to 200;
(ii) hydrothermally treating the mixture at 80-200° C. until formation of crystalline material,
(iii) recovering of the crystalline material,
(iv) removing OSDA1 and OSDA2 from the crystalline material.

2. The process according to claim 1 , wherein the OSDA1 comprises at least one of tetraethylenepentamine, triethylenetetramine, 1,4,8,11-tetraazacyclotetradecane, 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane.

3. The process of claim 1 , wherein the OSDA2 comprises at least one of diethylamine, dipropylamine, triethanolamine, cyclohexylamine, morpholine, salts of tetraethylammonium, pidepiridine.

4. The process of claim 1 , wherein the final synthesis mixture comprises the following molar compositions:
a Si:0.5 Al:b P:c Cu:d OSDA1:e OSDA2:fH2O
wherein a is in the range from 0.05 to 0.3;
wherein b is in the range from 0.2 to 0.45;
wherein c is in the range from 0.01 to 0.4;
wherein d is in the range from 0.01 to 0.4;
wherein e is in the range from 0.1 to 1; and
wherein f is in the range from 2 to 100.

5. The process of claim 1 , wherein the crystallization step (ii) is performed in an autoclave, under static or dynamic conditions.

6. The process of claim 1 , wherein the temperature in step (ii) is in the range of 100 to 200° C.

7. The process of claim 1 , wherein the crystallization time in step (ii) is in the range from 6 hours to 50 days.

8. The process of claim 1 , wherein crystals of a CHA zeolite or zeotype are added as seeds, in quantities up to 25% by weight with respect to the total amount of oxides in the synthesis mixture before or during the crystallization of Cu-SAPO-34.

9. The process of claim 1 , wherein the elimination of OSDA 1and OSDA2 in step (iv) from the crystalline material is performed by extraction and/or thermal treatment at temperatures above 25° C., during a period of time between 2 minutes and 25 hours.

10. The process of claim 1 , wherein the pH value of the synthesis mixture is below 9.

Assignees

• Franco Raquel Martinez
• Marin Manuel Moliner
• Canós Avelino Corma
• Kustov Arkady
• Thøgersen Joakim Reimer
• Haldor Topsoe As

Inventors

• Franco Raquel Martinez
• Marin Manuel Moliner
• Canós Avelino Corma
• Kustov Arkady
• Thøgersen Joakim Reimer

Classifications

• C01B39/54

  Phosphates, e.g. APO or SAPO compounds · CPC title

• C01B37/08

  Silicoaluminophosphates [SAPO compounds] {, e.g. CoSAPO} · CPC title

• B01J2229/186

  not in framework positions · CPC title

• B01J29/85 Primary

  Silicoaluminophosphates [SAPO compounds] · CPC title

• B01D53/9418

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