One-Pot Synthesis of Copper Containing Small-Pore Zeolites

Abstract

The present invention relates to a process for the manufacture of a copper containing small-pore zeolite which comprisespreparing a reaction mixture comprising a zeolite of the faujasite framework type, Cu-tetraethylenepentamine (Cu-TEPA) and at least one compound M(OH)x, which does not comprise the tetraethylammonium cation andheating the reaction mixture to form a copper containing small-pore zeolite.

Claims

1. A process for the manufacture of a copper containing small-pore zeolite which comprises preparing a reaction mixture comprising a zeolite of the faujasite framework type, Cu-tetraethylenepentamine (Cu-TEPA) and at least one compound M(OH).sub.x, wherein x is 1 if M is selected from the group consisting of lithium, sodium, potassium, rubidium and cesium, and wherein x is 2 if M is selected from the group consisting of magnesium, calcium, strontium and barium and which does not comprise the tetraethylammonium cation,. and heating the reaction mixture to form a copper containing small-pore zeolite.

2. The process according to claim 1, wherein tetraethylenepentamin is the only organic molecule in the reaction mixture.

3. The process according to claim 1, which comprises preparing an aqueous reaction mixture consisting of a zeolite of the faujasite framework type, Cu-tetraethylenepentamine (Cu-TEPA) and at least one compound M(OH).sub.x, wherein x is 1 if M is selected from the group consisting of lithium, sodium, potassium, rubidium and cesium, and wherein x is 2 if M is selected from the group consisting of magnesium, calcium, strontium and barium, and heating the reaction mixture to form a copper containing small-pore zeolite.

4. The process according to claim 1, wherein it is performed at temperatures of 80 to 150 C.

5. The process according to claim 1, wherein it is performed at temperatures of 90 to 98 C.

6. The process according to claim 1, wherein it is finished within 2 to 31 days.

7. The process according to claim 1, wherein the zeolite of the faujasite framework type has a Si/Al ratio in the range from 2.4 to 30.

8. The process according to claim 1, wherein the copper content of the copper containing small-pore zeolite is 1 to 10 wt %, calculated as CuO and based on the total weight of the copper containing small-pore zeolite.

9. The process according to claim 1, wherein Cu-TEPA is used in an amount of 0.0001 mole/wt Cu-TEPA/FAU zeolite to 0.0016 mole/wt Cu-TEPA/FAU zeolite.

10. The process according to claim 1, wherein the compound M(OH)x is CsOH and the copper containing small-pore zeolite obtained is of the ANA framework type.

11. The process according to claim 1, wherein the compound M(OH).sub.x is LiOH and the copper containing small-pore zeolite obtained is of the ABW framework type.

12. The process according to claim 1, wherein the compound M(OH).sub.x is NaOH and/or KOH and the copper containing small-pore zeolite obtained is of the CHA framework type.

13. The process according to claim 1, wherein M(OH).sub.x is used in an amount of 0.001 mole/wt MOH/FAU zeolite to 0.025mole/wt MOH/FAU zeolite.

14. The process according to claim 1, wherein crystallization of the resulting copper containing small-pore zeolite is supported by the addition of seed crystals of the respective framework type.

Description

EXAMPLE 1

[0048] a) Synthesis of Cu-Tetraethylenepentamine complex (Cu-TEPA): 37.9 g tetraethylenepentamine (0.2 mole) was added under stirring to a solution consisting of 50 g CuSO.sub.4.5H.sub.2O (0.2 mole) in 200 g of H.sub.2O (1 M solution) and left to stir for 2 h at room temperature.

[0049] b) 3 g of zeolite Y with SAR=30 (Si/Al=15) (CBV720 supplied by Zeolyst International) was suspended in 27 mL of a 1.2 M solution of sodium hydroxide. To this solution 1.5 mL of a 1 M Cu-TEPA solution was added. The final gel had the following molar ratios: 1 SiO.sub.2/0.033 Al.sub.2O.sub.3/0.033 Cu-TEPA/0.70 NaOH/34 H.sub.2O. The suspension was stirred for 10 minutes at room temperature, before being transferred to an oven at 95 C. and left statically for 7 days. After cooling to room temperature, the powder was separated from the mother liquor by filtration, washed with demineralized water and dried at 60 C. for 12 h. The zeolite produced was determined to have the CHA framework type code according to X-ray diffraction (see FIG. 1) with a Si/Al ratio of 4.3 and a CuO content of 7.5 wt. %. FIG. 2 shows the morphology and crystal size of the product obtained.

EXAMPLE 2

[0050] A mixture of 1.5 g of zeolite Y with SAR=30 (Si/Al=15) (CBV720 supplied by Zeolyst International) and 1.5 g of zeolite Y with SAR=5.1 (Si/Al=2.55) (CBV300 supplied by Zeolyst International) was suspended in 27 mL of a 1.2 M solution of potassium hydroxide. To this solution 3 mL of a 1 M Cu-TEPA solution was added. The final gel has the following molar ratios: 1 SiO.sub.2/0.10 Al.sub.2O.sub.3/0.076 Cu-TEPA/0.82 KOH/42 H.sub.2O. The suspension was stirred for 10 minutes at room temperature, before being transferred to an oven at 95 C. and left statically for 5 days. After cooling to room temperature, the powder was separated from the mother liquor by filtration, washed with demineralized water and dried at 60 C. for 12 h. The zeolite produced was determined to have the CHA framework type code with a Si/Al ratio of 3.3 and a CuO content of 6.4 wt. %

EXAMPLE b 3

[0051] Example 2 was repeated with the exception that 27 mL of a 1.2 M solution of sodium hydroxide was issued instead of potassium hydroxide. The final gel has the following molar ratios: 1 SiO.sub.2/0.10 Al.sub.2O.sub.3/0.076 Cu-TEPA/0.82 NaOH/42 H.sub.2O. The zeolite produced after 11 days was determined to have the CHA framework type code with a Si/Al ratio of 2.9 and a CuO content of 8 wt. %.

EXAMPLE 4

[0052] 6 g of zeolite Y with SAR=12 (Si/Al=6) (CBV712 supplied by Zeolyst International) was suspended in 54 mL of a 1.2 M solution of potassium hydroxide. To this solution 6 mL of a 1 M Cu-TEPA solution was added. The final gel has the following molar ratios: 1 SiO.sub.2/0.08 Al.sub.2O.sub.3/0.073 Cu-TEPA/0.79 KOH/40 H.sub.2O. The suspension was stirred for 10 minutes at room temperature, before being transferred to an oven at 95 C. and left statically for 6 days. After cooling to room temperature, the powder was separated from the mother liquor by filtrations, washed with demineralized water and dried at 60 C. for 12 h. The zeolite produced was determined to have the CHA framework type code with a Si/Al ratio of 3.6 and a CuO content of 5.5 wt. %

EXAMPLE 5

[0053] Example 4 was repeated with the exception that 54 mL of a 1.2 M solution of sodium hydroxide was issued instead if potassium hydroxide. The final gel has the following molar ratios: 1 SiO.sub.2/0.08 Al.sub.2O.sub.3/0.073 Cu-TEPA/0.79 NaOH/40 H.sub.2O. The zeolite produced after 31 days was determined to have the CHA framework type code

EXAMPLE 6

[0054] 2.5 g of zeolite Y with SAR=12 (Si/Al=6) (CBV712 supplied by Zeolyst International) was suspended in 25 mL of a 1 M Cu-TEPA solution. The suspension was stirred for 2 days at room temperature. The solids were recovered by filtration and washing with demineralized water and dried at 60 C. for 12 h. 1 g of the obtained powder was suspended in 9 mL of a 1.2 M solution of potassium hydroxide. The suspension was stirred for 10 minutes at room temperature, before being transferred to an oven at 95 C. and left statically for 2 days. After cooling to room temperature, the powder was separated from the mother liquor by filtrations, washed with demineralized water and dried at 60 C. for 12 h. The zeolite produced was determined to have the CHA framework type code.

EXAMPLE 7

[0055] 1.5 g of zeolite Y with SAR=12 (Si/Al=6) (CBV712 supplied by Zeolyst International) was suspended in 13.5 mL of a 1.2 M solution of cesium hydroxide. To this solution 1.5 mL of a 1 M Cu-TEPA solution was added. The final gel has the following molar ratios: 1 SiO.sub.2/0.08 Al.sub.2O.sub.3/0.073 Cu-TEPA/0.79 CsOH/40 H.sub.2O. The suspension was stirred for 10 minutes at room temperature, before being transferred to an oven at 95 C. and left statically for 11 days. After cooling to room temperature, the powder was separated from the mother liquor by filtrations, washed with demineralized water and dried at 60 C. for 12 h. The zeolite produced was determined to have the ANA framework type code.

EXAMPLE 8

[0056] 6 g of zeolite Y with SAR=5.1 (Si/Al=2.55) (CBV300 supplied by Zeolyst International) was suspended in 54 mL of a 1.2 M solution of lithium hydroxide. To this solution 6 mL of a 1 M Cu-TEPA solution was added. The suspension was stirred for 10 minutes at room temperature, before being transferred to an oven at 95 C. and left statically for 5 days. After cooling to room temperature, the powder was separated from the mother liquor by filtrations, washed with demineralized water and dried at 60 C. for 12 h. The zeolite produced was determined to have the ABW framework type code.

EXAMPLE 9

[0057] 1.5 g of zeolite Y with SAR=12 (Si/Al=6) (CBV712 supplied by Zeolyst International) was suspended in 13.5 mL of a 1.2 M solution of sodium hydroxide. To this solution 1.5 mL of a 1 M Cu-TEPA solution was added. The final gel has the following molar ratios: 1 SiO.sub.2/0.20 Al.sub.2O.sub.3/0.090 Cu-TEPA/0.98 LiOH/50 H.sub.2O. The suspension was stirred for 10 minutes at room temperature, before being transferred to an oven at 95 C. and left statically for 11 days. After cooling to room temperature, the powder was separated from the mother liquor by filtrations, washed with demineralized water and dried at 60 C. for 12 h. The zeolite produced was determined to have the PHI framework type code.

EXAMPLE 10

[0058] 4.5 g of zeolite Y with SAR=12 (Si/Al=6) (CBV712 supplied by Zeolyst International) was suspended in 40.5 mL of a 1.2 M solution of sodium hydroxide. To this solution 2.25 mL of a 1 M Cu-TEPA solution was added. The final gel has the following molar ratios: 1 SiO.sub.2/0.08 Al.sub.2O.sub.3/0.036 Cu-TEPA/0.79 NaOH/38 H.sub.2O. The suspension was stirred for 10 minutes at room temperature, before being transferred to an oven at 95 C. and left statically for 6 days. After cooling to room temperature, the powder was separated from the mother liquor by filtrations, washed with demineralized water and dried at 60 C. for 12 h. The zeolite produced was determined to be a mixture of CHA and GME framework types.