CHA type zeolitic materials and methods for their preparation using combinations of cycloalkyl-and tetraalkylammonium compounds

Patent metadata

Field	Value
Publication number	US-10315924-B2
Application number	US-201515315636-A
Country	US
Kind code	B2
Filing date	Jun 3, 2015
Priority date	Jun 5, 2014
Publication date	Jun 11, 2019
Grant date	Jun 11, 2019

Abstract

The present invention relates to a process for the preparation of a zeolitic material having a CHA-type framework structure comprising YO 2 and X 2 O 3 , wherein said process comprises the steps of:
(1) providing a mixture comprising one or more sources for YO 2 , one or more sources for X 2 O 3 , one or more tetraalkylammonium cation R 1 R 2 R 3 R 4 N + -containing compounds, and one or more tetraalkylammonium cation R 5 R 6 R 7 R 8 N + -containing compounds as structure directing agent; (2) crystallizing the mixture obtained in step (1) for obtaining a zeolitic material having a CHA-type framework structure; wherein Y is a tetravalent element and X is a trivalent element, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 independently from one another stand for alkyl, and wherein R 8 stands for cycloalkyl, as well as to zeolitic materials which may be obtained according to the inventive process and to their use.

First claim

The invention claimed is:

1. A process for the preparation of a zeolitic material having a CHA-type framework structure comprising SiO 2 and Al 2 O 3 , wherein said process comprises the steps of:
(1) providing a mixture comprising one or more sources for SiO 2 , one or more sources for Al 2 O 3 , one or more tetramethylammonium compounds, and one or more N,N,N-trimethyl-cyclohexylammonium compounds as structure directing agent;
(2) crystallizing the mixture obtained in step (1) for obtaining the zeolitic material having a CHA-type framework structure;
wherein the molar ratio of tetramethylammonium compounds to N,N,N-trimethyl-cyclohexylammonium compounds is comprised in the range from 0.45 to 0.65.

2. The process of claim 1 , wherein the crystallization in step (2) is conducted under solvothermal conditions.

3. The process of claim 1 , wherein the mixture provided in step (1) does not contain any substantial amount of a trimethyl benzyl ammonium containing compound.

4. The process of claim 1 , wherein the mixture provided in step (1) further comprises seed crystals.

5. A synthetic zeolitic material having a CHA-type framework structure prepared by the process of claim 1 .

6. A synthetic zeolitic material having a CHA-type framework structure, prepared by the process of claim 1 , wherein the CHA-type framework structure comprises SiO 2 and Al 2 O 3 , and wherein the IR-spectrum of the zeolitic material includes:
a first absorption band (B1) in the range of from 3,720 to 3,740 cm −1 ; and
a second absorption band (B2) in the range of from 1,850 to 1,890 cm −1 ;
wherein the ratio of the maximum absorbance of the first absorption band to the second absorption band B1:B2 is in the range of from 0.5 to 1.55.

7. The zeolitic material of claim 6 , wherein the particle size D10 of the zeolitic material is comprised in the range of from 400 to 2500 nm.

8. The zeolitic material of claim 6 , wherein the average particle size D50 of the zeolitic material is comprised in the range of from 600 to 3500 nm.

9. The zeolitic material of claim 6 , wherein the particle size D90 of the zeolitic material is comprised in the range of from 1200 to 4,500 nm.

10. The zeolitic material of claim 6 , wherein the CHA-type framework contains 5 wt.-% or less of the elements P and/or As based on 100 wt-% of SiO 2 contained in the framework structure.

11. The zeolitic material of claim 6 , wherein the 29 Si MAS NMR of the zeolitic material includes:
a first peak (P′1) in the range of from −102.0 to −106.0 ppm; and
a second peak (P′2) in the range of from −108.0 to −112.5 ppm,
wherein the integration of the first and second peaks in the 29 Si MAS NMR of the zeolitic material offers a ratio of the integration values P′1:P′2 comprised in the range of from 0.05 to 0.90.

12. The zeolitic material of claim 6 , wherein the SiO 2 :Al 2 O 3 molar ratio ranges from 4 to 200.

13. The synthetic zeolitic material of claim 6 , wherein the material is an adsorbent material, an ion-exchange material, a catalyst or a catalyst support.

14. A synthetic zeolitic material having a CHA-type framework structure, prepared by the process of claim 1 , wherein the CHA-type framework structure comprises SiO 2 and Al 2 O 3 , and wherein the IR-spectrum of the zeolitic material includes:
a first absorption band (B1) in the range of from 3,720 to 3,740 cm −1 ; and
a second absorption band (B2) in the range of from 1,850 to 1,890 cm −1 ;
wherein the ratio of the maximum absorbance of the first absorption band to the second absorption band B1:B2 is in the range of from 0.5 to 1.55;
wherein the particle size D10 of the zeolitic material is in a range of from 400 to 2500 nm, the average particle size D50 of the zeolitic material is in a range of from 600 to 3500 nm, and the particle size D90 of the zeolitic material is in a range of from 1200 to 4,500 nm, and
a 29 Si MAS NMR spectrum of the zeolitic material includes:

a first peak (P′1) in the range of from −102.0 to −106.0 ppm; and
a second peak (P′2) in the range of from −108.0 to −112.5 ppm,
wherein the integration of the first and second peaks in the 29 Si MAS NMR of the zeolitic material offers a ratio of the integration values P′1:P′2 comprised in the range of from 0.05 to 0.90.

Assignees

• Basf Se

Inventors

• Feyen Mathias
• Yang Jeff
• Ruetz Roger
• Müller Ulrich

Classifications

• C01B39/48 Primary

  using at least one organic template directing agent · CPC title

• B01J2229/42

  Addition of matrix or binder particles · CPC title

• B01J2229/186

  not in framework positions · CPC title

• B01J2220/42

  Materials comprising a mixture of inorganic materials (materials coated or impregnated on a carrier B01J20/32) · CPC title

• B01J37/0246

  Coatings comprising a zeolite · CPC title