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