A PROCESS FOR PREPARING A POROUS OXIDIC MATERIAL WHICH COMPRISES MICROPORES AND MESOPORES AND WHICH COMPRISES A ZEOLITIC MATERIAL HAVING A FRAMEWORK TYPE AEI

Abstract

A process for preparing a porous oxidic material with micropores and mesopores and a zeolitic material having an AEI framework with a tetravalent element Y, a trivalent element X and oxygen, the micropores having a pore diameter determined by nitrogen adsorption-desorption at 77 K of less than 2 nm and the mesopores having a pore diameter of from 2 to 50 nm, the process involving subjecting a synthesis mixture to hydrothermal crystallization at a crystallization temperature of from 90 to 200° C., to obtain a mother liquor containing the porous oxidic material having the zeolitic AEI framework. The synthesis mixture may have a zeolitic material with an FAU framework comprising Y, X, and O, water, a base source, a first organic structure directing agent as an AEI framework type structure directing agent, a second organic structure directing agent with a dimethyl-octadecyl[3-(trimethoxysilyl)-propyl]ammonium cation, and seed crystals

Claims

1. A process for preparing a porous oxidic material the process comprising: crystallizing, at a crystallization temperature in the range of from 90 to 200° C., a synthesis mixture, to obtain a mother liquor comprising the porous oxidic material comprising said zeolitic material having an AEI framework, wherein the synthesis mixture comprises a zeolitic material having an FAU framework comprising a tetravalent element Y, a trivalent element X, and O, and water, a base source, a first organic structure directing agent as an AEI framework structure directing agent, a second organic structure directing agent comprising a dimethyl-octadecyl[3-(trimethoxysilyl)-propyl]ammonium cation, and seed crystals, wherein Y comprises Si, Sn, Ti, Zr, and/or Ge, wherein X comprises Al, B, In, and/or Ga, and wherein the porous oxidic material comprises micropores and mesopores, and a zeolitic material having an AEI framework comprising a tetravalent element, Y, a trivalent element, X, and oxygen, the micropores having a pore diameter determined by nitrogen adsorption-desorption at 77 K of less than 2 nm and the mesopores having a pore diameter determined by nitrogen adsorption-desorption at 77 K in a range of from 2 to 50 nm.

2. The process of claim 1, wherein the first structure directing agent comprises: a quaternary phosphonium cation comprising compound; and a N,N-diethyl-2,6-dimethylpiperidinium cation comprising compound.

3. The process of claim 1, wherein the second organic structure directing agent comprises a salt of the dimethyloctadecyl[3-(trimethoxysilyl)propyl]-ammonium cation.

4. The process of claim 1, wherein Y is Si.

5. The process of claim 1, wherein the zeolitic material having the FAU framework type a faujasite zeolite, a zeolite Y, a zeolite X, an LSZ-210 zeolite, and/or a zeolite USY, and wherein, in the FAU framework, a molar ratio of Y:X, calculated as YO.sub.2:X.sub.2O.sub.3, is optionally in a range of from 5:1 to 100:1.

6. The process of claim 1, wherein, in the synthesis mixture, a molar ratio of the first organic structure directing agent, FOSDA, relative to Y, calculated as FOSDA:YO.sub.2, is in a range of from 0.05:1 to 0.30:1.

7. The process of claim 1, wherein, in the synthesis mixture, a molar ratio of the second organic structure directing agent, SOSDA, relative to Y, calculated as SOSDA:YO.sub.2, is in a range of from 0.001:1 to 0.070:1.

8. The process of claim 1, wherein, in the synthesis mixture, a molar ratio of the base source of a base relative to Y, calculated as base source: YO.sub.2, is in a range of from 0.10:1 to 0.70:1.

9. The process of claim 1, wherein, in the synthesis mixture, a molar ratio of H.sub.2O relative to Y, calculated as H.sub.2O:YO.sub.2, is in a range of from 2:1 to 80:1.

10. The process of claim 1, wherein, the seed crystals comprise a zeolitic material having an AEI, CHA, or RTH framework. wherein, in the synthesis mixture, a weight ratio of the seed crystals to the zeolitic material having the FAU framework is optionally in a range of from 0.001:1 to 0.1:1.

11. The process of claim 1, wherein the synthesis mixture is prepared by a process comprising: (i.1) preparing a first mixture comprising the zeolitic material having the FAU framework comprising the tetravalent element Y, trivalent element X, oxygen, water, and the first organic structure directing agent; (i.2) adding the base source to the first mixture to obtain a second mixture; (i.3) adding the second organic structure directing agent to the second mixture to obtain a third mixture; (i.4) adding the seed crystals to the third mixture, to obtain the synthesis mixture.

12. The process of claim 1, wherein the hydrothermally crystallizing comprises a crystallization duration in a range of from 0.75 to 20 days.

13. The process of claim 1, wherein during hydrothermally crystallizing the synthesis mixture is agitated.

14. The process of claim 1, further comprising: (iii) optionally cooling the mother liquor comprising the porous oxidic material comprising the zeolitic material having the AEl framework. (iv) separating the porous oxidic material from the mother liquor; and (vi) optionally subjecting the porous oxidic material after (iv) to ion-exchange conditions.

15. The process of claim 1, wherein the micropores have a micropore volume and the mesopores have a mesopore volume, wherein a ratio of the mesopore volume to the micropore volume of the porous oxidic material is at least 0.5:1, and wherein a ratio of the mesopore volume to a total pore volume of the porous oxidic material is at least 0.3:1.

16. The process of claim 14, wherein the subjecting (vi) comprises: (vi.1) bringing a solution comprising ammonium ions into contact with the porous oxidic material, to obtain a porous oxidic material in its ammonium form; (vi.2) calcining the porous oxidic material obtained in (vi.1) in a gas atmosphere, to obtain the H-form of the porous oxidic material; (vi.3) optionally bringing a solution comprising transition metal ion into contact with the porous oxidic material obtained from (vi.2) under ion-exchange conditions; (vi.4) calcining the porous oxidic material obtained in (vi.3) or after the calcining (vi.2) in a gas atmosphere.

17. A porous oxidic material, comprising: micropores; mesopores: a zeolitic material having an AEI framework comprising a tetravalent element Y, a trivalent element X, and oxygen, wherein the micropores have a pore diameter, determined by nitrogen adsorption-desorption at 77 K, of less than 2 nm, wherein the mesopores have a pore diameter, determined by nitrogen adsorption-desorption at 77 K, in a range of from 2 to 50 nm, wherein Y is Si, Sn, Ti, Zr, and/or Ge, wherein X is Al, B, In, and/or Ga, wherein the micropores have a micropore volume and the mesopores have a mesopore volume, wherein a ratio of the mesopore volume to the micropore volume is at least 0.5:1, and wherein a ratio of the mesopore volume to a total pore volume of the porous oxidic material is at least 0.3:1.

18. The material of claim 17, wherein, in the AEI framework, a molar ratio of Y:X, calculated as a YO.sub.2:X.sub.2O.sub.3, is in a range of from 2:1 to 40:1.

19. The material of claim 17, having a BET specific surface area, determined N.sub.2 sorption isotherms at liquid nitrogen temperature using a MICROMERITICS ASAP 2020M or FINESORB-3020M instrument and a TRISTAR system in a range of from 500 to 900 m.sup.2/g.

20. The material of claim 17, wherein the mesopore volume is in the range of from 0.15 to 0.80 cm.sup.3/g.

21. The porous oxidic material of claim 17, wherein the ratio of the mesopore volume to the micropore volume is in the range of from 0.5:1 to 3:1.

22. The material of claim 17, wherein the zeolitic material having the AIE framework has an X-ray diffraction pattern which comprising, with CuK (α1), reflections at: a diffraction angle 2 θ of 8.5 to 10.5°, and an intensity of 90 to 100%; a diffraction angle 2 θ of 15.1 to 17.1°, and an intensity of 75 to 95%; a diffraction angle 2 θ of 15.9 to 17.9°, and an intensity of 80 to 100%; a diffraction angle 2 θ of 16.2 to 18.2°, and an intensity of 80 to 100%; a diffraction angle 2 θ of 19.7 to 21.7°, and an intensity of 80 to 100%; a diffraction angle 2 θ of 20.4 to 22.4°, and an intensity of 50 to 70%; a diffraction angle 2 θ of 23.2 to 25.2°, and an intensity of 80 to 100%; a diffraction angle 2 θ of 25.3 to 27.3°, and an intensity of 30 to 50%; a diffraction angle 2 θ of 30.2 to 32.2°, and an intensity of 40 to 60%; wherein 100% relates to an intensity of a maximum peak in an X-ray powder diffraction pattern.

23. The material of claim 17, further comprising: a transition metal.

24. A method for catalytically converting methanol to one or more olefins, the method comprising: contacting a gas stream comprising methanol with a catalyst comprising the material of claim 17 in a reactor, obtaining a reaction mixture comprising one or more olefins.

25. A catalytically active material, as a catalyst, or as a catalyst component, comprising the material of claim 17.

Description

BRIEF DESCRIPTION OF THE FIGURES

[0448] FIG. 1: shows the XRD patterns of the respectively obtained AEI zeolitic materials according to a) of Examples 1 and 2 and of Comparative Example 1

[0449] FIG. 2a: shows the SEM image of the respectively obtained fresh AEI zeolitic material (low magnification: scale bar 1 micrometer) according to a) of Example 1.

[0450] FIG. 2b: shows the SEM image of the respectively obtained fresh AEI zeolitic material (high magnification: scale bar 500 nanometers) according to a) of Example 1.

[0451] FIG. 3: shows the crystallization curve of the zeolitic material according to a) of Example 1.

[0452] FIG. 4: shows the XRD patterns of the respectively obtained AEI zeolitic material according to a) of Example 1 after crystallization duration of 0 hour to 11 days. After 6 hours of crystallization, the XRD pattern of the zeolitic material shows the characteristic peaks related to zeolite Y (starting material), namely a high intensity peak around 6° (2Theta), a high intensity peak around 12° (2Theta), a high intensity peak around 16° (2Theta), a high intensity peak around 24° (2Theta) and a high intensity peak around 27° (2Theta). Alter 3 days of crystallization, the XRD pattern of the zeolitic material shows peaks associated with the framework structure AEI, namely a peak at around 9.5° 2Theta (highest intensity), a peak at around 16.1° 2Theta, a peak at around 16.9° 2Theta, a peak at around 17.2° 2Theta, a peak at around 20.7° 2Theta, a peak at around 21.4° 2Theta, a peak at 24.0 2Theta, a peak at 26.3° 2Theta and a peak at 31.2° 2Theta. After 5-7 days of crystallization, the XRD pattern of the zeolitic material shows the characteristic peaks of the framework structure type AEI. Further, increasing the crystallization to 9 days and 11 days does not change the intensity of the peaks of the XRD patterns associated with the framework structure type AEI. This illustrates that the zeolitic, material having a framework structure type AEI obtained according to the invention has a high stability in the synthesis mixture.

[0453] FIG. 5a: shows the SEM image of the respectively obtained fresh AEI zeolitic material (low magnification: scale bar 1 micrometer) according to a) of Example 2.

[0454] FIG. 5b: shows the SEM image of the respectively obtained fresh AEI zeolitic material (high magnification: scale bar 500 nanometers) according to a) of Example 2.

[0455] FIG. 6a: shows the SEM image of the respectively obtained fresh AEI zeolitic material (low magnification: scale bar 1 micrometer) according to a) of Comparative Example 1.

[0456] FIG. 6b: shows the SEM image of the respectively obtained fresh AEI zeolitic material (high magnification: scale bar 500 nanometers) according to a) of Comparative Example 1.

[0457] FIG. 7: shows the NOx conversion of fresh catalysts comprising a zeolitic material according to Examples 1, 2 and Comparative Example 1.

[0458] FIG. 8: shows the XRD patterns of the respectively obtained AEI zeolitic materials according to a) of Examples 5 (c) arid 6 (b) and of Comparative Example 2 (a).

[0459] FIG. 9: shows the SEM images of the respectively obtained AEI zeolitic materials according to a) of Examples 5 (c) and 6 (b) and of Comparative Example 2 (a) (magnification: scale bar 1 micrometer).

[0460] FIG. 10: shows the crystallization curve of the zeolitic material according to a) of Example 6.

[0461] FIG. 11: shows N.sub.2 sorption isotherms of the zeolitic materials of Examples 5 (b), 6 (c) and Comparative Example 2 (a) as determined in Reference Example 1 b) (FINESORB-3020M) herein. Obvious hysteresis loops in the range of 0.7<PIP.sub.0<1.0 can be observed for the zeolitic material of Example 5 and the zeolitic material of Example 6 indicating the existence of mesoporosity in the samples.

[0462] FIG. 12: shows the XRD patterns of the respectively obtained AEI zeolitic material according to a) of Example 6 after crystallization duration of 0 hour to 268 hours. After 9 hours of crystallization, the XRD pattern of the zeolitic material shows weak peaks related to AEI zeolitic material. Increasing the crystallization from 12 to 48 hours, the XRD peaks associated with AEI zeolitic material gradually increase, together with the gradual decrease of the characteristic peaks related to the starting material (zeolite Y). When the crystallization reaches 72 hours, the XRD pattern of the zeolitic material shows the characteristic peaks of the framework structure type AEI. Further, increasing the crystallization to 264 hours does not change the intensity of the peaks of the XRD patterns associated with the framework structure type AEI.

[0463] FIG. 13: shows the NH.sub.3-TPD curves of the zeolitic materials according to b) of Comparative Example 2 (a) and to b) of Example 6 (b). The NH.sub.3-TPD curves are determined as in Reference Example 1 g) herein. Both samples have similar peak position for ammonia desorption, giving at about 170° C. and about 510° C. Notably, the peak intensity of the H-SSZ-39 (a) is stronger than that of the mesoporous H-SSZ-39 (b), which is attributed to more four-coordinated Al species in the H-SSZ-39 than those in the mesoporous H-SSZ-39.

[0464] FIG. 14: shows the methanol conversion in MTO reaction using the zeoltic materials of Comparative Example 2 (a) and of Example 6 (b) on a stream at 350° C.

[0465] FIG. 15: shows the selectivities in MTO reaction for ethylene (a), propylene (b), butane (c) and C.sub.1-C.sub.4 alkane (d) over the zeolitic materials of Comparative Example 2 (A) and of Example 6 (B).

[0466] FIG. 16: shows the TG-DTA curves of the comparative catalyst a after reaction during 780 minutes (a) and of the inventive catalyst b (mesoporous) after reaction during 960 minutes. The TG-DTA curves are determined as in Reference Example 1 h) herein.

CITED LITERATURE

[0467] CN 107285333 A

[0468] CN 107285334 A