Synthesis and Use of a Zeolitic Material Having the ITH Framework Structure Type

Abstract

A zeolitic material having the ITH framework structure type.A process for the preparation of a zeolitic material having the ITH framework structure type, the process comprising: (1) preparing a mixture comprising one or more specific organotemplates as structure direct-ing agents, one or more sources of YO2, optionally one or more sources of X2O3, seed crystals, and a solvent system, wherein Y is tetravalent element and X is a trivalent ele-ment,(2) heating the mixture obtained in (1) for crystallizing a zeolitic material having the ITH framework structure type comprising YO2 and optionally X2O3 in its framework structure; wherein the one or more organotemplates comprise a specific polymeric cation.

Claims

1. A zeolitic material having the ITH framework structure type, wherein the zeolitic material comprises YO.sub.2 and optionally X.sub.2O.sub.3 in its framework structure, wherein Y is a tetravalent element and X is a trivalent element, wherein the framework structure of the zeolitic material comprises less than 4 weight-% of Ge calculated as GeO.sub.2 and based on 100 weight-% of YO.sub.2 contained in the framework structure, wherein the zeolitic material comprises less than 1.5 weight-% of B calculated as B.sub.203 and based on 100 weight-% of X.sub.2O.sub.3 contained in the framework structure, and wherein the zeolitic material has a molar ratio YO.sub.2: X.sub.2O.sub.3 of equal or greater than 50.

2. The zeolitic material of claim 1, wherein the zeolitic material comprises YO.sub.2 and X.sub.2O.sub.3 in its framework structure, wherein the zeolitic material has a molar ratio YO.sub.2: X.sub.203 in the range of from 100 to 250.

3. The zeolitic material of claim 1, wherein Y comprises Si, wherein the .sup.29Si MAS NMR of the zeolitic material comprises: a first peak having a maximum in the range of from −101.0 to −107.0 ppm; a second peak having a maximum in the range of from −105.0 to −112.7 ppm; a third peak having a maximum in the range of from −111.0 to −116.0 ppm; and a fourth peak having a maximum in the range of from −115.1 to −118.4 ppm.

4. The zeolitic material of claim 1, wherein the zeolitic material displays an X-ray powder diffraction pattern comprising at least the following reflections: TABLE-US-00010 Diffraction angle 2θ/° Intensity (%) [Cu K(alpha 1)] 100 [7.00-7.20] [33-53] [7.82-8.02] [22-42] [8.60-8.80] [42-62] [11.12-11.32] [28-48] [15.38-15.58] [19-39] [16.05-16.25] [19-39] [16.48-16.68] [17-37] [20.94-21.14] [14-34] [21.40-21.60] [77-97] [22.92-23.12] [57-77] [23.54-23.74] [31-51] [23.90-24.10] wherein 100% relates to the intensity of the maximum peak in the X-ray powder diffraction pattern.

5. A process for the preparation of a zeolitic material having the ITH framework structure type, wherein the process comprises (1) preparing a mixture comprising one or more organotemplates as structure directing agents, one or more sources of YO.sub.2, optionally one or more sources of X.sub.2O.sub.3, seed crystals, and a solvent system, wherein Y is tetravalent element and X is a trivalent element; (2) heating the mixture obtained in (1) for crystallizing a zeolitic material having the ITH framework structure type comprising YO.sub.2 and optionally X.sub.2O.sub.3 in its framework structure; wherein the one or more organotemplates comprise a polymeric cation comprising a unit of formula (I):
[R.sup.1R.sup.2N.sup.+−R.sup.5−N.sup.+R.sup.3R.sup.4−R.sup.6].sub.n  (I); wherein R.sup.1, R.sup.2, R.sup.3, and R.sup.4 independently from one another is (C1-C.sub.4)alkyl; wherein R.sup.5 is selected from the group consisting of tetramethylene, pentamethylene, hexamethylene, and heptamethylene; wherein R.sup.6 is selected from the group consisting of trimethylene, tetramethylene, and pentamethylene; wherein n is a natural number in the range of from 1 to 50.

6. The process of claim 5, wherein the organotemplate: YO.sub.2 molar ratio of the one or more organotemplates to the one or more sources of YO.sub.2 calculated as YO.sub.2 in the mixture prepared in (1) and heated in (2) is in the range of from 0.001 to 0.5.

7. The process of claim 5, wherein the seed crystals comprise one or more zeolitic materials having the ITH framework structure type.

8. The process of claim 5, wherein the amount of seed crystals comprised in the mixture prepared in (1) is in the range of from 0.1 to 15 weight-% based on 100 weight-% of the one or more sources of YO.sub.2 calculated as YO.sub.2.

9. The process of claim 5, wherein the mixture comprises one or more sources for X.sub.203, wherein the X.sub.2O.sub.3: YO.sub.2 molar ratio of the one or more sources of X.sub.2O.sub.3 calculated as X.sub.2O.sub.3 to the one or more sources of YO.sub.2 calculated as YO.sub.2 in the mixture prepared in (1) and heated in (2) is in the range of from 0.001 to 0.1.

10. The process of claim 5, wherein the mixture prepared in (1) further comprises one or more sources of fluoride, wherein the fluoride: YO.sub.2 molar ratio of the one or more sources of fluoride calculated as the element to the one or more sources of YO.sub.2 calculated as YO.sub.2 in the mixture prepared in (1) and heated in (2) is in the range of from 0.01 to 2.

11. The process of claim 5, wherein the one or more organotemplates are prepared according to a process comprising (a) preparing a reaction mixture comprising a compound having the formula (II)
R.sup.1R.sup.2N.sup.+−R.sup.5−N+R.sup.3R.sup.4  (II) a compound having the formula (III)
R.sub.a−R.sup.6−R.sub.b  (III) and a solvent system, to obtain a reaction mixture; (b) heating the reaction mixture, to obtain a mixture comprising one or more organotemplates; wherein R.sup.1, R.sup.2, R.sup.3, and R.sup.4 independently from one another is (C.sub.1-C.sub.4)alkyl; wherein R.sup.S is selected from the group consisting of tetramethylene, pentamethylene, hexamethylene, and heptamethylene; wherein R.sup.6 is selected from the group consisting of trimethylene, tetramethylene, and pentamethylene; and wherein R.sub.a and R.sub.b independently from each other is selected from the group consisting of F, Cl, Br, I, tosyl (OTs), mesyl, triflourmethansulfonate (OTf), and OH.

12. The process of claim 5, wherein the process further comprises (3) isolating the zeolitic material obtained in (2), and/or (4) washing the zeolitic material obtained in (2) or (3), and/or (5) drying the zeolitic material obtained in (2), (3), or (4), in a gas atmosphere, and/or (6) calcining the zeolitic material obtained in (2), (3), (4) or (5) in a gas atmosphere, and/or (7) subjecting the zeolitic material obtained in (2), (3), (4), (5) or (6) to an ionexchange procedure with one or more metal cations M, wherein the steps (3) and/or (4) and/or (5) and/or (6) and/or (7) can be conducted in any order.

13. A zeolitic material having the ITH framework structure type obtainable and/or obtained from the process of claim 5.

14. A method for the conversion of oxygenates to olefins comprising (i) providing a catalyst according to claim 1; (ii) providing a gas stream comprising one or more oxygenates and optionally one or more olefins and/or optionally one or more hydrocarbons; (iii) contacting the catalyst provided in (i) with the gas stream provided in (ii) and converting one or more oxygenates to one or more olefins and optionally to one or more hydrocarbons; (iv) optionally recycling one or more of the one or more olefins and/or of the one or more hydrocarbons contained in the gas stream obtained in (iii) to (ii).

15. (canceled)

16. A molecular sieve comprising a zeolitic material according to claim 1.

17. An adsorbent comprising a zeolitic material according to claim 1.

18. A catalyst comprising a zeolitic material according to claim 1.

19. A catalyst support comprising a zeolitic material according to claim 1.

Description

BRIEF DESCRIPTION OF FIGURES

[0281] FIG. 1: shows the catalytic performance of a zeolitic material according to the present invention relative to a conventional ZSM-5 zeolite in MTO reaction. In particular, dependences of methanol conversion and product selectivity on reaction time in MTO over the COE-7 zeolite (solid labels) and ZSM-5 (hollow labels) at 480 0° C. are shown.

[0282] FIG. 2: shows the powder X-ray diffraction pattern of a zeolitic material according to Example 7. On the abscissa, the 2theta angle is shown in degree and on the ordinate the intensity is shown in arbitrary units.

CITED LITERATURE

[0283] CN 106698456 A [0284] C. Zhang et al. “An Efficient, Rapid, and Non-Centrifugation Synthesis of Nanosized Zeolites by Accelerating the Nucleation Rate” in J. Mater. Chem. A 2018, 6 (42), 21156-21161 [0285] P. Zeng et al. “On the synthesis and catalytic cracking properties of AI-ITQ-13 zeolites” in Microporous and Mesoporous Materials 2017, 246, 186 [0286] G. Xu et al. “Synthesis of pure silica ITQ-13 zeolite using fumed silica as silica source” in Microporous and Mesoporous Materials 2010, 129, 278 [0287] X. Liu et al. “Synthesis of all-silica zeolites from highly concentrated gels containing hexamethonium cations” in Microporous and Mesoporous Materials 2012, 156, 257 [0288] R. CastaAeda et al. “Direct synthesis of a 9×10 member ring zeolite (AI-ITQ-13): A highly shape-selective catalyst for catalytic cracking” in Journal of Catalysis 2006, 238, 79-87 [0289] L. Liu et al. “Oriented control of Al locations in the framework of AI—Ge-ITQ-13 for catalyzing methanol conversion to propene” in Journal of Catalysis 2016, 344, 242-251 [0290] H. Ma, “Reaction mechanism for the conversion of methanol to olefins over H-ITQ-13 zeolite: a density functional theory study” in Catalysis Science and Technology 2018, 8, 521 [0291] A. Corma et al. “A Zeolite Structure (ITQ-13) with Three Sets of Medium-Pore Crossing Channels Formed by 9- and 10-Rings” in Angew. Chem./nt. Ed. 2003, 42 (10), 1156-1159 [0292] Q. Wu et al. “Solvent-Free Synthesis of ITQ-12, ITQ-13, and ITQ-17 zeolites” in Chin. J.

[0293] Chem. 2017, 35, 572