A PROCESS FOR PREPARING A ZEOLITIC MATERIAL HAVING FRAMEWORK TYPE AEI

Abstract

The present disclosure relates to a process for preparing a zeolitic material having framework type AEI and having a framework structure which comprises a tetravalent element Y, a trivalent element X, and O. Further, the present invention disclosure relates to a zeolitic material having framework type AEI and having a framework structure which comprises a tetravalent element Y, a trivalent element X, and O, preferably obtained by the process, and further relates to the use of the zeolitic material as a catalytically active material, as a catalyst, or as a catalyst component.

Claims

1-17. (canceled)

18. A process for preparing a zeolitic material having framework type AEI and a framework structure comprising a tetravalent element Y, a trivalent element X, and O, the process comprising: (i) preparing a synthesis mixture comprising water, a source of Y, a source of X, an AEI framework structure directing agent, and a source of sodium, wherein the source of Y and/or the source of X comprise sodium; and (ii) heating the synthesis mixture under autogenous pressure to a temperature ranging from 100° C. to 180° C. for at least 6 h, obtaining the zeolitic material having framework type AEI and a framework structure comprising a tetravalent element Y, a trivalent element X, and O, comprised in its mother liquor; wherein the source of Y and the source of X contribute a total of at least 50 weight-% of elemental sodium in the synthesis mixture prepared in (i); wherein Y is one or more of Si, Ge, S, Ti, and Zr; and wherein X is one or more of Al, B, Ga, and In.

19. The process of claim 18, wherein the source of Y and the source of X contribute a total of at least 75 weight-% of elemental sodium in the synthesis mixture prepared in (i).

20. The process of claim 18, wherein in the synthesis of mixture prepared in (i), the source of sodium is the source of Y and the source of X does not comprise sodium, the source of sodium is the source of X and the source of Y does not comprise sodium, or the source of sodium is the source of Y and the source of X

21. The process of claim 18, wherein Y comprises Si and X comprises Al.

22. The process of claim 18, wherein the source of Y comprises a sodium silicate having the formula (Na.sub.2SiO.sub.2).sub.nO wherein n is an integer.

23. The process of claim 18, wherein the source of X comprises a sodium aluminate.

24. The process of claim 18, wherein in the synthesis mixture prepared in (i), the synthesis mixture is characterized by a molar ratio of the source of Y, calculated as YO.sub.2, relative to the source of X, calculated as X.sub.2O.sub.3, ranging from 5:1 to 25:1, a molar ratio of the source of Y, calculated as YO.sub.2, relative to the AEI framework structure directing agent ranging from 1:1 to 10:1, and a molar ratio of the source of Y, calculated as YO.sub.2, relative to the water ranging from 0.01:1 to 1:1.

25. The process of claim 1, wherein in the synthesis mixture obtained from (i) in (ii), the synthesis mixture is heated to a temperature ranging from 140° C. to 160° C. or 100° C. to 140° C.

26. The process of claim 18, further comprising (iii) cooling the mixture obtained from (ii); and (iv) separating the zeolitic material from the obtained mixture.

27. The process of claim 18, wherein the zeolitic material having framework type AEI and a framework structure comprising a tetravalent element Y, a trivalent element X, and O is characterized by one or more of: (1) a BET specific surface area ranging from 200 m.sup.2/g to 340 m.sup.2/g; (2) a crystallinity of at least 60% determined by X-Ray Diffraction analysis; (3) a Langmuir surface area ranging from 290 m.sup.2/g to 430 m.sup.2/g determined according to DIN 66131.

28. The process of claim 26, further comprising contacting the zeolitic material with a solution comprising ammonium ions to obtain an ammonium form zeolitic material having framework type AEI.

29. The process of claim 26, further comprising supporting a metal M on the zeolitic material, and wherein the metal M is a transition metal of groups 7 to 12 of the periodic system of elements.

30. The process of claim 29, wherein supporting a metal M on the zeolitic material comprises heating a mixture comprising the zeolitic material, a source of the metal M, a solvent for the source of the metal M, and optionally an acid to a temperature ranging from 30° C. to 90° C.; and separating a zeolitic material comprising the metal M from the mixture.

31. The process of claim 30, wherein the metal M is supported on the zeolitic material in an amount ranging from 1 weight-% to 11 weight-% calculated as MO and based on the total weight of the zeolitic material.

32. A zeolitic material having framework type AEI and having a framework structure which comprises a tetravalent element Y, a trivalent element X, and O, and optionally a metal M, prepared by the process according to claim 1.

33. A zeolitic material having framework type AEI and having a framework structure which comprises a tetravalent element Y, a trivalent element X, and O, characterized by a .sup.27Al solid-state NMR spectrum, comprising resonances and a peak maximum ranging from 62.0 to 54.0 ppm; wherein Y is one or more of Si, Ge, S, Ti, and Zr; and wherein X is one or more of Al, B, Ga, and In.

34. A method for treating combustion exhaust gas comprising using the zeolitic material according to claim 32 as a catalytically active material, as a catalyst, or as a catalyst component.

Description

EXAMPLES

Reference Example 1.1: Determination of the Crystallinity

[0289] The crystallinity of the zeolitic materials according to the present invention was determined by XRD analysis. The data were collected using a standard Bragg-Brentano diffractometer with a Cu-X-ray source and a linear detector. The angular range of 2° to 70° (2 theta) was scanned with a step size of 0.02°, while the divergence slit was set to a constant opening angle of 0.1°. The quantification of the crystalline content was performed using DIFFRAC.TOPAS V5 soft-ware, based on the crystal structures. This was refined to fit the data. Included in the model were also a linear background, Lorentz and polarization corrections, lattice parameters, space group and crystallite size. The quantification of the amorphous versus crystalline content was performed using DIFFRAC.EVA as described in the user manual.

[0290] 1. User Manual DIFFRAC.TOPAS V5, 2014, Bruker AXS GmbH, Karlsruhe, Germany

[0291] 2. User Manual DIFFRAC.EVA, 2014, Bruker AXS GmbH, Karlsruhe, Germany

Reference Example 1.2: Determination of the BET Specific Surface Area

[0292] The BET specific surface area was determined according to ISO 9277, second edition 2010, via nitrogen physisorption at 77 K.

Reference Example 1.3: Determination of the C Value

[0293] The C value (BET parameter) was determined as described in ISO 9277, second edition 2010, section 7.2.

Reference Example 1.4: Determination of the XRD Patterns

[0294] The XRD diffraction patterns were determined as described in Reference Example 1.1.

Reference Example 1.5: Scanning Electron Microscopy

[0295] The SEM (Scanning Electron Microscopy) pictures (secondary electron (SE) picture at 15 kV (kiloVolt)) were made using a Hitachi TM3000.

Reference Example 1.6: .SUP.27.Al Solid-State NMR

[0296] .sup.27Al solid-state NMR spectra were recorded at 9.4 Tesla under 10 kHz magic-angle spinning using a 15°-single-pulse-acquisition sequence with 0.5 s repetition time and 10240 repetitions, 10 ms acquisition, processed without exponential line broadening, where the pulse angle refers to an external reference sample of Al in aqueous solution. The sample was stored at 62% relative humidity for at least 60h prior to measurement. Resonances were indirectly referenced to Al(NO.sub.3).sub.3 in D.sub.2O, 1.1 mol/kg, as zero reference, with a frequency of 0.26056859 on the unified shift scale, in line with IUPAC recommendations 2008 (Pure Appl. Chem., Vol. 80, No. 1, pp. 59-84, 2008), using external secondary standards.

Reference Example 1.7: .SUP.29.Si Solid-State NMR

[0297] .sup.29Si solid-state NMR spectra were recorded at 9.4 Tesla under 10 kHz magic-angle spinning using a 90°-single-pulse-acquisition sequence with heteronuclear radio-frequency proton-decoupling during acquisition, 120 s repetition time and 160 repetitions, 30 ms acquisition, processed with 30 Hz exponential line broadening. The sample was stored at 62% relative humidity for at least 60 h prior to measurement. Resonances were indirectly referenced to Me.sub.4Si in CDCl.sub.3, volume fraction 1%, as zero reference, with a frequency of 0.19867187 on the unified shift scale, in line with IUPAC recommendations 2008 (Pure Appl. Chem., Vol. 80, No. 1, pp. 59-84, 2008), using external secondary standards.

Reference Example 1.8: Elemental Analysis

[0298] Elemental analyses were performed on an inductively coupled plasma-atomic emission spectrometer (ICP-AES, Shimadzu ICPE-9000).

Example 1: Preparation of a Zeolitic Material Having Framework Type AEI According to the Invention

[0299] a) Providing the AEI Seed

[0300] Materials Used:

TABLE-US-00001 Deionised water 770.71 g Sodium hydroxide (aqueous solution, 50 weight-%)  70.73 g 1,1,3,5-tetramethylpiperidinium OH (Sachem; aq. mixture, 196.18 g 19.77 weight-%): Ludox ® AS40 (colloidal silica; aqueous solution, 40 weight-%): 219.80 g NH.sub.4-Y-Zeolith (Y-Zeolith seeds, Zeolist)  16.40 g

[0301] The NaOH solution was added to a beaker along with 670.71 g water, to which the Y-Zeolith seeds were added along with the template compound (1,1,3,5-tetramethylpiperidinium OH), under stirring at around 23° C. Said mixture was then stirred for one hour, followed by Ludox® AS40 being added over 30 minutes. The thus obtained mixture was then transferred from the beaker to an autoclave and rinsed with 100 g of deionised water. Then, the autoclave was sealed. Within 1 h, the mixture in the autoclave was heated to a temperature of 160° C. and kept at this crystallization temperature for 24 h under stirring. After pressure release and cooling to room temperature, the obtained suspension was subjected to filtration using a nutsch-type filter and the filter cake was thoroughly washed with de-ionized water. The thus washed zeolitic material was dried overnight at 120° C. under air in a convection oven, then calcined at 500° C. for 5 h under air. 32.5 g zeolitic material were obtained.

[0302] The crystallinity was 99%, determined as described in Reference Example 1.1.96% of the crystalline material was zeolitic material having framework type AEI, 4% of the material was zeolitic material having framework type FAU. The elemental Si:Al ratio was 8.6:1, determined as described in Reference Example 1.8.

[0303] b) Preparation of a Zeolitic Material Having Framework Type AEI

[0304] Materials Used:

TABLE-US-00002 Sodium Aluminate (NaAlO.sub.2; Sigma Aldrich CAS 11138-49-1)  3.7 g 1,1,3,5-tetramethylpiperidinium OH (Sachem; aq. mixture, 45.7 g 19.77 weight-%): Sodium silicate (Na.sub.2SiO.sub.3; Woellner; CAS-Nr. 1344-09-8; 38/40; 60.5 g ca. 26 weight-% SiO.sub.2 + 8 weight-% Na.sub.2O in water): Ludox ® AS40 (colloidal silica; aqueous solution, 40 weight-%): 18.2 g AEI Seeds (according to a) above):  1.1 g

[0305] The template compound (1,1,3,5-tetramethylpiperidinium hydroxide) was added to a Teflon lined autoclave, followed by adding the sodium aluminate under stirring at around 23° C. The thus obtained mixture was then stirred until the sodium aluminate had dissolved. The following further materials were then added to the autoclave under stirring at around 23° C.: AEI seeds, sodium silicate and the Ludox® AS40. Then, the autoclave was sealed. Within 1 h, the mixture in the autoclave was heated to a temperature of 160° C. and kept at this crystallization temperature for 48 h under stirring. After pressure release and cooling to room temperature, the obtained suspension was subjected to filtration using a nutsch-type filter and the filter cake was washed with de-ionized water until a pH of about 9. The thus washed zeolitic material was dried overnight at 120° C. under air in a convection oven. 11.5 g zeolitic material were obtained, the space-time yield was 57.5 kg/m.sup.3/d. The crystallinity was 90%, determined as described in Reference Example 1.1. The XRD pattern, determined as described in Reference Example 1.4, is shown in FIG. 1.

[0306] 58% of the crystalline material was zeolitic material having framework type AEI, 42% of the material was zeolitic material having framework type AFI. [0307] c) Preparing the ammonium form of the zeolitic material having framework type AEI prepared in b)

[0308] Ammonium nitrate treatment was carried out as follows: 80 g of distilled water was added to a 150 ml beaker, to which under stirring 8 g of the (Na-AEI) zeolitic material prepared in b) was added, followed by adding 8 g of ammonium nitrate. The beaker was then covered with a watch glass followed by stirring at 80° C. for 1 h. Using a nutsch-type filter, the filter cake was washed nitrate-free with deionized water. Said ammonium nitrate treatment (i) was then repeated once. The resulting filter cake was dried at 120° C. for 5 hours under air. [0309] d) Preparing the H form of the zeolitic material having framework type AEI prepared in c)

[0310] The zeolitic material prepared in c) was calcined at 500° C. for 5 h under air. 6.5 g zeolitic material were obtained.

Example 2: Preparation of a Zeolitic Material Having Framework Type AEI According to the Invention

[0311] a) Providing the AEI Seed

[0312] Materials Used:

TABLE-US-00003 Deionised water 708.90 g Sodium hydroxide (aqueous solution, 50 weight-%)  78.70 g 1,1,3,5-tetramethylpiperidinium OH (Sachem; aq. mixture, 218.30 g 19.77 weight-%): Ludox ® AS40 (colloidal silica; aqueous solution, 40 weight-%): 244.00 g NH.sub.4-Y-Zeolith (Y-Zeolith seeds, Zeolist)  23.48 g

[0313] The NaOH solution was added to a beaker along with 608.9 g water, to which the Y-Zeolith seeds were added along with the template compound (1,1,3,5-tetramethylpiperidinium OH), under stirring at around 23° C. Said mixture was then stirred for one hour, followed by Ludox® AS40 being added over 30 minutes. The thus obtained mixture was then transferred from the beaker to an autoclave and rinsed with 100 g of deionised water. Then, the autoclave was sealed. Within 1 h, the mixture in the autoclave was heated to a temperature of 140° C. and kept at this crystallization temperature for 72 h under stirring. After pressure release and cooling to room temperature, the obtained suspension was subjected to filtration using a nutsch-type filter and the filter cake was thoroughly washed with de-ionized water. The thus washed zeolitic material was dried overnight at 120° C. under air in a convection oven, then calcined at 500° C. for 5 h under air. 42.8 g zeolitic material were obtained.

[0314] The crystallinity was 95%, determined as described in Reference Example 1.1. 96.5% of the crystalline material was zeolitic material having framework type AEI, 3.5% of the material was zeolitic material having framework type FAU. The elemental Si:Al ratio was 7.6:1, determined as described in Reference Example 1.8.

[0315] b) Preparation of a Zeolitic Material Having Framework Type AEI

[0316] Materials Used:

TABLE-US-00004 Sodium Aluminate (NaAlO.sub.2; Sigma Aldrich CAS 11138-49-1)  6.51 g 1,1,3,5-tetramethylpiperidinium OH (Sachem; aq. mixture,  67.2 g 19.77 weight-%): Sodium silicate (Na.sub.2SiO.sub.3; Woellner; CAS-Nr. 1344-09-8; 38/40; 115.8 g ca. 26 weight-% SiO.sub.2 + 8% Na.sub.2O in water): AEI Seeds (according to a) above):  6.1 g

[0317] Using the materials listed above, the protocol according to Example 1 b) was employed, except for the following differences:

[0318] As one can see from the materials used in Example 2, Ludox® AS40 was not employed. Furthermore, in Example 2 the crystallization temperature employed was 120° C. for 5 days. 26.5 g zeolitic material were obtained, the space-time yield was 35.5 kg/m.sup.3/d. Elemental analysis of the zeolitic material, in weight-%: Si=29.1; Al=7.3; Na=4.9. The crystallinity was 74%, determined as described in Reference Example 1.1. The BET specific surface area was 266 m.sup.2/g, determined as described in Reference Example 1.2. The Langmuir surface area was 357 m.sup.2/g determined according to DIN 66131. The C value was −92, determined as described in Reference Example 1.3. The XRD pattern, determined as described in Reference Example 1.4, is shown in FIG. 2. The SEM picture, determined as described in Reference Example 1.5, is shown in FIG. 3.

[0319] 82% of the crystalline material was zeolitic material having framework type AEI, 18% of the material was zeolitic material having framework type GME. The .sup.27Al-NMR spectra, determined as described in Reference Example 1.6 is shown in FIG. 5. The .sup.29Si-NMR spectra, determined as described in Reference Example 1.7 is shown in FIG. 6.

[0320] c) Preparing the Ammonium Form of the Zeolitic Material Having Framework Type AEI Prepared in b)

[0321] The ammonium form was prepared using the same protocol as employed for Example 1 c).

[0322] d) Preparing the H Form of the Zeolitic Material Having Framework Type AEI Prepared in c)

[0323] The H form was prepared using the same protocol as employed for Example 1 d).

Example 3: Preparation of Zeolitic Materials Having Framework Type AEI and Comprising a Metal M (Cu)

[0324] Cu Doping

[0325] Each of the zeolitic materials obtained from Example 1 d) and Example 2 d) were impregnated via incipient wetness with an aqueous copper nitrate solution wherein the amount of Cu nitrate was chosen so that, in the finally obtained material containing Cu supported on the zeolitic material, was 4 weight-% and 6 weight-%, calculated as CuO and based on the total weight of the finally obtained calcined zeolitic material having Cu supported thereon. After the impregnation, the material was stored for 20 h at 50° C., dried, then calcined for 5 h at 450° C. in air.

[0326] Shaping Procedure

[0327] Based on the above obtained Cu doped powder material, moldings were prepared by mixing the respective powder material with a milled alumina slurry (Puralox® TM 100/150) (weight ratio of zeolitic material: alumina=70:30). Under stirring, the moldings were dried at 100° C., then calcined in air for 1 h at 550° C. The moldings were then crushed and sieved to a particle size of 250-500 micrometer for testing.

[0328] For the subsequent tests, respectively fresh and aged Cu containing material was used for the respective Example 3, 1 d) and Example 3, 2 d) materials. For aging, the crushed and sieved particles were subjected for 50 h to air comprising 10 weight-% water at 650° C. in a muffle oven (HDD aging), optionally followed by subjecting for 16 h to air comprising 10 weight-% water at 800° C. in a muffle oven (LDD aging).

Example 4: Use of the Zeolitic Material Having Framework Type AEI for Selectively Catalytically Reducing Nitrogen Oxides

[0329] The zeolitic materials Example 3, 1 d) and Example 3, 2 d) obtained from Example 3 were subjected to a selective catalytic reduction test. SCR tests were performed on a 48 fold parallel testing unit equipped with ABB LIMAS NO.sub.x/NH.sub.3 and ABB URAS N.sub.2O analyzers (ABB AO2020 series).

[0330] For this purpose, the respectively obtained fresh and aged samples (170 mg each) were diluted with 1 mL corundum having the same particle size as the samples were placed in each reactor. Under isothermal conditions (T=175, 200, 250, 300, 450, 550, 575° C.), a given sample was exposed to a feed stream (500 ppm NO, 500 ppm NH.sub.3, 10% H.sub.2O, 5% O.sub.2, balance N.sub.2) at a gas hourly space velocity of 80,000 h.sup.−1 through the catalyst bed. In addition to 30 min waiting time for thermal equilibration of the parallel reactor at each temperature, every position was equilibrated for 3 min followed by 30 sec sampling time. Data recorded by the analyzers at a frequency of 1 Hz was averaged for the sampling interval and used to calculated NO conversions and N.sub.2O yield.

[0331] The results obtained are shown in FIG. 4.

BRIEF DESCRIPTION OF THE FIGURES

[0332] FIG. 1: shows the XRD pattern of the zeolitic material according to Example 1.

[0333] FIG. 2: shows the XRD pattern of the zeolitic material according to Example 2.

[0334] FIG. 3: shows SEM pictures of the zeolitic material according to Example 2.

[0335] FIG. 4: shows the results obtained from the selective catalytic reduction testing of Example 4. The upper figure shows the results obtained from the Example 3, 1 d) zeolitic material and the lower figure shows the results obtained from the Example 3, 2 d) zeolitic material. In each of the six sets of results, the result on the left corresponds to 4 wt.-% CuO and the result on the right corresponds to 6 wt.-% CuO.

[0336] FIG. 5: .sup.27Al-NMR spectra of the zeolitic material according to Example 2. The spectrum shows a main resonance at 58 ppm with a full width at half height of 7.2 ppm, it has an asymmetric line shape; this resonance can be assigned to tetrahedrally coordinated Al. At the given scale, no distinct resonances at approximately 30 ppm or 0 ppm were observed, which would point to other coordinations. A spinning side band of the main resonance was observed at −38 ppm

[0337] FIG. 6: .sup.29Si-NMR spectra of the zeolitic material according to Example 2. The spectrum shows a resonance at −111 ppm with a full width at half height of 3.1 ppm, which we assign to Si(4 OSi, 0 OAl, 0 OH). The spectrum shows a second resonance, at −105 ppm, with a full width at half height of 3.3 ppm, which we assign to Si(3 OSi, 1 OAl, 0 OH). The spectrum shows a third resonance, at −99 ppm, with a full width at half height of 3.4 ppm, which may stem from Si(2 OSi, 2 OAl, 0 OH) or Si(3 OSi, 0 OAl, 1 OH).

CITED LITERATURE

[0338] WO 2016/080547 A1 [0339] U.S. Pat. No. 5,958,370 [0340] Pure Appl. Chem., Vol. 80, No. 1, pp. 59-84, 2008