PROCESS FOR THE PRODUCTION OF A ZEOLITIC MATERIAL HAVING AN AEI-TYPE FRAMEWORK STRUCTURE VIA SOLVENT-FREE INTERZEOLITIC CONVERSION

Abstract

The present disclosure relates to a process preparing a zeolitic material having an AEI-type framework structure, wherein the framework structure comprises SiO.sub.2 and X.sub.2O.sub.3 and X is a trivalent element, and wherein the process comprises: (1) preparing a mixture comprising one or more cationic structure directing agents comprising a heterocyclic amine ring, seed crystals, and a first zeolitic material comprising SiO.sub.2 and X.sub.2O.sub.3 in its framework structure and having an FAU-type framework structure; and (2) heating the mixture to obtain a second zeolitic material comprising SiO.sub.2 and X.sub.2O.sub.3 in its framework structure and having an AEI-type framework structure.

Claims

1-15. (canceled)

16. A process for preparing a zeolitic material having an AEI-type framework structure wherein the framework structure comprises SiO.sub.2 and X.sub.2O.sub.3 and X is a trivalent element, and wherein the process comprises: (1) preparing a mixture comprising one or more cationic structure directing agent comprising a heterocyclic amine ring, seed crystals, and a first zeolitic material comprising SiO.sub.2 and X.sub.2O.sub.3 in the framework structure and having an FAU-type framework structure; and (2) heating the mixture to obtain a second zeolitic material comprising SiO.sub.2 and X.sub.2O.sub.3 in its framework structure and having the AEI-type framework structure; wherein the mixture prepared in (1) and heated in (2) contains 1000 wt.-% or less of H.sub.2O based on 100 wt.-% of SiO.sub.2 in the framework structure of the first zeolitic material, and wherein the one or more cationic structure directing agents are chosen from N,N-di(C.sub.1-C.sub.4)alkyl-3,5-di(C.sub.1-C.sub.4)alkylpyrrolidinium, N,N-di(C.sub.1-C.sub.4)alkyl-3,5-di(C.sub.1-C.sub.4)alkylpiperidinium, N,N-di(C.sub.1-C.sub.4)alkyl-3,5-di(C.sub.1-C.sub.4)alkylhexahydroazepinium, and combinations thereof.

17. The process of claim 16, wherein a molar ratio of trans isomer to cis isomer in the one or more cationic structure directing agents relative to alkyl groups at 3 and 5 positions of the heterocyclic amine ring ranges from 0.01 to 0.95.

18. The process of claim 16, wherein X is chosen from Al, B, In, Ga, and combinations thereof.

19. The process of claim 16, wherein the mixture prepared in (1) and heated in (2) further comprises at least one OW source.

20. The process of claim 16, wherein the heating in (2) is conducted at a temperature ranging from 80° C. to 250° C.

21. The process of claim 16, wherein the heating in (2) is conducted under autogenous pressure.

22. The process of claim 16, further comprising calcining the second zeolitic material.

23. The process of claim 16, further comprising ion-exchanging the second zeolitic material.

24. The process of claim 23, wherein in at least one ionic extra-framework element contained in the zeolite framework is ion-exchanged against one or more cations chosen from Sr, Zr, Cr, Mg, Mo, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, and combinations thereof.

25. The process of claim 16, wherein preparing the mixture comprises milling the mixture.

26. A zeolitic material having an AEI-type framework structure prepared according to the process of claim 16.

27. A zeolitic material having an AEI-type framework structure wherein the framework structure comprises SiO.sub.2 and X.sub.2O.sub.3 and X is a trivalent element, and wherein primary crystals of the zeolitic material have a mean aspect ratio greater than 3.6.

28. The zeolitic material of claim 27, wherein X is chosen from Al, B, In, Ga, and combinations thereof.

29. A molecular sieve, an adsorbent, an ion-exchange material, a catalyst, and/or a catalyst support comprising the zeolitic material according to claim 27.

Description

DESCRIPTION OF THE FIGURES

[0095] FIG. 1 shows SEM images of SSZ-39 obtained according to Example 1, wherein the scale of 1 μm is indicated below the respective image. Furthermore, the manual assessment of the aspect ratio for individual primary crystallites is indicated in the figures, respectively.

[0096] FIG. 2 shows SEM images of SSZ-39 obtained according to Example 2, wherein the scale of 1 μm is indicated below the respective image. Furthermore, the manual assessment of the aspect ratio for individual primary crystallites is indicated in the figures, respectively.

[0097] FIG. 3 shows SEM images of SSZ-39 obtained according to Example 3, wherein the scale of 1 μm is indicated below the respective image. Furthermore, the manual assessment of the aspect ratio for individual primary crystallites is indicated in the figures, respectively.

[0098] FIG. 4 shows SEM images of SSZ-39 obtained according to Example 4, wherein the scale of 1 μm is indicated below the respective image. Furthermore, the manual assessment of the aspect ratio for individual primary crystallites is indicated in the figures, respectively.

[0099] FIG. 5 shows SEM images of SSZ-39 obtained according to Example 5, wherein the scale of 1 μm is indicated below the respective image. Furthermore, the manual assessment of the aspect ratio for individual primary crystallites is indicated in the figures, respectively.

[0100] FIG. 6 shows SEM images of SSZ-39 obtained according to Comparative Example 1, wherein the scale of 1 μm is indicated below the respective image. Furthermore, the manual assessment of the aspect ratio for individual primary crystallites is indicated in the figures, respectively.

[0101] FIG. 7 shows an SEM image of SSZ-39 obtained according to Comparative Example 2, wherein the scale of 2.00 μm is indicated in the lower right hand corner of the image.

[0102] FIG. 8 shows SEM images of SSZ-39 obtained according to Comparative Example 4, wherein the scale of 2 μm is indicated below the respective image. Furthermore, the manual assessment of the aspect ratio for individual primary crystallites is indicated in the figures, respectively.

[0103] FIG. 9 shows SEM images of H-AEI seeds employed in examples 1-7, wherein the scale of 1 μm is indicated below the respective image. Furthermore, the manual assessment of the aspect ratio for individual primary crystallites is indicated in the figure.

[0104] FIG. 10 shows an SEM image of SSZ-39 obtained according to example 6, wherein the scale of 1 μm is indicated in the lower right hand corner of the image.

[0105] FIG. 11 shows an SEM image of SSZ-39 obtained according to example 7, wherein the scale of 1 μm is indicated in the lower right hand corner of the image.

[0106] FIG. 12 displays the results from SCR testing performed on the zeolitic materials obtained from examples 6 and 7 after copper exchange and shaping thereof according to example 9, respectively, wherein the shaped body obtained with the material from example 6 is designated as “SP0005” and the shaped body obtained with the material from example 7 is designated as “SP0006”. In the figure, the temperature at which the SCR testing was performed is shown along the abscissa, and the NO.sub.x conversion in % is shown along with ordinate. The testing values for the fresh catalyst is shown as “.circle-solid.” for the material aged for 50 h at 650° C. is shown as “.diamond-solid.” and for the material aged for 16 h at 820° C. is shown as “.Math.”.

[0107] FIG. 13 displays the results for the N.sub.2O make during SCR testing performed on the zeolitic materials obtained from examples 6 and 7 after copper exchange and shaping thereof according to example 9, respectively, wherein the shaped body obtained with the material from example 6 is designated as “SP0005” and the shaped body obtained with the material from example 7 is designated as “SP0006”. In the figures, the temperature at which the SCR testing was performed is shown along the abscissa, and the N.sub.2O make in % is shown along with ordinate. The testing values for the fresh catalyst is shown as “.circle-solid.” for the material aged for 50 h at 650° C. is shown as “.diamond-solid.” and for the material aged for 16 h at 820° C. is shown as “.box-tangle-solidup.”.

EXAMPLES

Measurement of the SEM Images

[0108] The SEM images were measured with secondary electrons at 5 kV for providing topographic images. The samples were mounted for measurement using Leit-C Plast and were coated with around 8 nm Pt.

Determination of the Aspect Ratio

[0109] For determining the aspect ratio of the primary crystals of the zeolitic materials, zeolite primary crystallites oriented perpendicular to the electron probe were selected manually in the SEM images for evaluation. Both accessible dimensions for a given crystal (i.e. width and height of the crystal) were measured and documented for each particle. The procedure was conducted on as many SEM images displaying different portions of the surface of the sample as necessary for obtaining values for at least 120 different particles, preferably for at least 150 different particles, and more preferably for at least 200 different particles. The mean value of the aspect ratio, i.e. the ratio of the width to the height of each particle, obtained for all of the measured particles constituted then the mean aspect ratio of the sample.

Measurement of the x-Ray Diffraction Patterns

[0110] Powder X-ray diffraction (PXRD) data was collected using a diffractometer (D8 Advance Series II, Bruker AXS GmbH) equipped with a LYNXEYE detector operated with a Copper anode X-ray tube running at 40 kV and 40 mA. The geometry was Bragg-Brentano, and air scattering was reduced using an air scatter shield. The crystallinity was determined using DIFFRAC.EVA software (User Manual for DIFFRAC.EVA, Bruker AXS GmbH, Karlsruhe).

Example 1: Synthesis of SSZ-39 Displaying a High Aspect Ratio

[0111] 50 g commercial Y zeolite (from Qilu Huaxin Industry; SAR: 26), 10.0 g NaOH, and 2.5 g H-AEI seeds (from China Catalyst Group (CCG)) were pre-mixed in a mortar by hand. The H-AEI seeds employed for the synthesis displayed a crystallinity as determined by XRD of 92% and consisted of 100% of the AEI phase, displayed a composition as obtained from elemental analysis of 40 wt. % Si, 3.7 wt. % Al, <0.01 wt. % Al and <0.1 wt. % C, displayed a BET surface area of 617 m.sup.2/g, a micropore volume (from t-plot analysis) of 0.28 ml/g, and displayed an aspect ratio of 3.56 (see SEM in FIG. 9). Then, 54.0 g of 1,1,3,5-tetramethylpiperidinium hydroxide (TMPOH, 24% aqueous solution; from CCG) with a trans:cis isomer ratio content of 0.18 were slowly added and mixed into the mixture thus forming a thick paste. The mixture having a mass of 114.2 g was then placed in an autoclave and heated for 120 h at 140° C. in a drying oven.

Work-Up:

[0112] The pasty product was removed from the autoclave and placed on a filter for suction filtration and then washed with 5 L of distilled water and then dried.

[0113] The dried product was then placed in a porcelain dish and heated with a constant temperature rampe over 7 h to 450° C., held at that temperature for 2 h, then heated with a constant temperature rampe over 30 min to 500° C., held at that temperature for 2 h, then heated with a constant temperature rampe over 30 min to 550° C., and held at that temperature for 2 h. After letting the reaction product cool back to room temperature, 29.2 g of a crystalline material was obtained.

[0114] Elemental analysis: Si, 39 wt. %, Al, 4.9 wt. %, Na, 2.3 wt. %, C<0.1 wt. %. XRD analysis indicated a total crystallinity of 88% with 95% AEI, 2% GME and 3% analcime.

[0115] The aspect ratio was determined via SEM analysis, wherein two of the SEM images which were used indicating the assessment of the aspect ratio of manually selected primary crystals are shown in FIG. 1. In total, manual assessment of the aspect ratio of 154 different primary crystals in the sample via SEM was performed for affording a mean aspect ratio of 4.32.

Example 2: Synthesis of SSZ-39 Displaying a High Aspect Ratio

[0116] 50 g commercial Y zeolite (from Qilu Huaxin Industry; SAR: 26), 10.0 g NaOH(s), and 2.5 g H-AEI seeds (same as employed in example 1) were pre-mixed and pre-ground in a Microton mill. Then, 54.0 g of 1,1,3,5-tetramethylpiperidinium hydroxide (TMPOH, 24% aqueous solution; from CCG) with a trans:cis isomer ratio content of 0.18 were slowly added and mixed into the mixture thus forming a thick paste. The mixture having a mass of 112.8 g was then placed in an autoclave and heated for 120 h at 140° C. in a drying oven.

Work-Up:

[0117] The pasty product was removed from the autoclave and placed on a filter for suction filtration and then washed with 5 L of distilled water and then dried.

[0118] The dried product was then placed in a porcelain dish and heated with a constant temperature rampe over 7 h to 450° C., held at that temperature for 2 h, then heated with a constant temperature rampe over 30 min to 500° C., held at that temperature for 2 h, then heated with a constant temperature rampe over 30 min to 550° C., and held at that temperature for 2 h. After letting the reaction product cool back to room temperature, 28.0 g of a crystalline material was obtained. Elemental analysis Si 39 wt. %, Al 4.8 wt. %, Na 2.1 wt. %, C<0.1 wt. %. XRD analysis indicated a total crystallinity of 89% with 99% AEI, 2% GME.

[0119] The aspect ratio was determined via SEM analysis, wherein two of the SEM images which were used indicating the assessment of the aspect ratio of manually selected primary crystals are shown in FIG. 2. In total, manual assessment of the aspect ratio of 119 different primary crystals in the sample via SEM was performed for affording a mean aspect ratio of 6.02

Example 3: Synthesis of SSZ-39 Displaying a High Aspect Ratio

[0120] 50 g commercial Y zeolite (from Qilu Huaxin Industry; SAR: 34), 10.0 g NaOH(s), and 2.5 g H-AEI seeds (same as employed in example 1) were pre-mixed in a beaker by hand. Then, 54.0 g of 1,1,3,5-tetramethylpiperidinium hydroxide (TMPOH, 24% aqueous solution; from CCG) with a trans:cis isomer ratio content of 0.18 were slowly added and mixed into the mixture thus forming a thick paste. The mixture having a mass of 113.7 g was then placed in an autoclave and heated for 120 h at 140° C. in a drying oven.

Work-Up:

[0121] The pasty product was removed from the autoclave and placed on a filter for suction filtration and then washed with 5 L of distilled water and then dried.

[0122] The dried product was then placed in a porcelain dish and heated with a constant temperature rampe over 7 h to 450° C., held at that temperature for 2 h, then heated with a constant temperature rampe over 30 min to 500° C., held at that temperature for 2 h, then heated with a constant temperature rampe over 30 min to 550° C., and held at that temperature for 2 h. After letting the reaction product cool back to room temperature, 30.7 g of a crystalline material was obtained. Elemental analysis: Si, 37 wt. %, Al, 3.7 wt. %, Na, 1.5 wt. %, C<0.1 wt. %. XRD analysis indicated a total crystallinity of 92% with 97% AEI, 0.5% GME and 2.5% analcime.

[0123] The aspect ratio was determined via SEM analysis, wherein two of the SEM images which were used indicating the assessment of the aspect ratio of manually selected primary crystals are shown in FIG. 3. In total, manual assessment of the aspect ratio of 130 different primary crystals in the sample via SEM was performed for affording a mean aspect ratio of 4.33.

Example 4: Synthesis of SSZ-39 Displaying a High Aspect Ratio

[0124] 50 g commercial Y zeolite (from Qilu Huaxin Industry; SAR: 34), 10.0 g NaOH(s), and 2.5 g H-AEI seeds (same as employed in example 1) were pre-mixed in a beaker by hand Then, 54.0 g of 1,1,3,5-tetramethylpiperidinium hydroxide (TMPOH, 24% aqueous solution; from CCG) with a trans:cis isomer ratio content of 0.18 were slowly added and mixed with the zeolite. By thoroughly mixing by hand, a homogeneous and rather dry paste was obtained. The paste was then placed in a Microton mill and further mixed, as a result of which the paste became liquid in consistency, and droplets of liquid formed on the surface of the glass. When opening the mill thereafter, a slight rise in pressure was noticeable. The mixture having a mass of 100.8 g was then placed in an autoclave and heated for 120 h at 140° C. in a drying oven.

Work-up:

[0125] The pasty product was removed from the autoclave and placed on a filter for suction filtration and then washed with 5 L of distilled water and then dried.

[0126] The dried product was then placed in a porcelain dish and heated with a constant temperature rampe over 7 h to 450° C., held at that temperature for 2 h, then heated with a constant temperature rampe over 30 min to 500° C., held at that temperature for 2 h, then heated with a constant temperature rampe over 30 min to 550° C., and held at that temperature for 2 h. After letting the reaction product cool back to room temperature, 24.9 g of a crystalline material was obtained. Elemental analysis Si 39 wt. %, Al 3.7 wt. %, Na 1.0 wt. %, C<0.1 wt. %. XRD analysis indicated a total crystallinity of 91% with 100% AEI.

[0127] The aspect ratio was determined via SEM analysis, wherein two of the SEM images which were used indicating the assessment of the aspect ratio of manually selected primary crystals are shown in FIG. 4. In total, manual assessment of the aspect ratio of 116 different primary crystals in the sample via SEM was performed for affording a mean aspect ratio of 4.32

Example 5: Synthesis of SSZ-39 Displaying a High Aspect Ratio

[0128] 50 g commercial Y zeolite (from Qilu Huaxin Industry; SAR: 26), 10.0 g NaOH(s), and 2.5 g H-AEI seeds (same as employed in example 1) were pre-mixed by hand. Then, 54.2 g of 1,1,3,5-tetramethylpiperidinium hydroxide (TMPOH, 24% aqueous solution; from BASF) having an isomer ratio trans:cis of 0.17) were slowly added and mixed in a beaker and then placed in a Microton mill. The mixture having a mass of 95.1 g was then placed in an autoclave and heated for 137 h at 140° C. in a drying oven.

Work-up:

[0129] The pasty product was removed from the autoclave and placed on a filter and then washed five times with 0.5 L of distilled water with the aid of a centrifuge. The product was then pre-dried over night at 60° C.

[0130] The dried product was then placed in a porcelain dish and heated with a constant temperature rampe over 7 h to 450° C., held at that temperature for 2 h, then heated with a constant temperature rampe over 30 min to 500° C., held at that temperature for 2 h, then heated with a constant temperature rampe over 30 min to 550° C., and held at that temperature for 2 h. After letting the reaction product cool back to room temperature, a crystalline material was obtained. XRD analysis indicated a total crystallinity of 92% with 93% AEI, 1% Y zeolite and 6% analcime.

[0131] The aspect ratio was determined via SEM analysis, wherein two of the SEM images which were used indicating the assessment of the aspect ratio of manually selected primary crystals are shown in FIG. 5. In total, manual assessment of the aspect ratio of 121 different primary crystals in the sample via SEM was performed for affording a mean aspect ratio of 3.79.

Example 6: Synthesis of SSZ-39 Displaying a High Aspect Ratio

[0132] 50 g commercial Y zeolite (from Qilu Huaxin Industry; SAR: 26), 10.0 g NaOH(s), and 2.5 g H-AEI seeds (same as employed in example 1) were pre-mixed in a mortar by hand. Then, 54.0 g of 1,1,3,5-tetramethylpiperidinium hydroxide (TMPOH; 20% aqueous solution; from CCG) with a trans:cis isomer ratio content of 0.18 were slowly added and mixed into the mixture thus forming a thick paste. The mixture having a mass of 114.2 g was then placed in an autoclave and heated for 120 h at 140° C. in a drying oven.

Work-up:

[0133] The pasty product was removed from the autoclave and placed on a filter for suction filtration and then washed with 5 L of distilled water and then dried.

[0134] The dried product was then placed in a porcelain dish and heated with a constant temperature rampe over 7 h to 450° C., held at that temperature for 2 h, then heated with a constant temperature rampe over 100 min to 500° C., held at that temperature for 2 h, then heated with a constant temperature rampe over 100 min to 550° C., and held at that temperature for 2 h. After letting the reaction product cool back to room temperature, 29.2 g of a crystalline material was obtained.

[0135] Elemental analysis of the product afforded: 36 wt. % Si, 4.7 wt. % Al, 1.5 wt. % Na, and <0.1 wt. % C. The material displayed a BET surface area of 600 m.sup.2/g.

[0136] An SEM image of the product is shown in FIG. 10.

Example 7: Synthesis of SSZ-39 Displaying a High Aspect Ratio

[0137] 50 g commercial Y zeolite (from Qilu Huaxin Industry; SAR: 34), 10.0 g NaOH(s), and 2.5 g H-AEI seeds (same as employed in example 1) were pre-mixed in a mortar by hand. Then, 54.0 g of 1,1,3,5-tetramethylpiperidinium hydroxide (TMPOH; 24% aqueous solution; from CCG) with a trans:cis isomer ratio content of 0.18 were slowly added and mixed into the mixture thus forming a thick paste. The mixture having a mass of 114.2 g was then placed in an autoclave and heated for 120 h at 140° C. in a drying oven.

Work-up:

[0138] The pasty product was removed from the autoclave and placed on a filter for suction filtration and then washed with 5 L of distilled water and then dried.

[0139] The dried product was then placed in a porcelain dish and heated with a constant temperature rampe over 7 h to 450° C., held at that temperature for 2 h, then heated with a constant temperature rampe over 100 min to 500° C., held at that temperature for 2 h, then heated with a constant temperature rampe over 100 min to 550° C., and held at that temperature for 2 h. After letting the reaction product cool back to room temperature, 29.2 g of a crystalline material was obtained.

[0140] Elemental analysis of the product afforded: 38 wt. % Si, 3.7 wt. % Al, 0.77 wt. % Na, <0.1 wt. % C. The material displayed a BET surface area of 640 m.sup.2/g.

[0141] An SEM image of the product is shown in FIG. 11.

Comparative Example 1: Synthesis of SSZ-39 Displaying a Conventional Aspect Ratio

[0142] 1 g of Y zeolite (Si/Al=10.8), 0.7 g of template (50% (aq), TMAOH), 0.35 g of NaOH and 0.02 g of uncalcined SSZ-39 zeolite seeds were mixed together. After grinding for 5-7 min, the powder mixture was transferred to an autoclave and sealed. After heating at 140° C. for 72 hours, the sample was completely crystallized. The resulting crystalline product of SSZ-39 displayed an Si:Al molar ratio of 5.0 as determined by inductively coupled plasma.

[0143] The aspect ratio was determined via SEM analysis, wherein two of the SEM images which were used indicating the assessment of the aspect ratio of manually selected primary crystals are shown in FIG. 6. In total, manual assessment of the aspect ratio of 121 different primary crystals in the sample via SEM was performed for affording a mean aspect ratio of 2.11.

Comparative Example 2: Synthesis of SSZ-39 According to Example 4 of WO 2018/113566 A1

[0144] For repeating Example 4 of WO 2018/113566 A1, 1 g of zeolite Y (Si/Al=10.8) containing H.sub.2O (0.625 g of Y and 0.375 g H.sub.2O), 0.7 g of template (40 wt.-% aqueous solution of N,N-dimethyl-2,6-dimethylpiperridinium hydroxide), 0.35 g of NaOH and 0.02 g of uncalcined SSZ-39 zeolite seeds were mixed together for affording a reaction mixture which contained 137 wt.-% of H.sub.2O based on 100 wt.-% of SiO.sub.2 contained in the zeolite Y of the mixture. After grinding for 5-7 min, the powder mixture was transferred to an autoclave and sealed. After heating at 140° C. for 72 hours, the sample was completely crystallized. The obtained sample was calcined at 550° C. for 5 hours to remove the template. The H-form of the sample was prepared by triple ion-exchange with 1 M NH.sub.4NO.sub.3 solution at 80° C. for 1 h and calcination at 550° C. for 5 h. The resulting crystalline product of SSZ-39 displayed an Si:Al molar ratio of 5.0 as determined by inductively coupled plasma.

Comparative Example 3: Synthesis of SSZ-39(N) Using Quaternary Ammonium Containing Structure Directing Agent

[0145] The following synthesis of SSZ-39(N) is based on the synthetic methodologies described in U.S. Pat. No. 5,958,370 and M. Moliner et al. in Chem. Commun. 2012, 48, pages 8264-8266.

Synthesis of N,N-dimethyl-3,5-dimethylpiperidinium Hydroxide (Nitrogen Containing Compound Structure Directing Agent)

[0146] N,N-dimethyl-3,5-dimethylpiperidinium hydroxide was prepared as described in M. Moliner et al., Chem. Comm., 2012, 48, 8264-8266 as detailed in the Electronic Supplementary Information (ESI) thereof, under heading 1.1.2.1—SSZ-39-OSDA Synthesis.

Synthesis of SSZ-39(N)

[0147] 4 g of a solution of the above obtained N,N-dimethyl-3,5-dimethylpiperidinium hydroxide (0.56 mmol OH.sup.−/g) is mixed with 6.1 g of water and 0.20 g of aqeuous 1.0 M NaOH solution. 0.25 g of Ammonium exchanged Y zeolite (JRC-HY-5.3; Si/Al.sub.2O.sub.3=5.3; JGC Catalysts and Chemicals Ltd.) is added to this solution and, finally, 2.5 g of Fumed Silica (Cab-O-Sil M5D) is added. The thus obtained mixture has the molar composition: 1 Si: 0.05 Al: 0.15 OSDA: 0.45 Na: 30 H.sub.2O.

[0148] The resulting mixture is then sealed in an autoclave and heated at 150° C. and stirred at 30 rpm for 3 days. After pressure release and cooling to room temperature the SSZ-39(N) product was obtained having a SiO.sub.2/Al.sub.2O.sub.3 mole ratio of 40.

[0149] The thus obtained SSZ-39(N) product was then calcined in air in a muffle furnace at 600° C. for 6 hours which provided the Na—SSZ-39(N).

[0150] Subsequently, the Na—SSZ-39(N) was then NH.sub.4.sup.+ ion exchanged using NH.sub.4NO.sub.3 by treating a 1:1 mixture of the Na—SSZ-39(N): NH.sub.4NO.sub.3 by slurrying in water in a weight ratio of water: Na—SSZ-39 of 25-50:1 at 95° C. for 2 hours, followed by filtration to provide NH.sub.4.sup.+ SSZ-39(N).

[0151] The thus obtained NH.sub.4.sup.+ SSZ-39(N) was then calcined in air in a muffle furnace at 600° C. for 3 hours which provided the H-form, H—SSZ-39(N).

[0152] The XRD for the H—SSZ-39(N) is provided in FIG. 1.

Comparative Example 4: Preparation of an AEI Zeolitic Material

[0153] 20.194 kg of distilled water were placed in a 60 L autoclave reactor and stirred at 200 rpm. 2.405 kg of a solution of 50 wt.-% NaOH in distilled water were then added followed by the addition of 6.670 kg of 1,1,3,5-tetramethylpiperidinium hydroxide. 560 g of zeolite Y seeds (N H.sub.4-zeolite Y; CBV-500 from Zeolyst) were then suspended in 3 L of distilled water and the suspension was the added to the reactor while stirring, after which 7.473 kg of Ludox® AS40 (Grace; colloidal silica; aqueous solution, 40 weight-%) were added. The resulting mixture displaying molar ratios of 1.00 SiO.sub.2: 0.30 Na.sub.2O: 0.17 template: 0.19 zeolite Y: 41.5 H.sub.2O was further stirred for 30 min at room temperature, after which the reactor was closed and the reaction mixture was heated under autogenous pressure in 1.5 h to 160° C. and subsequently maintained at that temperature for 48 h while further stirring.

[0154] The resulting suspension was filled into five 10 L canisters and the suspension allowed to settle, after which the clear supernatant was decanted off. The solid residue was placed in a filter and washed with distilled water to <200 μS. The filter cake was then dried at 120° C. over night to afford 1.1848 kg of a crystalline solid, which was subsequently heated at 2° C./min to 500° C. and calcined at that temperature for 5 hours under air. After said calcination, the calcined zeolitic material was subject to a further calcination step, wherein it was heated at 2° C./min to 550° C. and calcined at that temperature for 5 h to afford 1.0810 kg of the sodium form of a zeolitic material. X-ray diffraction analysis of the zeolitic material revealed an AEI type framework structure. The Na-AEI zeolite displayed a BET surface area as obtained from the nitrogen isotherms of 506 m.sup.2/g and a Langmuir surface area of 685 m.sup.2/g.

[0155] Elemental analysis of the resulting Na-AEI zeolite afforded values of 34 wt.-% of Si, 5.1 wt.-% of Al, and 2 wt.-% of Na. Accordingly the zeolite displayed an SiO.sub.2:Al.sub.2O.sub.3 molar ratio of 12.9.

[0156] The aspect ratio was determined via SEM analysis, wherein two of the SEM images which were used indicating the assessment of the aspect ratio of manually selected primary crystals are shown in FIG. 8. In total, manual assessment of the aspect ratio of 118 different primary crystals in the sample via SEM was performed for affording a mean aspect ratio of 1.94.

Example 8: MTO Catalytic Testing

[0157] Testing was conducted in a tubular reactor with heatable mantle. 10 g of a ground catalyst sample (fraction 1—1.6 mm) and 2-3 mm steatite beads (as inert material) were placed into the reactor. The reactor bed consisted of:

[0158] reactor exit: 4 cm steatite beads (ca. 5 ml)

[0159] catalyst bed: 10 g catalyst

[0160] reactor entrance: filled to 6 cm before the end of the reactor

[0161] Methanol (ca. 30% in nitrogen) was guided through a saturator (60° C.) with cooling spiral (40° C.) to a pre-evaporator (200° C.) and then through the reactor (400-500° C.) at a WHSV of about 0.8 for 24 h, and the gas produced in the reactor was then continuously analyzed with a gas chromatograph.

[0162] Using the aforementioned experimental set-up, the sample from example 5 was tested and compared to the performance observed with the H-AEI which was used as seeding material in the synthetic procedures of examples 1-7. The results from catalytic testing are described in the table below:

TABLE-US-00001 Sel. .sub.C2 % Sel..sub.C3 % Sel..sub.C2% Sel. .sub.C3 % C2/C3 av. 24 h av. 24 h C.sub.2/C3 >5 h >5 h >5 h example 5 25.4 31.9 0.8 32.1 38.9 0.8 commercial 35.4 19.5 1.8 36.6 16.3 2.2 H-AEI

[0163] Thus, as may be taken from the results presented in the table, it has quite unexpectedly been found that when used as a catalyst in the methanol to olefin reaction, the inventive zeolitic material leads to more that twice the selectivity towards propylene than when using a zeolitic material according to the prior art. In particular, it is tentatively assumed that said highly surprising advantages are due to the shorter diffusion paths in the primary crystals, in particular along the uniquely shorter axis of the inventive materials.

Example 9: SCR Catalytic Testing

[0164] 22.4 g ammonium nitrate and 200 g distilled water were placed in a 500 ml flask and the ammonium nitrate dissolved under stirring at 80° C. 22.4 g of the zeolitic material from example 6 were then added together with 24 g distilled water and the mixture was stirred at 80° C. for 2 h at 200 rpm. The solid product was then filtered off and washed with distilled water to electroneutrality of the washing solution (<200 μS/cm.sup.3). The solid was then dried over night at 120° C. and calcined by heating to 450° C. at 1° C./min and calcining at that temperature for 6 h, thus affording 26.4 g of ion exchanged zeolite displaying a composition as obtained from elemental analysis of: 4.4 wt.-% Al, 0.04 wt.-% Na, and 35 wt.-% Si. The material was then wet impregnated with an aqueous copper nitrate solution (incipient wetness impregnation). The material was then dried and calcined at 450° C. for 5 h for affording a zeolitic material loaded with 5.5 wt.-% of copper calculated as CuO.

[0165] 20.7 g ammonium nitrate and 180 g distilled water were placed in a 500 ml flask and the ammonium nitrate dissolved under stirring at 80° C. 20.7 g of the zeolitic material from example 7 were then added together with 27 g distilled water and the mixture was stirred at 80° C. for 2 h at 200 rpm. The solid product was then filtered off and washed with distilled water to electroneutrality of the washing solution (<200 μS/cm.sup.3). The solid was then dried over night at 120° C. and calcined by heating to 450° C. at 1° C./min and calcining at that temperature for 6 h, thus affording 22.7 g of ion exchanged zeolite displaying a composition as obtained from elemental analysis of: 3.4 wt.-% Al, <0.01 wt.-% Na, and 36 wt.-% Si. The material was then wet impregnated with an aqueous copper nitrate solution (incipient wetness impregnation). The material was then dried and calcined at 450° C. for 5 h for affording a zeolitic material loaded with 4.3 wt.-% of copper calculated as CuO.

[0166] The zeolitic materials which had been loaded with copper as described above, were then respectively shaped by preparing an aqueous slurry to which zirconium acetate was added as binder material precursor (5 weight-% based on zeolitic material). The slurry was then shaped to a tablet, dried under stirring and calcined for 1 h at 550° C. The respectively obtained tablet was then crushed and sieved to a particle size in the range of from 250 to 500 micrometer. The catalyst was then aged for 50 h at 650° C. in 10% steam/air, and for 16 h at 800° C. in 10% steam/air. Standard SCR conditions were applied by subjecting the catalytic material to a gas stream (500 ppm NO, 500 ppm NH.sub.3, 5% H.sub.2O, 10% O.sub.2, balance N.sub.2) at a gas hourly space velocity of 80,000 h.sup.−1, at temperatures of the gas stream of 200° C., 400° C., 575° C. (first run for degreening); and 175° C., 200° C., 225° C., 250° C., 300° C., 450° C., 550° C., 575° C. The amount of the catalytic material was adjusted to 120 mg per reactor; the material was diluted with corundum to about 1 ml volume. The space velocities simulated 1 mL of a coated catalyst.

[0167] The results of the SCR tests are shown in FIGS. 12 and 13, wherein the shaped body obtained with the material from example 6 is designated as “SP0005” and the shaped body obtained with the material from example 7 is designated as “SP0006”. More specifically, FIG. 12 shows the results depending on the temperature of the catalyst testing for the fresh zeolitic material (.circle-solid.) for the material aged for 50 h at 650° C. (.diamond-solid.) and for the material aged for 16 h at 820° C. (.Math.). FIG. 13, on the other hand, displays the N.sub.2O make during SCR, wherein the results are again shown depending on the temperature of the catalyst testing for the fresh zeolitic material (.circle-solid.) for the material aged for 50 h at 650° C. (.diamond-solid.) and for the material aged for 16 h at 820° C. (.box-tangle-solidup.).

[0168] The results from SCR testing relative to the NO.sub.x conversion is shown in the table below for testing of the shaped bodies at 200° C., respectively.

TABLE-US-00002 SCR testing NO.sub.x conversion [%] temperature aging Example 6 Example 7 200° C. none 89 78 200° C. 50 h at 650° C. 82 74 200° C. 16 h at 820° C. 75 59

[0169] Thus, as may be taken from the results from SCR testing, the inventive materials display excellent performance in SCR, both with regard to high NO.sub.x conversion and low N.sub.2O make both in the fresh and aged states.

CITED PRIOR ART

[0170] U.S. Pat. No. 5,958,370 [0171] Moliner, M. et al. in Chem. Commun. 2012, 48, pages 8264-8266 [0172] Maruo, T. et al. in Chem. Lett. 2014, 43, page 302-304 [0173] Martin, N. et al. in Chem. Commun. 2015, 51, 11030-11033 [0174] Dusselier, M. et al. in ACS Catal. 2015, 5, 10, 6078-6085 [0175] US 2015/0118150 A1 [0176] WO 2016/149234 A1 [0177] Ransom, R. et al. in Ind. Eng. Chem. Res. 2017, 56, 4350-4356 [0178] WO 2018/113566 A1