A ZEOLITIC MATERIAL HAVING FRAMEWORK TYPE CHA AND COMPRISING A TRANSITION METAL AND ONE OR MORE OF POTASSIUM AND CESIUM

Abstract

A zeolitic material having framework type CHA, comprising a transition metal M and an alkali metal A, and having a framework structure comprising a tetravalent element Y, a trivalent element X and 0, wherein the transition metal M is a transition metal of groups 7 to 12 of the periodic table, A is one or more of K and Cs, Y is one or more of Si, Ge, Ti, Sn and Zr, and X is one or more of Al, B, Ga and In. A process for preparing such a zeolitic material. Use of such a zeolitic material.

Claims

1. A zeolitic material having framework type CHA, comprising a transition metal M and an alkali metal A, and having a framework structure comprising a tetravalent element Y, and a trivalent element X and O, wherein the transition metal M is a transition metal of groups 7 to 12 of a periodic table, A is one or more of K and Cs, Y is one or more of Si, Ge, Ti, Sn and Zr, and X is one or more of Al, B, Ga and In.

2. The zeolitic material of claim 1, comprising M in an amount in a range of from 0.5 to 7.5 weight-%, calculated as elemental M and based on a total weight of the zeolitic material, and wherein M comprises one or more of Cu and Fe.

3. The zeolitic material of claim 1, comprising A in an amount in a range of from 0.05 to 5 weight-%, calculated as elemental A and based on a total weight of the zeolitic material.

4. The zeolitic material of claim 1, wherein in the framework structure, a molar ratio of Y relative to X, calculated as YO.sub.2:X.sub.2O.sub.3, is in a range of from 3:1 to 20:1.

5. The zeolitic material of claim 1, further comprising Na.

6. The zeolitic material of claim 1, wherein at least 98 weight-%, of the zeolitic material consist of M, A, Y, O, H, and optionally Na, and wherein at least 98 weight-% of the framework structure consist of Y, X, O, and H.

7. The zeolitic material of claim 1, having one or more of the following characteristics: a total amount of acid sites in a range of from 2.0 to 3.2 mmol/g, wherein the total amount of acid sites is defined as a total molar amount of desorbed ammonia per mass of the zeolitic material determined according to a temperature programmed desorption of ammonia; wherein the zeolitic material has an amount of medium acid sites in a range of from 1.0 to 1.7 mmol/g, wherein the amount of medium acid sites is defined as an amount of desorbed ammonia per mass of the zeolitic material determined according to the temperature programmed desorption of ammonia in a temperature range of from 250 to 450 C., a peak having a maximum in a range of from 210 to 205 nm, determined according to UV-Vis spectroscopy; and a peak having a maximum in a range of from 1,945 to 1,950 cm.sup.1, a peak having a maximum in a range of from 2,245 to 2,250 cm.sup.1, a peak having a maximum in a range of from 1,925 to 1,930 cm.sup.1, a peak having a maximum in a range of from 1,870 to 1,880 cm.sup.1, and a peak having a maximum in a range of from 1,805 to 1,810 cm.sup.1, determined according to NO adsorption via FT-IR at a pressure of 1,000 Pa.

8. A process for preparing the zeolitic material according to claim 1, the process comprising (i) providing a zeolitic material having framework type CHA in its ammonium form, the zeolitic material comprising an alkali metal A, and having a framework structure comprising a tetravalent element Y. and a trivalent element X and O, wherein A is one or more of K and Cs, Y is one or more of Si, Ge, Ti, Sn and Zr, and X is one or more of Al, B, Ga and In; (ii) subjecting the zeolitic material having framework type CHA in its ammonium form obtained from (i) to ion exchange conditions, comprising bringing the zeolitic material having framework type CHA in its ammonium m in contact with a solution comprising ions of a transition metal M of groups 7 to 12 of the periodic table, obtaining a mixture comprising a zeolitic material having framework type CHA, comprising a transition metal M and an alkali metal A, and having a framework structure comprising a tetravalent element Y, and a trivalent element X and O; and (iii) separating the zeolitic material having framework type CHA from the mixture.

9. The process of claim 8, wherein the providing a zeolitic material having framework type CRA in its ammonium form comprises: (i.1) preparing a synthesis mixture comprising water, a source of Y, a source of X, and a source of A; (i.2) subjecting the synthesis mixture to hydrothermal crystallization conditions comprising heating the synthesis mixture to a temperature in a range of from 150 to 200 C. and keeping the synthesis mixture at a temperature in the range of from 150 to 200 C. under autogenous pressure, obtaining a mother liquor comprising a zeolitic material having framework type CHA which comprises A. (i.3) separating the zeolitic material obtained from (i.2) from the mother liquor; (i.4) subjecting the zeolitic material obtained from (i.3) to ion exchange conditions, comprising bringing a solution comprising ammonium ions in contact with the zeolitic material obtained from (i.3), obtaining a zeolitic material having framework type CHA in its ammonium form.

10. The process of claim 9, wherein Y is Si and the source of Y comprises one or of silica and a silicate wherein X is Al and the source of X comprises one or more of alumina and an aluminum salt, and wherein the source of A comprises one or more of a halide of A, a nitrate of A, and a hydroxide of A.

11. The process of claim 9, wherein the synthesis mixture prepared further comprises a seed crystal material comprising a zeolitic material having framework type CHA.

12. The process of claim 9, wherein the solution comprising ammonium ions according to (i.4) has an ammonium concentration in the range of from 1 to 5 mol/l.

13. The process of claim 8, wherein the solution comprising ions of a transition metal is an aqueous solution comprising a dissolved salt of the transition metal M.

14. The process of claim 8, further comprising (iv) calcining the zeolitic material obtained from obtaining the zeolitic material having framework type CHA, comprising a transition metal M and an alkali metal A, and having a framework structure comprising a tetravalent element Y, and a trivalent element X and O.

15. A zeolitic material, obtained by the process according to claim 8.

16. A catalyst, comprising the zeolitic material according to claim 1.

Description

EXAMPLES

Reference Example 1.1: Determination of NH3-TPD Profiles

[0165] Temperature-programmed desorption of ammonia (NH3-TPD) profiles were recorded on a Multitrack TPD equipment (Japan BEL). Typically, 25 mg catalyst were pretreated at 873 K in a He flow (50 mL/min) for 1 h and then cooled to 373 K. Prior to the adsorption of NH3, the sample was evacuated at 373 K for 1 h. Approximately 2500 Pa of NH3 were allowed to make contact with the sample at 373 K for 30 min. Subsequently, the sample was evacuated to remove weakly adsorbed NH.sub.3 at the same temperature for 30 min. Finally, the sample was heated from 373 to 873 K at a ramping rate of 10 K/min in a He flow (50 mL/min). A thermal conductivity detector (TCD) was used to monitor desorbed NH3.

Reference Example 1.2: Determination of UV-Vis Spectra

[0166] UVvis diffuse reflectance spectra were recorded on a V-650DS spectrometer (JASCO). The diffuse reflectance spectra were converted into the absorption spectra by using the Kubelka Munk function.

Reference Example 1.3: Determination of FT-IR Spectra

[0167] FTIR spectra were obtained at a resolution of 4 cm.sup.1 using a Jasco FTIR 4100 spectrometer equipped with a TGS detector. The powdered samples (about 30 mg) were pelletized into a self-supporting disk of 1 cm in diameter, which was held in a glass cell. After evacuation at 500 C. for 2 h, the sample was cooled back to ambient temperature prior to background spectra acquisition. Then NO was introduced into the cell in a pulse mode fashion (about 5 Pa for the first pulse, until total pressure in the IR cell reached about 1,000 Pa). After equilibrium NO pressure was reached after each pulse of NO, an IR spectrum was obtained.

Reference Example 1.4: Elemental Analysis

[0168] Elemental analyses were performed on an inductively coupled plasma-atomic emission spectrometer (ICP-AES, Shimadzu ICPE-9000).

Reference Example 2: Preparation of Seed Crystalline Material

[0169] 2.31 g of Y zeolite (CBV712, Zeolyst) were added to an aqueous solution containing 0.28 g of NaOH (97%, from Wako Chemicals) and 1.42 g of trimethyladamantylammonium hydroxide (TMAdaOH) (7.28 g of TMAdaOH aqueous 20 weight-%), with stirring for 1 h. The molar composition of the resultant gel was 1 SiO.sub.2:0.083 Al.sub.2O.sub.3:0.1 NaOH:0.2 TMAdaOH:10 H.sub.2O. The thus prepared mother gel was crystallized in an autoclave at 150 C. for 2 days under tumbling condition (40 r.p.m.). The crystalline solid product, a zeolitic material having framework type CHA, was recovered by filtration, washed with distilled water, dried overnight at 100 C., and calcined at 600 C. for 6 h under air.

Reference Example 3: Preparation of a Comparative Zeolitic Materiala Zeolitic Material having Framework type CHA and Comprising Cu

[0170] a) 277 kg of a 20 weight-% aqueous solution of cyclohexyltrimethylammonium hydroxide (CHTMAOH) and 78 kg of a 25 weight-% aqueous solution of tetramethylammonium hydroxide (TMAOH) were placed in an autoclave after which 34.8 kg of aluminumtriisopropylate were added under stirring at 50 r.p.m., and further stirred at that rate until the aluminumtriisopropylate had entirely dissolved. 358 kg of a 40 weight-% solution of colloidal silica (Ludox AS40) were then added, and the mixture stirred an additional 10 min. Finally, 5.7 kg of SSZ-13 zeolite (prepared according to Reference Example 2) were added to the mixture under stirring, wherein the pH of the resulting mixture was measured to be 14.24. The mixture was then crystallized at 170 C. for 18 h, wherein the mixture was first progressively heated to the reaction temperature using a constant temperature ramp over a period of 7 h. A white suspension having a pH of 13.14 was obtained, which was filtered and the solid washed with distilled water until substantial electroneutrality of the washwater was achieved. The resulting solid was dried and subsequently calcined at 550 C. for 5 h under air, obtaining a zeolitic material having framework type CHA in powder form. Elemental analysis of the product afforded (in weight-%): Si: 34.0; Al: 2.6; Na: 0.12. 1.3 kg of distilled water and 202.2 g of the calcined zeolitic material were placed in a 4 L receptacle and heated to 60 C. and held at that temperature for 30 min. Subsequently, 20.13 g of copper(II) acetate and 2.22 g of 70% acetic acid were added and the mixture further heated at 60 C. for 1 h under constant stirring of the mixture at 200 r.p.m. Heating was then discontinued, and 975 g of distilled water were added to the mixture which was then filtered and washed with distilled water until the wastewater displayed a conductivity of 138 microSiemens. The filter cake was then dried over night at 120 C. affording 208 g of copper ion exchanged zeolitic material having framework type CHA. Elemental analysis of the copper ion-exchanged product afforded (in weight-%): Si: 49.0; Al: 3.1; Cu: 2.2; Na: 0.02. The product is also referred to herein as Cu(2.2)-CHA(BASF)-15.8. [0171] b) Another material was prepared according to the process above, however with a Si:Al ratio of 12.2 and a Cu content of 2.4 weight-%. This product is also referred to herein as Cu(2.4)-CHA(BASF)-12.2.

Example 1: Preparation of a Zeolitic Material of the Present Invention Comprising K

1.1 Template-Free Preparation of a Zeolitic Material Having Framework Type CHA

[0172] 0.817 g aluminum triisopropylate (Al(OiPr)3, >99.9%, from Kanto Chemical) were added to an aqueous solution containing 0.96 g NaOH (>99%; from Wako Chemicals) and 0.224 g KOH (>85%, from Wako Chemicals) with stirring for 1 h. Then, 2.4 g fumed silica (Cab-O-Si M5, from Cabot) were added to the mixture and stirred for 1 h. The molar composition of the resultant gel was 1 SiO.sub.2:0.1 Al(OiPr).sub.3:0.6 NaOH:0.1 KOH : 100 H.sub.2O. Then, 0.48 g calcined seed crystalline material prepared as described in Reference Example 2 above (20 weight-% based on silica) were added to the mixture. The thus prepared mother gel was crystallized in an autoclave at 170 C. for 2 days under tumbling condition (20 r.p.m.). The solid crystalline product, a zeolitic material having framework type CHA, was recovered by filtration, washed with distilled water, and dried overnight at 100 C. in air. [0173] b) 1 g of the zeolitic material obtained according to a) was treated with 100 mL aqueous 2.5 M NH.sub.4NO.sub.3 at 80 C. for 3 h twice to obtain the ammonium form of the zeolitic material. The product is also referred to herein as NH4-TF-SSZ-13(K). [0174] c) The zeolitic material in it ammonium form obtained according to b) was calcined at 500 C. for 5 h under air to obtain the H-form of the zeolitic, material, also referred to herein as H-TF-SSZ-13(K).

[0175] The composition of the zeolitic materials, analyzed by elemental analysis according to Reference Example 1.4, was as follows:

TABLE-US-00001 TABLE 1 Composition of the zeolitic materials prepared according to Example 1.1 Zeolitic material Na content/ Na exchange K content/ K exchange according to weight-% level/% .sup.1) weight-% level/% .sup.1) Example 1.1 a) 4.0 4.7 Example 1.1 b) 0.3 92.5 0.5 89.4 .sup.1) ion exchange level/% = {1 [(ion content after ammonium exchange/weight-%)/(ion content before ammonium exchange/weight-%)]} * 100

1.2 Preparation of a Cu Containing Zeolitic Material Having Framework Type CHA

[0176] Cu(NO.sub.3).sub.33H.sub.2O (>99%, from Wako Chemicals) was used as Cu source. 1 g of NH4-TF-SSZ-13(K) prepared according the 1.1 b) above was ion-exchanged with 100 g aqueous 0.005, 0.1 and 0.2 M 2 M Cu(NO.sub.3).sub.3 at room temperature for 24 h. The solid product was recovered by filtration, washed with distilled water, dried overnight at 100 C., and calcined at 500 C. for 5 h under air. The product is also referred to herein as Cu-TF-SSZ-13(K).

[0177] The composition of the zeolitic materials, analyzed by elemental analysis according to Reference Example 1.4, was as follows:

TABLE-US-00002 TABLE 2 Composition of the zeolitic materials prepared according to Example 1.2 Content Content Content Ion SiO.sub.2/ Cu/ K/ Na/ Zeolitic exchange Al.sub.2O.sub.3 Si/ Cu/ weight- weight- weight- material conditions (Si/Al) Cu Al % % % Cu(2.7)- 0.005M 7.4 (3.7) 30.8 0.12 2.7 0.3 0.3 TF-SSZ- 13(K) Cu(3.8)- 0.01M 7.4 (3.7) 21.4 0.17 3.8 0.3 0.3 TF-SSZ- 13(K) Cu(4.8)- 0.02M 7.4 (3.7) 16.7 0.22 4.8 0.4 0.3 TF-SSZ- 13(K)

[0178] The UV-Vis spectra of the three materials are shown in FIG. 1. According to the spectra, the Cu is well-dispersed or exists as isolated ions at the exchange sites.

[0179] In FIGS. 3, 4, and 5, the NO adsorption FT-IR spectra of the three materials are shown. According to the spectra, the Cu, as Cu.sup.2', is mainly located in the faces of the 6 MR (1947 cm.sup.1, 1929 cm.sup.1), and the ratio [Cu.sup.2+]/[Cu.sup.+] is high.

[0180] In FIG. 9, the NH3-TPD profiles of the three materials are shown, compared to the NH3-TPD profile of the zeolitic material prepared according to example 1.1 c) (zeolitic material, calcined, H form). According to the profiles, the Cu ions shows medium acid strength (reference is made to peak III, and with increasing Cu content, the number of the weak acid sites increased (peak II). The following results were obtained from the profiles:

TABLE-US-00003 TABLE 3 Results from the NH3-TPD profiles of the zeolitic material prepared according to Example 1.2 and Example 1.1 c) peak I/ peak II/ peak III/ peak IV/ mmol/g mmol/g mmol/g mmol/g Zeolitic material ( C.) ( C.) ( C.) ( C.) H-TF-SSZ-13(K) 0.303 0.432 0.496 0.473 (167) (203) (325) 469 Cu(2.7)-TF-SSZ- 0.261 0.289 (1.236) 0.635 13(K) (166) (201) (309) (473) Cu(3.8)-TF-SSZ- 0.352 0.542 1.353 0.515 13(K) (171) (227) (344) (492) Cu(4.8)-TF-SSZ- 0.364 0.603 1.370 0.425 13(K) (173) (234) (354) (501)

Example 2: Preparation of a Zeolitic Material of the Present Invention Comprising Cs

[0181] 2.1 Template-free preparation of a zeolitic material having framework type CHA 0.817 g aluminum triisopropylate (Al(OiPr).sub.3, >99.9%, from Kanto Chemical) were added to an aqueous solution containing 0.64 g NaOH (>99%; from Wako Chemicals) and 0.672 g CsOHH.sub.2O (>99.95%, from Sigma-Aldrich) with stirring for 1 h. Then, 2.4 g fumed silica (Cab-O-Sil M5, from Cabot) were added to the mixture and stirred for 1 h. The molar composition of the resultant gel was 1 SiO.sub.2:0.1 Al(OiPr).sub.3:0.4 NaOH:0.1 CsOH:100 H.sub.2O. Then, 0.48 g calcined seed crystalline material prepared as described in

[0182] Reference Example 2 above (20 weight-% based on silica) were added to the mixture. The thus prepared mother gel was crystallized in an autoclave at 170 C. for 2 days under tumbling condition (20 r.p.m.). The solid crystalline product, a zeolitic material having framework type CHA, was recovered by filtration, washed with distilled water, and dried overnight at 100 C. in air. [0183] b) 1 g of the zeolitic material obtained according to a) was treated with 100 mL aqueous 2.5 M NH.sub.4NO.sub.3 at 80 C. for 3 h twice to obtain the ammonium form of the zeolitic material. The product is also referred to herein as NH4-TF-SSZ-13(Cs). [0184] c) The zeolitic material in it ammonium form obtained according to b) was calcined at 500 C. for 5 h under air to obtain the H-form of the zeolitic material, also referred to herein as H-TF-SSZ-13(Cs).

[0185] The composition of the zeolitic materials, analyzed by elemental analysis according to Reference Example 1.4, was as follows:

TABLE-US-00004 TABLE 4 Composition of the zeolitic materials prepared according to Example 2.1 Na Na Cs Cs Zeolitic material content/ exchange content/ exchange according to weight-% level/% .sup.1) weight-% level/% .sup.1) Example 2.1 a) 3.4 10.7 Example 2.1 b) 0.3 91.2 2.0 81.3 .sup.1) ion exchange level/% = {1 [(ion content after ammonium exchange/weight-%)/(ion content before ammonium exchange/weight-%)]} * 100

2.2 Preparation of a Cu Containing Zeolitic Material Having Framework type CHA

[0186] Cu(NO.sub.3).sub.33H.sub.2O (>99%, from Wako Chemicals) was used as Cu source. 1 g of NH4-TF-SSZ-13(Cs) prepared according the 2.1 b) above was ion-exchanged with 100 g aqueous 0.005, 0.01 and 0.02 M Cu(NO3)3 at room temperature for 24 h. The solid product was recovered by filtration, washed with distilled water, dried overnight at 100 C., and calcined at 500 C. for 5 h under air. The product is also referred to herein as Cu-TF-SSZ-13(Cs).

[0187] The composition of the zeolitic materials, analyzed by elemental analysis according to Reference Example 1.4, was as follows:

TABLE-US-00005 TABLE 5 Composition of the zeolitic materials prepared according to Example 2.2 Content Content Content Ion SiO.sub.2/ Cu/ Cs/ Na/ Zeolitic exchange A1.sub.2O.sub.3 Si/ Cu/ weight- weight- weight- material conditions (Si/A1) Cu Al % % % Cu(2.6)- 0.005M 8.4 (4.2) 31.6 0.13 2.6 0.7 0.2 TF-SSZ- 13(Cs) Cu(3.8)- 0.01M 8.4 (4.2) 22.5 0.19 3.8 0.6 0.2 TF-SSZ- 13(Cs) Cu(4.2)- 0.02M 8.4 (4.2) 19.9 0.21 4.2 0.7 0.2 TF-SSZ- 13(Cs)

[0188] The UV-Vis spectra of the three materials are shown in FIG. 2. Clearly, the Cu is well-dispersed or exists as isolated ions at the exchange sites. In FIGS. 6, 7, and 8, the NO adsorption FT-IR spectra of the three materials are shown. According to the spectra, the Cu, as Cu.sup.2+, is mainly located in the faces of the 6 MR (1947 cm.sup.1, 1929 cm.sup.1), and the ratio [Cu.sup.2+]/[Cu.sup.+] is high. In FIG. 10, the NH3-TPD profiles of the three materials are shown, compared to the NH3-TPD profile of the zeolitic material prepared according to example 2.1 c) (zeolitic material, calcined, H form). According to the profiles, the Cu ions shows medium acid strength (reference is made to peak III, and with increasing Cu content, the number of the weak acid sites increased (peak II). The following results were obtained from the profiles:

TABLE-US-00006 TABLE 6 Results from the NH3-TPD profiles of the zeolitic material prepared according to Example 2.2 and Example 2.1 c) peak I/ peak II/ peak III/ peak IV/ mmol/g mmol/g mmol/g mmol/g Zeolitic material ( C.) ( C.) ( C.) ( C.) H-TF-SSZ-13(Cs) 0.391 0.285 0.491 0.579 (170) (206) (334) (470) Cu(2.6)-TF-SSZ-13(Cs) 0.460 0.462 (1.177) 0.544 (172) (231) (352) (489) Cu(3.8)-TF-SSZ-13(Cs) 0.379 0.566 1.345 0.479 (171) (240) (361) (496) Cu(4.2)-TF-SSZ-13(Cs) 0.365 0.596 1.444 0.481 (173) (233) (356) (500)

Example 3: Catalytic Testing of the Zeolitic Materials of the Present Invention

[0189] Based on the zeolitic powder materials prepared according to the Examples above, catalyst 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 and calcined for 1 h at 550 C. The moldings were then crushed and sieved to as particle size of 250-500 micrometer. For the subsequent tests, respectively fresh and aged Cu containing materials were used. For ageing, the crushed and sieved particles were subjected for 6 h to air comprising 10 volume-% water at 750 C. The materials used were:

[0190] Cu(2.4)-CHA(BASF)-12.2 (see Reference Example 3 b) hereinabove) [0191] Cu(2.7)-TF-SSZ-13(K) (see Example 1, Table 2 hereinabove) [0192] Cu(2.6)-TF-SSZ-13(Cs) (see Example 2, Table 5 hereinabove)

[0193] The moldings comprising the zeolitic materials were subjected to a selective catalytic reduction test. 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. A given sample was exposed to a feed stream (500 ppm NO, 500 ppm NH.sub.3, 5% H.sub.2O, 10% O.sub.2, balance He) at a gas hourly space velocity of 80,000 h.sup.1, at temperatures of the feed stream of 150 C., 200 C., 250 C., 300 C., 350 C., 400 C., 450 C., 500 C., and 550 C. Reference is made to FIG. 11 showing the NO conversion as a function of the temperature of the gas stream for the fresh samples, and to FIG. 12 showing the NO conversion as a function of the temperature of the gas stream for the aged samples.

[0194] From FIG. 11, it can be derived that in the temperature range of from 200 to 550 C., both the fresh inventive materials Cu(2.7)-TF-SSZ-13(K) and Cu(2.6)-TF-SSZ-13(Cs) show either the same or a significantly better NO conversion than the comparative fresh material Cu(2.4)-CHA(BASF)-12.2. In particular Cu(2.6)-TF-SSZ-13(Cs) shows a very high NO conversion over this entire temperature range, and Cu(2.7)-TF-SSZ-13(K) a slightly decreased yet still remarkable NO conversion.

[0195] From FIG. 12, it an be derived that in the temperature range of from 250 to 550 C., both the aged inventive materials Cu(2.7)-TF-SSZ-13(K) and Cu(2.6)-TF-SSZ-13(Cs) show either the same or a better NO conversion than the comparative aged material Cu(2.4)-CHA(BASF)-12.2. Again, starting from a temperature of 300 C., Cu(2.6)-TF-SSZ-13(Cs) shows the best NO conversion, and Cu(2.7)-TF-SSZ-13(K) a slightly decreased yet still remarkable NO conversion.

SHORT DESCRIPTION OF THE FIGURES

[0196] FIG. 1 shows the UV-Vis spectra of the three zeolitic materials prepared according to Example 1.2.

[0197] FIG. 2 shows the UV-Vis spectra of the three zeolitic materials prepared according to Example 2.2.

[0198] FIG. 3 shows the shows the UV-Vis spectra of a zeolitic materials prepared according to Example 1.2 (Cu(2.7)-TF-SSZ13(K)-3.7).

[0199] FIG. 4 shows the shows the UV-Vis spectra of a zeolitic materials prepared according to Example 1.2 (Cu(3.8)-TF-SSZ13(K)-3.7).

[0200] FIG. 5 shows the shows the UV-Vis spectra of a zeolitic materials prepared according to Example 1.2 (Cu(4.8)-TF-SSZ13(K)-3.7).

[0201] FIG. 6 shows the shows the UV-Vis spectra of a zeolitic materials prepared according to Example 2.2 (Cu(2.6)-TF-SSZ13(Cs)-4.2).

[0202] FIG. 7 shows the shows the UV-Vis spectra of a zeolitic materials prepared according to Example 2.2 (Cu(3.8)-TF-SSZ13(Cs)-4.2).

[0203] FIG. 8 shows the shows the UV-Vis spectra of a zeolitic materials prepared according to Example 2.2 (Cu(4.2)-TF-SSZ13(K)-4.2).

[0204] FIG. 9 shows the NH3-TPD profiles of the three materials prepared according to Example 1.2 and the material prepared according to Example 1.1 c).

[0205] FIG. 10 shows the NH3-TPD profiles of the three materials prepared according to Example 2.2 and the material prepared according to Example 2.1 c).

[0206] FIG. 11 shows the NO conversion as a function of the applied temperature for the NH.sub.3-SCR testing according to Example 3 of two fresh catalysts comprising a zeolitic material according to the present invention and one catalyst comprising a fresh comparative zeolitic material.

[0207] FIG. 12 shows the NO conversion as a function of the applied temperature for the NH.sub.3-SCR testing according to Example 3 of two aged catalysts comprising a zeolitic material according to the present invention and one catalyst comprising an aged comparative zeolitic material.