PRODUCTION OF HYDROTHERMALLY STABLE CHA ZEOLITES

Abstract

A method of producing hydrothermally stable chabazite (CHA) zeolites is disclosed. The disclosed method is based on the use of reaction mixtures that (1) are essentially void of alkali metal cations and (2) contain the N,N,N-trimethyl-1-adamantyl ammonium (TMAda+) organic as the sole OSDA. The disclosed method results in a higher crystalline CHA zeolite that exhibits hydrothermal stability. There is also disclosed a zeolite material having a CHA-type framework structure made by the disclosed method. A method of selective catalytic reduction of NOx in exhaust gas using the material described herein is also disclosed.

Claims

1. A method of making a microporous crystalline material from reaction mixtures that (1) are essentially void of alkali metal cations and (2) contain the N,N,N-trimethyl-1-adamantyl ammonium (TMAda+) organic as the sole OSDA, the method comprising: mixing sources of alumina, silica, water, TMAdaOH and optionally a chabazite seed material to form a gel; heating the gel in a vessel at a temperature ranging from 80 C. to 200 C. to form a crystalline chabazite product; and calcining the product to produce an aluminosilicate zeolite having a CHA structure, and a silica-to-alumina ratio (SAR) ranging from 20 to 100.

2. The method of claim 1, wherein the reaction mixtures with (A) molar composition 1 SiO.sub.2:w Al.sub.2O.sub.3:x TMAdaOH:y H.sub.2O, where w=0.010-0.050, x=0.04-0.20, y=1-25 and (B) trace concentrations of alkali cations.

3. The method of claim 2, wherein w ranges from 0.014-0.050.

4. The method of claim 2, wherein x ranges from 0.05-0.15.

5. The method of claim 2, wherein y ranges from 5-20.

6. The method of claim 1, wherein the aluminosilicate zeolite has a silica-to-alumina ratio (SAR) ranging from 20-70.

7. The method of claim 1, further comprising adding to the microporous crystalline material at least one metal chosen from copper, iron or combinations thereof to form a metal containing chabazite.

8. The method of claim 7, wherein the metal containing chabazite retains at least 70% of its initial surface area and micropore volume after exposure to temperatures of up to 900 C. in the presence of up to 10 volume percent water vapor for up to 1 hour.

9. The method of claim 7, wherein copper and/or iron are introduced by liquid-phase or solid ion-exchange or impregnation or incorporated by direct-synthesis.

10. The method of claim 9, wherein copper comprises at least 1.0 weight percent of the total weight of the material.

11. The method of claim 10, wherein copper comprises an amount ranging from 1.0 to 6.0 weight percent of the total weight of the material.

12. The method of claim 7, wherein iron comprises at least 0.5 weight percent of the total weight of said material.

13. The method of claim 12, wherein iron comprises an amount ranging from 0.5 to 6.0 weight percent of the total weight of said material.

14. The method of claim 1, wherein the source of alumina is aluminum trihydroxide.

15. The method of claim 14, wherein the aluminum trihydroxide is dissolved into a TMAdaOH solution.

16. The method of claim 1, wherein the source of silica is a silica sol.

17. The method of claim 1, wherein during heating, the gel is stirred while a seed material with a CHA topology is added before loading into an autoclave.

18. The method of claim 1, wherein after calcining the calcined zeolite was ion-exchanged with copper in a copper (II) acetate solution.

19. The method of claim 18, wherein the initial surface area of the copper containing chabazite is at least 650 m.sup.2/g.

20. The method of claim 18, wherein the initial micropore volume of the copper containing chabazite is at least 0.25 cc/g.

21. An alkali-free zeolite material having a CHA-type framework structure, having a micropore volume to total pore volume ratio greater than 90% and derived from a pre-calcined, organic containing zeolite having a measured TMAda+/cage ratio of less than 1.05.

22. The zeolite of claim 21, which has an SAR ranging from 20-100.

23. The zeolite of claim 22, which has an SAR ranging from 20-70.

24. The zeolite of claim 21, further comprising at least one metal chosen from copper, iron or combinations thereof.

25. The zeolite of claim 24, wherein the metal containing chabazite retains at least 70% of its initial surface area and micropore volume after exposure to temperatures of up to 900 C. in the presence of up to 10 volume percent water vapor for up to 1 hour.

26. The zeolite of claim 24, which contains copper in an amount of at least 1.0 weight percent of the total weight of the material.

27. The zeolite of claim 26, which contains copper in an amount ranging from 1.0 to 6.0 weight percent of the total weight of said material.

28. The zeolite of claim 24, which contains iron in an amount of at least 0.5 weight percent of the total weight of said material.

29. The zeolite of claim 28, which contains iron in an amount ranging from 0.5 to 6.0 weight percent of the total weight of said material.

30. The zeolite of claim 21, wherein the micropore volume to total pore volume ratio is greater than 92%

31. A method of selective catalytic reduction (SCR) of NOx in exhaust gas, said method comprising: contacting exhaust gas with a zeolitic material comprising a copper containing CHA-type zeolites having a micropore volume to total pore volume ratio greater than 90% and a measured TMAda+/cage ratio of less than 1.05, wherein said copper containing chabazite retains at least 70% of its initial surface area and micropore volume after exposure to temperatures of up to 900 C. in the presence of up to 10 volume % water vapor for up to 1 hr.

32. The method of claim 31, wherein said contacting step is performed in the presence of ammonia or urea.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0019] The accompanying figures are incorporated in, and constitute a part of this specification.

[0020] FIG. 1 shows X-ray diffraction patterns of Cu-CHA zeolites from entries 3, 4, 8, and 32 in Table 1.

[0021] FIG. 2 shows X-ray diffraction patterns of Cu-CHA zeolites from entries 11 and 12 in Table 1.

[0022] FIG. 3 shows X-ray diffraction patterns of Cu-CHA zeolites from entries 15 and 16 in Table 1.

[0023] FIG. 4 shows X-ray diffraction patterns of Cu-CHA zeolites from entries 19 and 20 in Table 1.

[0024] FIG. 5 shows X-ray diffraction patterns of Cu-CHA zeolites from entries 23 and 24 in Table 1.

[0025] FIG. 6 shows X-ray diffraction patterns of Cu-CHA zeolites from entries 27 and 28 in Table 1.

[0026] FIG. 7 is a Comparison of Inventive Examples vs. Comparative Examples: XRD patterns of hydrothermally treated materials.

[0027] FIG. 8 SEM image of Example 1.

[0028] FIG. 9 SEM image of Example 2.

[0029] FIG. 10 SEM image of Comparative Example 1.

[0030] FIG. 11 SEM image of Comparative Example 2.

[0031] FIG. 12 SEM image of Comparative Example 3.

[0032] FIG. 13 SEM image of Comparative Example 5.

[0033] FIG. 14 SEM image of Comparative Example 6.

[0034] FIG. 15 SEM image of Comparative Example 7.

[0035] FIG. 16 SEM image of Comparative Example 9.

[0036] FIG. 17 SEM image of Example 3.

DETAILED DESCRIPTION

[0037] Generally zeolite materials that are highly crystalline are more thermally and hydrothermally stable than zeolite materials that are partially non-crystalline.

[0038] As used herein, Initial Surface Area refers to the surface area of the freshly made crystalline material before exposing it to any aging conditions.

[0039] As used herein, Micropore volume refers to indicate the total volume of pores having a diameter of less than 20 angstroms. Initial Micropore Volume means the micropore volume of the freshly made crystalline material, i.e., before exposing it to any aging conditions. The assessment of micropore volume is particularly derived from the BET measurement techniques by an evaluation method called the t-plot method (or sometimes just termed the t-method) as described in the literature (Journal of Catalysis 3, 32 (1964)).

[0040] As used herein, Mesopore volume refers to the volume of pores having a diameter of greater than 20 angstroms up to the limit of 600 angstroms.

[0041] As used herein, Total pore volume refers to the sum of the micropore volume and mesopore volume.

[0042] As used herein, micropore area refers to the surface area in pores less than 20 angstroms, and mesopore area refers to the surface area in pores between 20 angstroms and 600 angstroms.

[0043] As used herein, essentially void of alkali metal cations, means that the method of making a zeolite was done without the use of alkali cations, such as Li, Na, K, Rb and Cs, during synthesis. This term also refers to fact that the resulting material has never been in contact with an alkali cation during any processing step.

[0044] There is described a method of making a microporous crystalline material from reaction mixtures that (1) are essentially void of alkali metal cations and (2) contain the N,N,N-trimethyl-1-adamantyl ammonium (TMAda+) organic as the sole OSDA. In an embodiment, the method comprises mixing sources of alumina, such as aluminum trihydroxide, silica, such as silica sol, water, TMAdaOH and optionally a chabazite seed material to form a gel. Next the gel is heated in a vessel at a temperature ranging from 80 C. to 200 C. to form a crystalline chabazite product; and calcining the product to produce an aluminosilicate zeolite having a CHA structure, and a silica-to-alumina ratio (SAR) ranging from 20 to 100, such as from 20 to 70.

[0045] Non-limiting examples of sources of alumina that may be used in the present disclosure include aluminum hydroxide, alumina, alumina hydrates, aluminum alkoxides, aluminum nitrate, aluminum sulfate and aluminum acetate. In an embodiment, the source of alumina, e.g., aluminum trihydroxide, is dissolved into a TMAdaOH solution.

[0046] Non-limiting examples of sources of silica that may be used in the present disclosure include colloidal silica, silica gel, precipitated silica, silica-alumina, fumed silica, silicon alkoxides, and the like. In an embodiment, the colloidal silica (silica sol) is stabilized with ammonium ions rather than alkali ion, such as sodium and potassium.

[0047] The disclosed method describes ratios for various aspects of the gel. For example, the gel may have a water to silica (H.sub.2O/SiO.sub.2) molar ratio of 5-20. The gel may also have a TMAdaOH to silica (TMAdaOH/SiO.sub.2) molar ratio ranging from 0.05-0.15.

[0048] In an embodiment, the reaction mixtures comprise (A) molar composition 1 SiO.sub.2:w Al.sub.2O.sub.3:x TMAdaOH:y H.sub.2O, where w ranges from 0.010-0.050, such as from 0.014-0.050; x ranges from 0.04-0.20, such as from 0.05-0.15; and y ranges from 1-25, such as from 5-20 and (B) trace concentrations of alkali cations.

[0049] In one embodiment, the method further comprises adding to the microporous crystalline material at least one metal chosen from copper, iron or combinations thereof to form a metal containing chabazite. In an embodiment, the metal containing chabazite described herein retains at least 70% of its initial surface area and micropore volume after exposure to temperatures of up to 900 C. in the presence of up to 10 volume percent water vapor for up to 1 hour.

[0050] The metal may be added by known methods. For example, copper and/or iron may be introduced by liquid-phase or solid ion-exchange or impregnation or incorporated by direct-synthesis. In an embodiment, the metal comprises copper in an amount of at least 1.0 weight percent of the total weight of the material, such as an amount ranging from 1.0 to 6.0 weight percent of the total weight of the material. In addition, or alternatively, the metal comprises iron comprises in an amount of at least 0.5 weight percent of the total weight of the material, such as an amount ranging from 0.5 to 6.0 weight percent of the total weight of the material.

[0051] In one embodiment, during the described heating step, the gel is stirred while a seed material with the CHA topology is added before loading into an autoclave to ensure a chabazite crystal structure is formed.

[0052] Non-limiting examples of sources of copper that may be used in the present disclosure include copper salts such as cupric acetate, cupric nitrate, cupric sulfate, cupric hydroxide and cupric chloride. In an embodiment, there is described a method in which after calcining, the resulting calcined zeolite is ion-exchanged with copper using a copper (II) acetate solution. The resulting copper containing chabazite has an initial surface area of the is at least 650 m.sup.2/g and an initial micropore volume of at least 0.25 cc/g.

[0053] The method described herein is used to make an alkali-free zeolite material having a CHA-type framework structure. In one embodiment, this alkali-free zeolite material has a micropore volume to total pore volume ratio greater than 90% and derived from a pre-calcined, organic containing zeolite having a measured TMAda+/cage ratio of less than 1.05.

[0054] As stated, the disclosed zeolite typically has an SAR ranging from 20-100, such as from 20-70. The disclosed zeolite may further comprise at least one metal chosen from copper, iron or combinations thereof, in the amounts previously mentioned, copper in an amount of at least 1.0 weight percent of the total weight of the material, such as an amount ranging from 1.0 to 6.0 weight percent of the total weight of the material. In addition, or alternatively, the metal comprises iron comprises in an amount of at least 0.5 weight percent of the total weight of the material, such as an amount ranging from 0.5 to 6.0 weight percent of the total weight of the material.

[0055] As stated, the metal containing chabazite retains at least 70% of its initial surface area and micropore volume after exposure to temperatures of up to 900 C. in the presence of up to 10 volume percent water vapor for up to 1 hour.

[0056] In an embodiment, the zeolite described herein may have a micropore volume to total pore volume ratio that is greater than 90%, such as greater than 92% or even greater than 95%.

[0057] There is also disclosed a method of selective catalytic reduction (SCR) of NOx in exhaust gas using the disclosed CHA-type zeolites. This method comprises contacting exhaust gas with a zeolitic material comprising a copper containing CHA-type zeolites having a micropore volume to total pore volume ratio greater than 90% and a measured TMAda+/cage ratio of less than 1.05, wherein said copper containing chabazite retains at least 70% of its initial surface area and micropore volume after exposure to temperatures of up to 900 C. in the presence of up to 10 volume % water vapor for up to 1 hr. The method of SCR described herein is typically performed in the presence of ammonia or urea.

EXAMPLES

[0058] The following non-limiting examples, which are intended to be exemplary, further clarify the present disclosure.

Example 1Alkali-Free CHA Synthesis

[0059] Aluminum trihydroxide (55% Al.sub.2O.sub.3, Sigma-Aldrich) is dissolved into a TMAdaOH solution (25 wt. % in water) for about 15 minutes followed by slow addition of silica sol (40% SiO.sub.2, Ludox AS-40). The gel is stirred for 80 minutes and seed material with the CHA topology was added (2.5 wt. % of total silica) before loading into a stainless steel autoclave (Parr Instruments, 2000 ml). The molar composition of the gel was 1.0 SiO.sub.2/0.033 Al.sub.2O.sub.3/0.11 TMAdaOH/9.0 H.sub.2O. The autoclave was heated to 160 C. and maintained at the temperature for 36 hours while stirring at 200 RPM. After cooling, the product was recovered by filtration, washed with deionized water, and dried in a 110 C. convection oven. The as-synthesized product had the X-ray diffraction pattern of chabazite, a SiO.sub.2/Al.sub.2O.sub.3 ratio (SAR) of 32.9 and contained 0.04 wt. % Na.sub.2O as summarized in Table 1. The occluded organic in the dried as-synthesized zeolite was removed by calcination in air at 600 C. for 6 hours. The calcined zeolite was ion-exchanged in a copper (II) acetate solution at 60 C.

Example 2Alkali-Free CHA Synthesis

[0060] Another sample was prepared using the same protocol as described in Comparative Example 2, except the molar composition of the final mixture was adjusted to prepare a CHA zeolite with a different SAR. The composition of the final reaction mixture was 1.0 SiO.sub.2/0.036 Al.sub.2O.sub.3/0.12 TMAdaOH/9.37 H.sub.2O. The autoclave was heated to 160 C. and maintained at the temperature for 96 hours while stirring at 200 RPM.

Example 3Alkali-Free CHA Synthesis

[0061] Aluminum trihydroxide (55% Al.sub.2O.sub.3, Sigma-Aldrich) is dissolved into a TMAdaOH solution (20 wt. % in water) for about 15 minutes followed by slow addition of silica sol (40% SiO.sub.2, Ludox AS-40). The gel is stirred for 80 minutes and seed material with the CHA topology was added (2.5 wt. % of total silica) before loading into a stainless steel autoclave (Parr Instruments, 2000 ml). The molar composition of the gel was 1.0 SiO.sub.2/0.027 Al.sub.2O.sub.3/0.10 TMAdaOH/9.79 H.sub.2O. The autoclave was heated to 160 C. and maintained at the temperature for 36 hours while stirring at 200 RPM. After cooling, the product was recovered by filtration, washed with deionized water, and dried in a 110 C. convection oven. The as-synthesized product had the X-ray diffraction pattern of chabazite, a SiO.sub.2/Al.sub.2O.sub.3 ratio (SAR) of 40.5 and contained 0.00 wt. % Na.sub.2O as summarized in Table 1. The occluded organic in the dried as-synthesized zeolite was removed by calcination in air at 600 C. for 6 hours. The calcined zeolite was ion-exchanged in a copper (II) acetate solution at 60 C.

Example 4Hydrothermal Stability Testing

[0062] The hydrothermally stability of the Cu-CHA zeolites in Example 1, Example 2, and Example 3 were tested by heating to 900 C. for 1 hour in flowing air containing 10% moisture. The surface area, micropore volumes, and X-ray diffraction (XRD) patterns of the material were compared before and after the hydrothermal treatment and the results are summarized in Table 1 and FIG. 1. The zeolite prepared using the disclosed methods described herein remained highly crystalline after hydrothermal treatment at 900 C.

TABLE-US-00001 TABLE 1 Analytical data for materials prepared in Inventive and Comparative Examples. Na.sub.2O CuO SA MPV Entry Form SAR (wt %) (wt %) XRD (m.sup.2/g) (cm.sup.3/g) Example 1 -- Current Invention 1 As-synthesized 32.9 0.04 CHA 2 Calcined CHA 824 0.31 3 Cu-exchanged 29.9 0.00 3.1 CHA 743 0.28 4 Hydrothermally aged CHA 696 0.26 Example 2 -- Current Invention 5 As-synthesized CHA 6 Calcined 28.9 0.10 CHA 795 0.30 7 Cu-exchanged 26.7 0.00 3.0 CHA 779 0.29 8 Hydrothermally aged CHA 728 0.27 Comparative Example 1 -- Bull et al. U.S. Pat. No. 8,883,119 B2 9 As-synthesized 28.9 0.21 CHA 10 Calcined CHA 862 0.31 11 Cu-exchanged 26.6 0.02 3.1 CHA 815 0.29 12 Hydrothermally aged CHA + 414 0.13 amorph. Comparative Example 3 -- Di Iorio et al., Chem. Mater. 2016, 28, 2236-2247 13 As-synthesized 20.1 0.77 CHA 14 Calcined CHA 879 0.32 15 Cu-exchanged 18.1 0.07 3.1 CHA 832 0.30 16 Hydrothermally aged amorph. 4 0.00 Comparative Example 4 -- Di Iorio et al., Chem. Mater. 2016, 28, 2236-2247 17 As-synthesized CHA 18 Calcined 28.1 0.40 CHA 886 0.32 19 Cu-exchanged 26.1 0.04 3.3 CHA 837 0.30 20 Hydrothermally aged amorph. Comparative Example 7 -- Loiland, et al., Jour. Catal. 2014, 311, 412-423 and Pham, et al., Langmuir 2013, 29, 832-839 21 As-synthesized 21.6 0.08 CHA 22 Calcined CHA 917 0.33 23 Cu-exchanged 19.4 0.01 3.0 CHA 867 0.31 24 Hydrothermally aged amorph. 10 0.00 Comparative Example 8 -- Loiland, et al., Jour. Catal. 2014, 311, 412-423 and Pham, et al., Langmuir 2013, 29, 832-839 25 As-synthesized CHA 26 Calcined CHA 899 0.33 27 Cu-exchanged 26.7 0.03 3.1 CHA 839 0.30 28 Hydrothermally aged amorph. Example 3 -- Current Invention 29 As-synthesized 40.5 0.00 CHA 30 Calcined CHA 750 0.29 31 Cu-exchanged 37.0 0.01 3.14 CHA 712 0.28 32 Hydrothermally aged CHA 663 0.25

Comparative Example 1

[0063] The method disclosed by Bull et al. in U.S. Pat. No. 8,883,119 B2 in Comparative Example 4 is an example of the preparation of CHA zeolites from a gel that contains N,N,N-trimethyl-1-adamantyl ammonium (TMAda.sup.+) cations only without the addition of alkali cations. In this Example, the method was reproduced as closely as possible for comparison to the current disclosed methods. Aluminum isopropoxide (Sigma-Aldrich) was added to a TMAdaOH solution (20 wt. % in water) and the resulting suspension was stirred for about 60 minutes. Next, Ludox AS-40 was added and the resulting gel was stirred for 20 minutes. The pH of the gel was measured to be 13.28 and is close to the reported 13.5. The gel was loaded into a stainless steel autoclave (Parr Instruments, 2000 ml). The molar composition of the gel was 36 SiO.sub.2/2.4 Al isopropoxide/6.2 TMAdaOH/469 H.sub.2O and is nearly identical to the reported gel composition of 36 SiO.sub.2/2.4 Al isopropoxide/6.2 TMAdaOH/468 H.sub.2O. The autoclave was heated to 170 C. and maintained at the temperature for 48 hours while stirring at 200 RPM.

[0064] After cooling, the product was recovered by filtration, washed with deionized water, and dried in a convection oven at 110 C. The occluded organic in the dried as-synthesized zeolite was removed by calcination in air at 600 C. for 6 hours. The Na.sub.2O content and SAR of the material (0.21 wt % Na.sub.2O and 28.9 SAR) was very similar to those reported in Comparative Example 4 of U.S. Pat. No. 8,883,119 B2 (0.17 wt Na.sub.2O & and 30 SAR). The SEM image also indicates a similar material to that reported in Comparative Example 4 of U.S. Pat. No. 8,883,119 B2 and appears to consist of large agglomerates of small crystallites.

[0065] The calcined zeolite was ion-exchanged in a copper (II) acetate solution at 60 C.

Comparative Example 2

[0066] Another sample was prepared using the same protocol as described in Comparative Example 1. The molar composition of the gel was 36 SiO.sub.2/2.4 Al isopropoxide/6.2 TMAdaOH/469 H.sub.2O. The Na.sub.2O content and SAR of the produced material (0.19 wt % Na.sub.2O and 29.0 SAR) was very similar to those reported in U.S. Pat. No. 8,883,119 B2 (0.17 wt Na.sub.2O and an SAR of 30). The SEM image also indicates a similar material to that reported in U.S. Pat. No. 8,883,119 B2 and appears to consist of large agglomerates of small crystallites.

Comparative Example 3

[0067] The methods disclosed by Di Iorio et al., Chem. Mater. 2016, 28, 2236-2247 for the synthesis of SSZ-13 zeolites describes the preparation of CHA zeolites from a gel that contains N,N,N-trimethyl-1-adamantyl ammonium (TMAda.sup.+) cations only without the addition of alkali cations. In this example, the method was reproduced as closely as possible for comparison to the current disclosed methods. A TMAdaOH solution (25 wt. % in water) was added to DI water and the mixture was stirred for 15 minutes at ambient conditions. To this solution, aluminum trihydroxide (SPI Pharma, Product 110-0200) was added and the mixture was stirred for 15 minutes. Next, a silica sol (40% SiO.sub.2, Ludox HS-40) was added and the resulting gel was stirred for 2 more hours at ambient conditions. The final mixture was loaded into a series of 45 ml Teflon-lined stainless steel autoclaves (Parr Instruments) that were heated to 160 C. under rotating (40 RPM) conditions for 6 days. The molar composition of the final mixture was 1.0 SiO.sub.2/0.032 Al.sub.2O.sub.3/0.5 TMAdaOH/44.1 H.sub.2O. After cooling, the product was recovered by filtration, washed with deionized water, and dried in a 110 C. convection oven. The occluded organic in the dried as-synthesized zeolite was removed by calcination in air at 600 C. for 6 hours. The calcined zeolite was ion-exchanged in a copper (II) acetate solution at 60 C.

Comparative Example 4

[0068] Another sample was prepared using the same protocol as described in Comparative Example 3, except the molar composition of the final mixture was adjusted to prepare a CHA zeolite with a different SAR. The composition of the final reaction mixture was 1.0 SiO.sub.2/0.0205 Al.sub.2O.sub.3/0.5 TMAdaOH/44.1 H.sub.2O.

Comparative Example 5

[0069] Another sample was prepared using the same protocol as described in Comparative Example 3, except the molar composition of the final mixture was adjusted to prepare a CHA zeolite with a different SAR. The composition of the final reaction mixture was 1.0 SiO.sub.2/0.0145 Al.sub.2O.sub.3/0.5 TMAdaOH/44.1 H.sub.2O.

Comparative Example 6

[0070] Another sample was prepared using the same protocol as described in Comparative Example 4. The composition of the final reaction mixture was 1.0 SiO.sub.2/0.0205 Al.sub.2O.sub.3/0.5 TMAdaOH/44.1 H.sub.2O.

Comparative Example 7

[0071] The methods disclosed by Loiland, et al., Journal of Catalysis 2014, 311, 412-423 and Pham, et al., Langmuir 2013, 29, 832-839 for the synthesis of SSZ-13 zeolites describes the preparation of CHA zeolites from a gel that contains N,N,N-trimethyl-1-adamantyl ammonium (TMAda.sup.+) cations only without the addition of alkali cations. In this Example, the method was reproduced as closely as possible for comparison to the current disclosed methods. To a TMAdaOH solution (25 wt. % in water), DI water and tetraethyl orthosilicate (98%, Sigma-Aldrich) was added and the mixture was stirred for 2 hours at ambient conditions. Next, aluminum ethoxide (99%, Strem Chemical) was added and the mixture was stirred while covered for 24 hr at ambient conditions.

[0072] The mixture was loaded into 125 ml Teflon-lined stainless steel autoclaves and heated statically at 140 C. for 6 days. The molar composition of the final mixture, based on the assumption that the masses of reagents used in the Loiland et al. reference were correct, was 1.0 SiO.sub.2/0.036 Al.sub.2O.sub.3/0.51 TMAdaOH/20.7 H.sub.2O. After cooling, the product was recovered by filtration, washed with deionized water, and dried in a 110 C. convection oven. The occluded organic in the dried as-synthesized zeolite was removed by calcination in air at 600 C. for 6 hours. The SEM image of the prepared material (FIG. 15) is very similar to that reported in Loiland, et al. and Pham, et al. consisting mainly of 0.5-1 m particles. The calcined zeolite was ion-exchanged in a copper (II) acetate solution at 60 C.

Comparative Example 8

[0073] Another sample was prepared using the same protocol as described in Comparative Example 7, except the molar composition of the final mixture was adjusted to prepare a CHA zeolite with a different SAR. The composition of the final reaction mixture was 1.0 SiO.sub.2/0.0245 Al.sub.2O.sub.3/0.51 TMAdaOH/20.7 H.sub.2O.

Comparative Example 9

[0074] Another sample was prepared using the same protocol as described in Comparative Example 8. The composition of the final reaction mixture was 1.0 SiO.sub.2/0.0245 Al.sub.2O.sub.3/0.51 TMAdaOH/20.7 H.sub.2O. The SEM image of the prepared material (FIG. 16) is very similar to that reported in Loiland, et al. and Pham et al. consisting mainly of 0.5-1 m particles.

Comparative Example 10Hydrothermal Stability Testing

[0075] The hydrothermally stability of the Cu-CHA zeolites prepared from the different prior methods was tested by heating to 900 C. for 1 hour in flowing air containing 10% moisture. The surface area, micropore volumes, and X-ray diffraction (XRD) patterns of the materials were compared before and after the hydrothermal treatment and the results are summarized in Table 1. The zeolites prepared using the disclosed methods of this invention remained highly crystalline after hydrothermal treatment at 900 C. while the comparative materials lost most or all of the starting crystallinity.

Comparative Example 11

[0076] This comparative examples summarizes methods used to identify and differentiate CHA zeolites prepared using the disclosed synthetic method from non-stable CHA zeolites prepared using prior synthetic methods.

[0077] It is well known that zeolite materials exhibiting high crystallinity are more thermally and hydrothermally stable than zeolite materials that are partially non-crystalline. The stable CHA zeolites produced by the disclosed method are shown here to be highly crystalline with very low levels of non-crystalline material, and these materials can be uniquely identified by methods that measure levels of crystallinity. As shown, micropore volume measurements, thermogravimetric analysis, and scanning electron microscope images can be used to differentiate the CHA zeolites prepared from the current disclosed methods from CHA zeolites produced from prior synthetic methods that contain non-crystalline material.

[0078] Micropore Volume Measurements:

[0079] For highly crystalline zeolites, most of the measured pore volume will be attributed to micropore volume since zeolites are purely microporous materials. Additional pore volume, due to mesoporosity and macroporosity, can be measured for samples that contain non-zeolitic material. The ratio of micropore volume to total pore volume is measured and compared in Table 2 for several samples. For the samples prepared using the disclosed method, this ratio is typically very high and is measured to be between 91-94% for the samples in Examples 1, 2, and 3. For the Comparative examples, this ratio is low and is normally below 90%. These data indicate that CHA zeolite samples prepared using the disclosed methods have higher crystallinity than the comparative samples.

[0080] Surface Area Measurements:

[0081] Surface area was determined in accordance with the well-known BET (Brunauer-Emmett-Teller) nitrogen adsorption technique, also referred to as the BET method. Herein the general procedure and guidance of ASTM D4365-95 is followed in the application of the BET method to the materials according to the present disclosure. To ensure a consistent state of the sample to be measured, all samples are pretreated. Suitably pretreatment involves heating the sample, for example to a temperature of 400 to 500 C., for a time sufficient to eliminate free water, such as 3 to 5 hours. In one embodiment, the pretreatment comprises heating each sample to 500 C. for 4 hours.

[0082] Thermogravimetric Analysis:

[0083] It is well known that CHA zeolites prepared exclusively in the presence of the N,N,N-trimethyl-1-adamantyl ammonium (TMAda.sup.+) OSDA contain one TMAda.sup.+ cation per CHA zeolite cage. This allows for simple determination of the crystallinity of a CHA zeolite sample by measuring the amount of organic material that is removed during thermogravimetric analysis (TGA). A highly crystalline sample will have a TMAda.sup.+/cage value of 1, while CHA samples containing excess TMAda.sup.+ cations associated with non-crystalline regions will have values in excess of 1. For the samples prepared using the disclosed method, this ratio is typically very close to 1 and is measured to be 0.98-1.03 for the samples in Examples 1, 2, and 3. For the Comparative examples, this ratio is significantly greater than 1 and is between 1.07 and 1.19. TGA experiments were performed on a Mettler Toledo TGA/DSC 1 w/GC200 Gas Controller with sample weights of 20 mg and Ultra Zero Air flowing at 80 mL/min. Heating profile was 25 C. to 1000 C. at 2 C./min. SDA cations per CHA cage calculations include the assumption that the weight loss in the organic decomposition region of the TGA profile (T360-640 C.) is essentially all N,N,N-trimethyl-1-adamantyl ammonium (TMAda.sup.+) cations.

[0084] Scanning Electron Microscope (SEM) Images:

[0085] Zeolite materials with meso- and macroporosity are often characterized using SEM imaging because the materials are expected to have enhanced surface roughness (for example, see Zeolites and Catalysis, Synthesis, Reactions and Applications, Vol. 1., Edited by Cejka, Corma, Zones, 2010 Wiley-VCH). For the CHA zeolite samples prepared using the disclosed methods (Examples 1, 2, and 3), the SEM images show crystals with smooth crystal surfaces (FIGS. 8, 9, and 17). The SEM images of the comparative examples (FIGS. 10-16) all indicate crystals with increased surface roughness that can be attributed to non-zeolitic material on the surfaces of the zeolite crystals. This non-zeolitic material results in a Cu-CHA catalyst with poor stability.

TABLE-US-00002 TABLE 2 Analytical data for samples prepared from method described in this patent application compared to samples prepared from prior reported methods. Calculated Calculated No. SDA No. SDA Micro Total MicroPV cations per cations per Entry PV PV Total PV CHA cage.sup.+ CHA cage SEM analysis Example 1 0.31 0.33 94% 1.03 1.05 Smooth crystal surface Example 2 0.30 0.32 93% 1.03 1.06 Smooth crystal surface Example 3 0.29 0.31 91% 0.98 Smooth crystal surface Comp. 0.31 0.37 84% 1.08 1.11 Rough crystal Example 1 surface Comp. 0.31 0.36 85% 1.07 1.11 Rough crystal Example 2 surface Comp. 0.32 0.37 86% Rough crystal Example 3 surface Comp. 0.32 0.36 88% Rough crystal Example 4 surface Comp. 0.33 0.36 91% 1.13 1.14 Rough crystal Example 5 surface Comp. 0.32 0.36 87% 1.10 1.11 Rough crystal Example 6 surface Comp. 0.33 0.40 84% Rough crystal Example 7 surface Comp. 0.33 0.39 85% 1.19 Rough crystal Example 8 surface Comp. 0.32 0.37 86% 1.13 1.16 Rough crystal Example 9 surface .sup.+Determined by thermogravimetric analysis, .sup.Determined by nitrogen content analysis.

[0086] Unless otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term about. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present disclosure.

[0087] Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with the true scope of the invention being indicated by the following claims.