A FAST BATCH PROCESS FOR PREPARING A ZEOLITIC MATERIAL HAVING FRAMEWORK TYPE CHA

Abstract

A batch process for preparing a zeolitic material having framework type CHA and a framework structure comprising Si, Al, O, and H, comprising (i) providing a seeding material comprising a zeolitic material having framework type CHA and a framework structure comprising Si, Al, O, and H; (ii) preparing a mixture comprising a source of Si, a source of Al, a seeding material provided in (i), a CHA framework structure directing agent comprising a cycloalkylammonium compound, and water, wherein the cycloalkylammonium compound is a compound comprising a cation R.sup.1R.sup.2R.sup.3R.sup.4N.sup.+ wherein R.sup.1, R.sup.2, R.sup.3 are, independently from one another, an alkyl residue having from 1 to 6 carbon atoms, and R.sup.4 is a 5- to 8-membered cycloalkyl residue, wherein in mixture, the molar ratio of water relative to Si comprised in the source of Si and in the seeding material, calculated as SiO.sub.2, is in the range of from 5:1 to 15:1, wherein the mixture, the molar ratio of sodium, calculated as Na.sub.2O, relative to Si comprised in the source of Si and in the seeding material, calculated as SiO.sub.2, is in the range of from 0:1 to 0.1:1; (iii) heating the mixture prepared in (ii) in its liquid state to a temperature of the mixture in the range of from 50 to 90 C. and keeping the liquid mixture at a temperature in this range for 5 to 100 h; (iv) heating the heated mixture of (iii) to a temperature of the mixture in the range of from 190 to 230 C. in a crystallization vessel and keeping the mixture at a temperature in this range under autogenous pressure in the crystallization vessel for 0.5 to 10 h, obtaining a solid material comprising a zeolitic material having framework type CHA and a framework structure comprising Si, Al, O, and H, suspended in its mother liquor.

Claims

1. A process for preparing a zeolitic material having a framework type CHA and a framework structure comprising Si, Al, O, and H, the process comprising: providing a seeding material comprising a zeolitic material having a framework type CHA and a framework structure comprising Si, Al, O, and H; (ii) preparing a mixture comprising a source of Si, a source of Al, the seeding material provided in (i), a CHA framework structure directing agent comprising a cycloalkylammonium compound, and water, wherein the cycloalkylammonium compound is a compound comprising comprises a cation R.sup.1R.sup.2R.sup.3R.sup.4N.sup.+, wherein R.sup.1, R.sup.2, R.sup.3 are, each independently from one another, an alkyl residue having from 1 to 6 carbon atoms, wherein R.sup.4 is a 5- to 8-membered cycloalkyl residue, wherein in the mixture, a molar ratio of water relative to Si comprised in the source of Si and in the seeding material, calculated as SiO.sub.2, is in a range of from 5:1 to 15:1, wherein the mixture further comprises sodium and in the mixture, a molar ratio of sodium, calculated as Na.sub.2O, relative to Si comprised in the source of Si and in the seeding material, calculated as SiO.sub.2, is in a range of from 0:1 to 0.1:1; (iii) heating the mixture prepared in (ii) in its liquid state to a temperature of the mixture in a range of from 50 to 90 C. and keeping the mixture at a temperature in this range for 5 to 100 I.sub.L forming a heated mixture; and (iv) heating the heated mixture of (iii) to a temperature of the heated mixture in a range of from 190 to 230 C. in a crystallization vessel and keeping the heated mixture at a temperature in this range under autogenous pressure in the crystallization vessel for 0.5 to 10 h, obtaining a solid material comprising the zeolitic material having a framework type CHA and a framework structure comprising Si, Al, O, and H, the solid material suspended in a mother liquor.

2. The process of claim 1, wherein providing the seeding material according to (i) comprises preparing the seeding material by a method comprising (i.1) providing a zeolitic material having a framework type CHA and a framework structure comprising Si, Al, O, and H; (i.2) preparing a suspension comprising the zeolitic material provided in (i.1) and a liquid; and (i.3) milling the suspension prepared in (i.2).

3. The process of claim 2, wherein providing the seeding material according to (i) further comprises, after (i.3), (i.4) separating the zeolitic material of the milled suspension obtained from (i.3) from the liquid, obtaining a separated zeolitic material, wherein the separating comprises subjecting the milled suspension obtained from (i.3) to a solid-liquid separation, and optionally drying the separated zeolitic material in gas atmosphere having a temperature in a range of from 20 to 100 C., wherein the gas atmosphere comprises oxygen and/or nitrogen.

4. The process of claim 1, wherein in the mixture prepared in (ii): a weight ratio of the seeding material, relative to the Si comprised in the source of Si, calculated as SiO.sub.2, is in a range of from 0.025:1 to 0.15:1, a molar ratio of the CHA framework structure directing agent relative to Si comprised in the source of Si and in the seeding material, calculated as SiO.sub.2, is in a range of from 0.20:1 to 0.30:1, and a molar ratio of water relative to Si comprised in the source of Si and in the seeding material, calculated as SiO.sub.2, is in a range of from 7:1 to 15:1.

5. The process of claim 1, wherein R.sup.1, R.sup.2, R.sup.3 are, each independently from one another, an alkyl residue having from 1 to 5 carbon atoms, wherein R.sup.4 is a 5- to 7-membered cycloalkyl residue, wherein the cycloalkylammonium compound comprises a hydroxide, and wherein the CHA framework structure directing agent according to (ii) further comprises a tetraalkylammonium compound comprising a cation R.sup.5R.sup.6R.sup.7R.sup.8N.sup.+, wherein R.sup.5, R.sup.6, R.sup.7, R.sup.8 are, each independently from one another, an optionally substituted alkyl residue having from 1 to 4 carbon atoms, and wherein the tetraalkylammonium compound comprises a hydroxide.

6. The process of claim 1, wherein in the mixture prepared in (ii), a molar ratio of the CHA framework structure directing agent relative to Si comprised in the source of Si and in the seeding material, calculated as SiO.sub.2, is in a range of from 0.20:1 to 0.30:1.

7. The process of claim 1, wherein the source of Si comprises at least one selected from the group consisting of a silica, a silicate, a fumed silica, a silica sol, an amorphous silica, a silica gel, a silicic acid, a silic acid ester, a colloidal silica, a tetraalkoxysilane, a disilicate, a sesquisilcate, and a silica hydrosol, wherein the source of Al comprises at least one selected from the group consisting of an alumina, an aluminate, an aluminum salt, a tri(C1-C5)alkoxide, an AlO(OH), an Al(OH).sub.3, an aluminum halide, an aluminum fluoride, an aluminum chloride, an aluminum bromide, an aluminum sulfate, an aluminum phosphate, an aluminum fluorosilicate, a crystalline Al(OH).sub.3, and a gibbsite, and wherein in the mixture prepared in (ii), a molar ratio of the source of Al, calculated as Al.sub.2O.sub.3, relative to Si comprised in the source of Si and in the seeding material, calculated as SiO.sub.2, is in a range of from 0.001:1 to 0.5:1.

8. The process of claim 1, wherein preparing the mixture according to (ii) comprises (ii.1) preparing a precursor mixture comprising the source of Si, the source of Al, the CHA framework structure directing agent comprising a cycloalkylammonium compound, and water, wherein (ii1.) comprises the steps of (ii.1.1) preparing a mixture comprising the source of Al and the CHA framework structure directing agent comprising a cycloalkylammonium compound; (ii.1.2) agitating the mixture prepared in (ii.1.1) at a temperature of the mixture in a range of from 10 to 50 C. for 5 to 60 min; (ii.1.3) adding the source of Si to the mixture obtained from (ii.1.2); and (ii.1.4) agitating the mixture prepared in (ii.1.3) at a temperature of the mixture in a range of from 10 to 50 C. for 1 to 30 min, obtaining the precursor mixture; and (ii.2) adding the seeding material to the precursor mixture prepared in (ii.1), obtaining the mixture to be subjected to (iii).

9. The process of claim 1, wherein according to (iii), the mixture prepared in (ii) is heated in its liquid state to a temperature of the mixture in a range of from 55 to 80 C., and kept at the temperature for 5 to 80 h, wherein during the keeping the mixture at the temperature the mixture is agitated.

10. The process of claim 1, wherein according to (iv), the heated mixture of (iii) is heated to a temperature of the heated mixture in a range of from 195 to 225 C., and kept at the temperature for 0.75 to 7.5 h.

11. The process of claim 1, further comprising: (v) cooling the suspension of the solid material and the mother liquor obtained from (iv); (vi) separating the solid material comprising a zeolitic material having a framework type CHA and a framework structure comprising Si, Al, O, and H, obtained from (v) from the mother liquor, obtaining a solid material comprising the zeolitic material having a framework type CHA and a framework structure comprising Si, Al, O, and H, the separating comprising (vi.1) subjecting the suspension obtained from (v) to solid-liquid separation, obtaining the mother liquor and a solid material comprising the zeolitic material having a framework type CHA and a framework structure comprising Si, Al, O, and H; (vi.2) washing the solid material obtained from (vi.1), obtaining a solid material comprising the zeolitic material having a framework type CHA and a framework structure comprising Si, Al, O, and H; and (vi.3) drying the solid material obtained from (vi.1) and/or (v.2), obtaining a solid material comprising the zeolitic material having a framework type CHA and a framework structure comprising Si, Al, O, and H; (vii) calcining the solid material obtained from (vi), obtaining a zeolitic material having a framework type CHA and a framework structure comprising Si, Al, O, and H; and (viii) optionally cooling the zeolitic material obtained from (vii).

12. The process of claim 11, further comprising: (ix) subjecting the zeolitic material having a framework type CHA and a framework structure comprising Si, Al, O, and H obtained from (vi), (vii), and/or (viii) to an ion-exchange process, obtaining a mixture comprising one or more cations M and a zeolitic material having a framework type CHA; wherein according to (ix), the zeolitic material comprises one or more ionic non-framework elements that are ion-exchanged against one or more cations M, and wherein the one or more cations M are selected from the group consisting of Sr, Zr, Cr, Mg, Mo, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Os, Ir, and Pt.

13. A zeolitic material having a framework type CHA and a framework structure comprising Si, Al, O, and H, obtained by the process according to claim 1.

14. A zeolitic material having a framework type CHA and a framework structure comprising Si, Al, O, and H, wherein in the framework structure of the zeolitic material, a molar ratio of aluminum relative to silicon, calculated as a molar ratio of Al.sub.2O.sub.3:SiO.sub.2, is in a range of from 0.001:1 to 0.5:1, wherein: the zeolitic material is in the form of crystals having a crystal size, determined via SEM, in a range of from 50 to 1,500 nm, wherein at least 50% of the crystals have a size in this range; the zeolitic material has a BET specific surface area of at least 500 m.sup.2/g; the zeolitic material has a .sup.27Al solid NMR spectrum exhibiting resonances and a peak maximum in a range of from 62.0 to 54.0 ppm with a full width at half height of at most 7.0 ppm; the zeolitic material has a .sup.29Si solid NMR spectrum exhibiting resonances and a peak maximum in a first range of from 108.1 to 114.5 ppm; resonances and a peak maximum in a second range of from 102.6 to 108.1 ppm; and a resonance with or without a peak maximum in a third range of from 97.7 to 102.6 ppm; and a ratio of an integral according to the second range to an integral according to the first range is in a range of from 0.25:1 to 0.45:1.

15. A method for selective catalytic reduction of nitrogen oxides in an exhaust gas stream, the method comprising: contacting the exhaust gas stream with a zeolitic material according to claim 14, wherein the zeolitic material is used as at least one selected from the group consisting of an adsorbent, an absorbent, a molecular sieve, a catalytically active material, a catalyst, and a catalyst component.

16. A method for converting a Cl compound to one or more olefins, the method comprising: contacting the Cl compound with a zeolitic material according to claim 14, wherein the zeolitic material is used as at least one selected from the group consisting of an adsorbent, an absorbent, a molecular sieve, a catalytically active material, a catalyst, and a catalyst component.

17. A method for converting a synthetic gas comprising carbon monoxide and hydrogen to one or more olefins, the method comprising: contacting the synthetic gas with a zeolitic material according to claim 14, wherein the zeolitic material is used as at least one selected from the group consisting of an adsorbent, an absorbent, a molecular sieve, a catalytically active material, a catalyst, and a catalyst component.

Description

BRIEF DESCRIPTION OF THE FIGURES

[0430] FIG. 1 shows XRD of the zeolitic seed material prepared according to Example 1.

[0431] FIG. 2 shows particle size distribution of the seed material prepared according to Example 1.

[0432] FIG. 3 shows SEM, prepared according to Reference Example 2.4, of the seed material prepared according to Example 1 (magnification 50,000).

[0433] FIG. 4 shows SEM, prepared according to Reference Example 2.4, of the seed material prepared according to Example 1 (magnification 75,000).

[0434] FIG. 5 shows the SEM, prepared according to Reference Example 2.4, of the zeolitic material prepared according to Comparative Example 1 (magnification 30,000).

[0435] FIG. 6 shows the XRD plots of the zeolitic materials prepared according to Comparative Example 1. From bottom to top: crystallization time=20 h, 24 h, 48 h.

[0436] FIG. 7 shows the SEM, prepared according to Reference Example 2.4, of the zeolitic material prepared according to Comparative Example 2 (magnification 25,000).

[0437] FIG. 8 shows the XRD plots of the zeolitic materials prepared according to Comparative Example 2. From bottom to top: crystallization time=3 h, 5 h, 16 h, 20 h.

[0438] FIG. 9 shows the SEM, prepared according to Reference Example 2.4, of the zeolitic material prepared according to Comparative Example 3 (magnification 25,000).

[0439] FIG. 10 shows the XRD plots of the zeolitic materials prepared according to Comparative Example 3. From bottom to top: crystallization time=3 h, 5 h, 16 h, 20 h.

[0440] FIG. 11 shows the SEM, prepared according to Reference Example 2.4, of the zeolitic material prepared according to Example 2 (magnification 75,000).

[0441] FIG. 12 shows the XRD plots of the zeolitic materials prepared according to Example 2. From bottom to top: crystallization time=1 h, 2 h, 3 h, 4 h.

[0442] FIG. 13 shows the SEM, prepared according to Reference Example 2.4, of the zeolitic material prepared according to Example 3 (magnification 75,000).

[0443] FIG. 14 shows the XRD plots of the zeolitic materials prepared according to Example 3. From bottom to top: crystallization time=1 h, 2 h, 3 h, 4 h.

[0444] FIG. 15 shows the SEM, prepared according to Reference Example 2.4, of the zeolitic material prepared according to Example 4 (magnification 75,000 upper left, 50,000 upper right, 25,000 lower left, 10,000 lower right).

[0445] FIG. 16 shows the XRD plots of 6 samples of the zeolitic materials prepared according to Example 4, at a crystallization time of 5 h.

[0446] FIG. 17 shows the SEM, prepared according to Reference Example 2.4, of the zeolitic material prepared according to Example 5 after a crystallization time of 2 h (magnification 75,000).

[0447] FIG. 18 shows the XRD plots of 3 samples of the zeolitic materials prepared according to Example 5, at a crystallization time, from bottom to top, of 1 h, 2 h, and 3 h.

[0448] FIG. 19 shows the SEM, prepared according to Reference Example 2.4, of the zeolitic material prepared according to Example 6 (magnification 30,000).

[0449] FIG. 20 shows the .sup.27AI solid-state NMR spectrum of the material prepared according to Example 6.

[0450] FIG. 21 shows the .sup.29Si solid-state NMR spectrum of the material prepared according to Example 6.

[0451] FIG. 22 shows the results of the catalytic testings according to Example 7 wherein the y axis shows XNOx/%, wherein the curve with triangles down (7) shows the behavior of the catalytic material aged for 16 h, 800 C., run 2, the curve with triangles up (A) shows the behavior of the catalytic material aged for 50 h, 650 C., run 2, and the curve with circles show the behavior of a fresh standard SCR material.

[0452] FIG. 23 shows the results of the catalytic testings according to Example 7 wherein the y axis shows N.sub.2O/ppm, wherein the curve with triangles up (A) shows the behavior of the catalytic material aged for 16 h, 800 C., the curve with squares shows the behavior of the catalytic material aged for 50 h, 650 C. , and the curve with circles show the behavior of the fresh material.

CITED PRIOR ART

[0453] U.S. Pat. No. 4,544,538

[0454] WO 2015/185625 A

[0455] US 20170113941 A