WO2020156506A1 - Matériau zéolithique ayant un type de structure cha - Google Patents

Matériau zéolithique ayant un type de structure cha Download PDF

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WO2020156506A1
WO2020156506A1 PCT/CN2020/074094 CN2020074094W WO2020156506A1 WO 2020156506 A1 WO2020156506 A1 WO 2020156506A1 CN 2020074094 W CN2020074094 W CN 2020074094W WO 2020156506 A1 WO2020156506 A1 WO 2020156506A1
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range
zeolitic material
containing compounds
acid
cation containing
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PCT/CN2020/074094
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English (en)
Inventor
Mathias Feyen
Ulrich Mueller
Xinhe Bao
Weiping Zhang
Dirk De Vos
Hermann Gies
Feng-Shou Xiao
Toshiyuki Yokoi
Ute KOLB
Bernd Marler
Yong Wang
Trees De Baerdemaeker
Chuan SHI
Xiangju MENG
Xiulian Pan
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Basf Se
Basf (China) Company Limited
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Publication of WO2020156506A1 publication Critical patent/WO2020156506A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7015—CHA-type, e.g. Chabazite, LZ-218
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions

Definitions

  • the present invention relates to a process for preparing a zeolitic material having framework type CHA and having a framework structure which comprises a tetravalent element Y, B, and O, comprising preparing a synthesis mixture comprising water, a source of the tetravalent element Y, a source of B, and a CHA framework structure directing agent, and heating the synthesis mixture to a temperature in the range of from 100 to 200 °C and keeping the synthesis mixture at a temperature in this range under autogenous pressure, and subjecting the zeolitic material obtained to an acid treatment.
  • the present invention relates to a zeolitic material ob-tainable or obtained by said process.
  • the present invention relates to the use of said zeolitic material preferably as a catalytically active material.
  • Zeolitic materials having framework type CHA are known to be potentially effective as catalysts or catalyst components for treating combustion exhaust gas in industrial applications, for exam-ple for converting nitrogen oxides (NO x ) in an exhaust gas stream.
  • Synthetic CHA zeolitic mate-rials are generally produced by precipitating crystals of the zeolitic material from a synthesis mixture which contains the sources of the elements from which the zeolitic framework is built, such as a source of silicon and a source of aluminum.
  • a CHA zeolitic material is produced from a synthesis mixture comprising water, a source of the tetravalent element Y, a source of B, and a CHA framework structure directing agent, that following a suitable acid treatment step a zeolitic material having framework type CHA is formed which surprisingly has new NH 3 adsorp-tion properties.
  • the present invention gives access to a zeolitic material having framework type CHA with specific NH 3 adsorption properties.
  • the present invention relates to a zeolitic material having framework type CHA and a framework structure comprising a tetravalent element Y, B, and O, wherein Y is one or more of Si, Ge, Zr, Zn and Ti, wherein in the framework structure, the molar ratio Y: B, calculated as el-emental Y: B, is in the range of from 20: 1 to 110: 1, and the molar ratio Al: Y, calculated as ele-mental Al: Y, is in the range of from 0: 1 to 0.001: 1, and wherein the zeolitic material has an NH 3 adsorption capacity in the range of from 0.09 to 0.45 mmol/g, wherein the NH 3 adsorption ca-pacity is defined as the NH 3 adsorption capacity per mass of the zeolitic material determined according to Reference Example 1.4.
  • the zeolitic material having framework type CHA preferably has a NH 3 adsorption capacity in the range of from 0.095 to 0.25 mmol/g, more preferably in the range of from 0.1 to 0.15 mmol/g, more preferably in the range of from 0.105 to 0.12 mmol/g.
  • the molar ratio Al:Y, calculated as elemental Al: Y, is preferably in the range of from 0: 1 to 0.0001: 1, more pref-erably in the range of from 0: 1 to 0.00001: 1.
  • the zeolitic material exhibits an alkali metal content, calculated as molar ratio of the alkali metal AM relative to Y, AM: Y, in the range of from 0: 1 to 0.001: 1, more preferably in the range of from 0: 1 to 0.0001: 1, more preferably in the range of from 0: 1 to 0.00001: 1.
  • the molar ratio Y:B is preferably in the range of from 20: 1 to 50: 1, more preferably in the range of from 20: 1 to 40:1, more preferably in the range of from 20: 1 to 35: 1.
  • the molar ratio Y: B is in the range of from 85: 1 to 110: 1, more preferably in the range of from 90: 1 to 110: 1, more preferably in the range of from 95: 1 to 110: 1, more preferably in the range of from 100: 1 to 110: 1.
  • the molar ratio Y: B is in the range of from 65: 1 to 80: 1, more preferably in the range of from 70: 1 to 80: 1, more preferably in the range of from 75: 1 to 80: 1.
  • the zeolitic material having framework type CHA preferably Y is Si.
  • the zeolitic material having framework type CHA preferably further comprises a metal M of groups 7 to 12 of the periodic table of the elements. More preferably, M is one or more of Fe, Co, Ni, Cu, and Zn, more preferably one or more of Fe and Cu, wherein more preferably, the metal M compris-es, more preferably is Cu.
  • the metal M is comprised in an amount in the range of from 0.25 to 6 weight-%, more preferably in the range of from 0.5 to 5 weight-%, more prefera-bly in the range of from 0.75 to 4 weight-%, more preferably in the range of from 1 to 3 weight-%, calculated as metal oxide MO and based on the total weight of the zeolitic material.
  • the zeolitic material has a crystal size of at least 0.5 micrometer, more preferably in the range of from 0.5 to 4 micrometer, more preferably in the range of from 0.5 to 3 micrometer, more preferably in the range of from 0.5 to 1.5 micrometer, more preferably in the range of from 0.6 to 1.0 micrometer, more preferably in the range of from 0.6 to 0.8 micrometer, determined according to SEM as described in Reference Example 1.2.
  • the present invention further relates to a process for preparing a zeolitic material having framework type CHA and having a framework structure which comprises a tetravalent element Y, B, and O, preferably the zeolitic material according to the present invention, said process comprising
  • Y is one or more of Si, Ge, Zr, Zn and Ti;
  • the molar ratio Al: Y calculated as elemental Al: Y, is in the range of from 0: 1 to 0.001: 1.
  • Y comprises, more preferably is Si.
  • any suitable source of the tetravalent element Y can be used.
  • the source of the tetravalent element Y according to (i) comprises silica, more preferably a fumed silica, more preferably is a fumed silica.
  • the synthesis mixture prepared in (i) which is subjected to (ii) does not com-prise a zeolitic material having framework type CHA.
  • the CHA framework structure directing agent according to (i) can be any agent which results in the preparation of a zeolitic material having framework type CHA according to (iii) .
  • the CHA framework structure directing agent comprises one or more quaternary phosphonium cation containing compounds and/or one or more quaternary ammonium cation containing compounds, more preferably one or more quaternary ammonium cation containing compounds; more preferably the one or more phosphonium cation containing compounds comprise one or more R 1 R 2 R 3 R 4 P + -containing compounds, wherein R 1 , R 2 , R 3 , and R 4 independently from one another stand for optionally substituted and/or optionally branched (C 1 -C 6 ) alkyl, more preferably (C 1 -C 5 ) alkyl, more preferably (C 1 -C 4 ) alkyl, more preferably (C 2 -C 3 ) alkyl, more preferably for op-tion
  • the one or more quaternary ammonium cation containing compounds comprise one or more N, N-dialkyl-dialkylpiperidinium cation containing compounds, more preferably one or more N, N- (C 1 -C 3 ) dialkyl- (C 1 -C 3 ) dialkylpiperidinium cation containing compounds, more pref-erably one or more N, N- (C 1 -C 2 ) dialkyl- (C 1 -C 2 ) dialkylpiperidinium cation containing compounds, wherein more preferably, the one or more quaternary ammonium cation containing compounds are selected from the group consisting of N, N- (C 1 -C 2 ) dialkyl-2, 6- (C 1 -C 2 ) dialkylpiperidinium cati-on and N, N- (C 1 -C 2 ) dialkyl-3, 5- (C 1 -C 2 ) di-alkylpiperidinium cation containing compounds
  • the one or more quaternary ammonium cation containing compounds are se-lected from the group consisting of one or more N, N, N-trialkyl-1-adamantylammonium cation containing compounds, more preferably one or more N, N, N- (C1-C3) trialkyl-1-adamantylammonium cation containing compounds, more preferably one or more N, N, N- (C1-C2)trialkyl-1-adamantylammonium cation containing compounds;
  • the one or more quaternary phosphonium cation containing compounds and/or the one or more quaternary ammonium cation containing compounds are salts, more preferably select-ed from the group consisting of halides, more preferably chloride and/or bromide, more prefera-bly chloride; hydroxide; sulfate; nitrate; phosphate; acetate; and mixtures of two or more thereof, more preferably from the group consisting of chloride, hydroxide, sulfate, and mixtures of two or more thereof, wherein more preferably the one or more quaternary phosphonium cation contain-ing compounds and/or the one or more quaternary ammonium cation containing compounds are hydroxides and/or chlorides, and more preferably hydroxides.
  • the CHA frame-work structure directing agent comprises, more preferably is N, N, N-
  • preparing the synthesis mixture according to (i) preferably comprises
  • the mixture is preferably prepared at a temperature of the mixture in the range of from 20 to 30 °C.
  • preparing the mixture according to (i. 1) comprises agitat-ing, preferably mechanically agitating, more preferably stirring the mixture.
  • the mixture is preferably kept at a temperature in the above said range for a time in the range of from 2 to 30 minutes, more preferably for a time in the range of from 10 to 20 minutes.
  • the molar ratio Al: Y calculated as elemental Al: Y, preferably is in the range of from 0: 1 to 0.0001: 1, more preferably in the range of from 0: 1 to 0.00001: 1.
  • the synthesis mixture prepared in (i) which is subjected to (ii) preferably exhibits an alkali metal content, calculated as molar ratio of the alkali metal AM relative to Y, AM: Y, in the range of from 0:1 to 0.001: 1, more preferably in the range of from 0: 1 to 0.0001: 1, more preferably in the range of from 0: 1 to 0.00001: 1.
  • the molar ratio of the source of B, calculated as H 3 BO 3 relative to the source of the tetravalent element Y, calculated as YO 2 , de-fined as H 3 BO 3 : YO 2 preferably is in the range of from 0.01: 1 to 0.6: 1, more preferably in the range of from 0.02: 1 to 0.5: 1, more preferably in the range of from 0.03: 1 to 0.4: 1.
  • the molar ratio of the source of B, calculated as H 3 BO 3 relative to the source of the tetravalent element Y, calculated as YO 2 , defined as H 3 BO 3 : YO 2 is in the range of from 0.02: 1 to 0.14: 1, more preferably in the range of from 0.04: 1 to 0.12: 1, more preferably in the range of from 0.06: 1 to 0.10: 1.
  • the molar ratio of the source of B, calculated as H 3 BO 3 relative to the source of the tetravalent element Y, calculated as YO 2 , defined as H 3 BO 3 : YO 2 is in the range of from 0.15: 1 to 0.45: 1, more preferably in the range of from 0.2: 1 to 0.4.1, more preferably in the range of from 0.25: 1 to 0.35: 1.
  • the molar ratio of the CHA framework structure directing agent relative to the source of the tetravalent element Y, calculat-ed as YO 2 , defined as SDA: YO 2 is preferably in the range of from 0.1: 1 to 0.8: 1, more prefera-bly in the range of from 0.15: 1 to 0.7: 1, more preferably in the range of from 0.2: 1 to 0.6: 1.
  • the molar ratio of water relative to the source of the tetravalent element Y is preferably in the range of from 7: 1 to 30: 1, more preferably in the range of from 10: 1 to 27: 1, more preferably in the range of from 13: 1 to 25: 1.
  • the synthesis mixture prepared in (i) may comprise one or more further additional components.
  • the synthesis mixture obtained from (i) and subjected to (ii) consist of water, the source of the tetravalent element Y, the source of B, and the CHA framework structure directing agent.
  • Step (ii) of the inventive process comprises subjecting the synthesis mixture prepared in (i) to hydrothermal synthesis conditions comprising heating the synthesis mixture to a temperature in the range of from 100 to 200 °C and keeping the synthesis mixture at a temperature in this range under autogenous pressure.
  • the hydrothermal synthesis according to (ii) is preferably carried out in an autoclave.
  • heating according to (ii) is carried out at a heating rate in the range of from 0.5 to 4 K /min, more preferably in the range of from 1 to 3 K/min.
  • the synthesis mixture is preferably heated to a temperature in the range of from 125 to 185 °C, more preferably in the range of from 135 to 175 °C, more preferably in the range of from 145 to 165 °C.
  • the hydrothermal synthesis according to (ii) preferably comprises a hydrothermal synthesis time in the range of from 2 to 9 d, more preferably in the range of from 3 to 8 d, more preferably in the range of from 4 to 7 d.
  • the hydrothermal synthesis conditions according to (ii) comprise agitating, preferably mechanically agitating, more preferably stirring the synthesis mix- ture. It is alternatively preferred that the hydrothermal synthesis according to (ii) is carried out without agitating the synthesis mixture.
  • step (ii) of the inventive process comprises heating the synthesis mixture prepared from (i) under autogenous pressure it is preferred that (ii) comprises depressurizing the mixture.
  • step (ii) of the inventive process preferably compris-es cooling the mother liquor comprising the zeolitic material having framework type CHA, pref-erably to a temperature in the range of from 10 to 50 °C, more preferably in the range of from 20 to 35 °C.
  • the separating according to (ii) preferably comprises separating the zeolitic material from the mother liquor.
  • separating comprises subjecting the mother liquor comprising the zeolitic material having framework type CHA to a solid-liquid separation method, more prefera-bly comprising a filtration method or a spraying method; preferably washing the obtained zeolitic material obtained; drying the preferably washed zeolitic material.
  • the zeolitic material is washed with water, more preferably until the washing water has a conductivity of at most 500 microSiemens, more preferably at most 200 microSiemens.
  • the zeolitic material is dried in a gas atmosphere having a temperature in the range of from 30 to 140 °C, more prefer-ably in the range of from 35 to 120 °C, more preferably in the range of from 40 to 80 °C.
  • the gas atmosphere comprises oxygen, more preferably is air, lean air, or synthetic air.
  • the separating according to (ii) described above preferably further comprises calcining the zeo-litic material, preferably after drying.
  • the zeolitic material is calcined in a gas atmos-phere having a temperature in the range of from 500 to 660 °C, more preferably in the range of from 550 to 610 °C.
  • the gas atmosphere comprises oxygen, more preferably is air, lean air, or synthetic air.
  • the calcination is carried out for a time in the range of 2 to 9 hours, more preferably in the range of from 2.5 to 7 hours, more preferably in the range of from 3 to 5 hours.
  • the molar ratio Y: B, calculated as elemental Y: B is preferably in the range of from 5: 1 to 29: 1, more preferably in the range of from 7: 1 to 28: 1, more prefera-bly in the range of from 9: 1 to 27: 1, more preferably in the range of from 10: 1 to 26: 1, more preferably in the range of from 11: 1 to 25: 1, more preferably in the range of from 12: 1 to 24: 1.
  • the molar ratio Y: B is in the range of from 12: 1 to 18: 1, more preferably in the range of from 12:1 to 17: 1, more preferably in the range of from 12: 1 to 16: 1.
  • the molar ratio Y: B is in the range of from 19: 1 to 24: 1, more preferably in the range of from 20: 1 to 24: 1.
  • Step (iii) of the inventive process comprises subjecting the zeolitic material obtained in (ii) to an acid treatment.
  • the acid according to (iii. 1) is preferably one or more inorganic acids, or one or more organic acids, or a mixture of one or more inorganic acids and one or more organic acids, wherein the acid is more preferably selected from the group consisting of nitric acid, sulfuric acid, perchloric acid, hydrochloric acid, hydrobromic acid, acetic acid, tri-fluoroacetic acid, oxalic acid, and mixtures of two or more thereof, wherein more preferably, the inorganic acid comprises, more preferably is nitric acid.
  • the aqueous liquid phase preferably contains the acid at a concentration in the range of from 0.05 to 1 mol/L. More preferably, according to (iii. 1) , the aqueous liquid phase contains the acid at a concentration in the range of from 0.05 to 0.4 mol/L, more preferably in the range of from 0.05 to 0.3 mol/L, more preferably in the range of from 0.05 to 0.2 mol/L. Preferably, according to (iii. 1) , the aqueous liquid phase has a pH in the range of from 1.2 to 1.6.
  • the aqueous liquid phase contains the acid at a concentration in the range of from 0.1 to 1 mol/L, more preferably in the range of from 0.2 to 0.8 mol/L, more preferably in the range of from 0.3 to 0.7 mol/L, more preferably in the range of from 0.4 to 0.6 mol/L.
  • the aqueous liquid phase has a pH in the range of from 0.5 to 1.
  • the inventive process preferably further comprises
  • (iii. 2) keeping the mixture obtained from (iii. 1) at a temperature of the mixture in the range of from 15 to 90 °C for a period of time, preferably for a period of time in the range of 0.25 to 5 hours, more preferably in the range of from 0.5 to 4 hours, more preferably in the range of from 1 to 3 hours.
  • the acid treatment in (iii. 1) is preferably carried out at a temperature of the mixture in the range of from 35 to 90 °C for a period of time, more preferably in the range of from 45 to 80 °C, more preferably in the range of from 50 to 70 °C.
  • the acid treatment in (iii. 1) preferably in (iii. 2) , is carried out at a temperature of the mixture in the range of from 15 to 40 °C for a period of time, more preferably in the range of from 17 to 35 °C, more preferably in the range of from 18 to 30 °C, more prefer-ably in the range of from 20 to 25 °C.
  • the acid treatment in (iii. 1) preferably in (iii. 2) , is preferably carried out for a period of time in the range of 0.25 to 5 hours, more preferably in the range of from 0.5 to 4 hours, more prefera-bly in the range of from 1 to 3 hours.
  • the acid treatment in (iii. 1) is preferably carried out at a pressure in the range of from 980 mbar to 1020 mbar (abs) , more preferably in the range of from 990 to 1010 mbar (abs) , more preferably in the range of from 995 to 1005 mbar (abs) .
  • the acid treatment in (iii. 1) comprises agitating, preferably mechanically agitat-ing, more preferably stirring.
  • the molar ratio Y: B calculated as elemental Y: B is in the range of from 20: 1 to 110: 1.
  • the molar ratio Y: B is in the range of from 20: 1 to 40: 1, more preferably in the range of from 20: 1 to 35: 1.
  • the molar ratio Y: B is in the range of from 65: 1 to 110: 1, more preferably in the range of from 75: 1 to 110: 1, more preferably in the range of from 85: 1 to 110: 1, more preferably in the range of from 90: 1 to 100: 1, more preferably in the range of from 95: 1 to 110: 1, more preferably in the range of from 100: 1 to 110: 1.
  • the molar ratio Y: B is in the range of from 60: 1 to 95: 1, more preferably in the range of from 65: 1 to 90: 1, more preferably in the range of from 70: 1 to 85: 1, more preferably in the range of from 75: 1 to 80: 1.
  • the zeolitic material obtained in (iii) preferably has an NH 3 adsorption capacity in the range of from 0.09 to 0.45 mmol/g, more preferably in the range of from 0.095 to 0.25 mmol/g, more preferably in the range of from 0.1 to 0.15 mmol/g, more preferably in the range of from 0.105 to 0.12 mmol/g, wherein the NH 3 adsorption capacity is defined as the NH 3 adsorption capacity per mass of the zeolitic material determined according to reference example 1.4.
  • the inventive process preferably further comprises
  • the inventive process preferably further comprises
  • (v) comprises
  • (v. 3) preferably drying the zeolitic material obtained from (v. 1) or (v. 2) , preferably from (v. 2) .
  • the solid-liquid separation method is preferably a centrifugation method.
  • the zeolitic material is washed with water, preferably until the washing water has a conductivity of at most 500 microSiemens, preferably at most 200 microSiemens.
  • the zeolitic material is dried in a gas atmosphere having a temperature in the range of from 30 to 140 °C, more preferably in the range of from 35 to 120 °C, more preferably in the range of from 40 to 80 °C.
  • the gas atmosphere comprises oxygen, more preferably is air, lean air, or synthetic air.
  • the inventive process further comprises
  • the zeolitic material is preferably calcined in a gas atmosphere having a temperature in the range of from 500 to 660 °C, more preferably in the range of from 550 to 610 °C.
  • the gas atmosphere comprises oxygen, more preferably is air, lean air, or synthetic air.
  • the inventive process preferably further comprises
  • the solution comprising ammonium ions according to (vii) is preferably an aqueous solution comprising a dissolved ammonium salt, more preferably a dissolved inorganic ammonium salt, more preferably dissolved ammonium nitrate.
  • the solution comprising ammonium ions according to (vii) has an ammonium concentration in the range of from 1 to 5 mol/l, more preferably in the range of from 1.5 to 4 mol/l, more preferably in the range of from 2 to 3 mol/l.
  • the solution comprising ammonium ions is brought in contact with the zeolitic material obtained from (v) or (vi) , more preferably from (v) , at a temperature of the solution in the range of from 50 to 95 °C, preferably in the range of from 60 to 90 °C, more pref-erably in the range of from 70 to 85 °C.
  • the solution comprising ammonium ions is brought in contact with the zeolitic material obtained from (v) or (vi) , more preferably from (v) , for a period of time in the range of from 1 to 5 hours, preferably from 2 to 4 hours, more preferably in the range of from 2.5 to 3.5 h.
  • bringing the solution in contact with the zeolitic ma-terial according to (vii) is repeated at least once, more preferably once or twice, more preferably once.
  • bringing the solution in contact with the zeolitic material according to (vii) comprises one or more of impregnating the zeolitic material with the solution and spraying the solution onto the zeolitic material, more preferably impregnating the zeolitic material with the solution.
  • the inventive process preferably further comprises
  • the zeolitic material is preferably calcined in a gas atmosphere having a tem-perature in the range of from 300 to 700 °C, more preferably in the range of from 350 to 600 °C, more preferably in the range of from 400 to 600 °C, more preferably in the range of from 450 to 550 °C.
  • the gas atmosphere comprises oxygen, more preferably is air, lean air, or synthetic air.
  • the material, preferably obtained from (viii) can be employed as such. Further, it is conceivable that this zeo-litic material is subjected to one or more further post-treatment steps.
  • the zeolitic material which is most preferably obtained as a powder can be suitably processed to a molding or a shaped body by any suitable method, including, but no restricted to, extruding, tabletting, spraying and the like.
  • the shaped body may have a rectangular, a triangular, a hex-agonal, a square, an oval or a circular cross section, and/or preferably is in the form of a star, a tablet, a sphere, a cylinder, a strand, or a hollow cylinder.
  • binders can be used which may be chosen according to the intended use of the shaped body. Possible binder materials include, but are not restricted to, graphite, silica, titania, zirco-nia, alumina, and a mixed oxide of two or more of silicon, titanium and zirconium.
  • the weight ratio of the zeolitic material relative to the binder is generally not subject to any specific re-strictions and may be, for example, in the range of from 10: 1 to 1: 10.
  • the zeolitic material is used, for example, as a catalyst or as a catalyst component for treating an exhaust gas stream, for example an exhaust gas stream of an en-gine, it is possible that the zeolitic material is used as a component of a washcoat to be applied onto a suitable substrate, such as a wall-flow filter or the like.
  • the zeolitic material is subjected to a post-treatment which comprises adding a metal M to the zeolitic material. Therefore, the present invention further preferably relates to the process as described above, further compris-ing
  • step (ix) it is preferred that (ix) comprises
  • (ix. 2) preferably heating the mixture prepared in (ix. 1) to a temperature in the range of from 15 to 90 °C, preferably in the range of from 40 to 80 °C;
  • (ix. 5) preferably drying the zeolitic material comprising the metal M obtained from (ix. 4) in a gas atmosphere, preferably at a temperature of the gas atmosphere in the range of from 75 to 170 °C, more preferably in the range of from 80 to 150 °C, more preferably in the range of from 85 to 130 °C, more preferably in the range of from 90 to 110 °C; wherein the gas at-mosphere preferably comprises oxygen;
  • (ix. 6) preferably calcining the zeolitic material comprising the metal M obtained from (ix. 4) or (ix. 5) , preferably (ix. 5) , in a gas atmosphere, preferably at a temperature of the gas at-mosphere in the range of from 350 to 600 °C, more preferably in the range of from 400 to 550 °C, wherein the gas atmosphere preferably comprises oxygen.
  • step (ix. 2) the mixture is preferably heated to a temperature in the range of from 15 to 35 °C, more preferably in the range of from 17 to 30 °C, more preferably in the range of from 20 to 25 °C.
  • the mixture is heated for a time in the range of 0.25 to 5 hours, more preferably in the range of from 0.5 to 4 hours, more preferably in the range of from 1 to 3 hours.
  • the metal M is a transition metal of groups 7 to 12 of the periodic table. More preferably, the metal M is one or more of Fe, Co, Ni, Cu, and Zn, more preferably one or more of Fe and Cu. More preferably, the metal M comprises, more pref-erably is Cu.
  • the metal M is comprised in the zeolitic material in an amount in the range of from 0.25 to 6 weight-%, more preferably in the range of from 0.5 to 5 weight-%, more preferably in the range of from 0.75 to 4 weight-%, more preferably in the range of from 1 to 3 weight-%, calculated as MO and based on the total weight of the zeolitic material.
  • the zeolitic material having framework type CHA obtained in (ii) or (iii) , more preferably in (ix) has a crystal size of at least 0.5 micrometer, preferably in the range of from 0.5 to 1.5 micrometer, more preferably in the range of from 0.6 to 1.0 micrometer, more preferably in the range of from 0.6 to 0.8 micrometer, determined accord-ing to SEM as described in reference example 1.2 herein.
  • the present invention further relates to a zeolitic material having framework type CHA and hav-ing a framework structure which comprises a tetravalent element Y, B, and O, wherein Y is one or more of Si, Ge, Zr, Zn and Ti, obtainable or obtained or preparable or prepared by a process described herein above, preferably obtainable or obtained or preparable or prepared by a pro-cess described herein above further comprising step (v) as described herein above.
  • the present invention yet further relates to a zeolitic material comprising a metal M, having framework type CHA and having a framework structure which comprises a tetravalent element Y, B, and O, wherein Y is one or more of Si, Ge, Zr, Zn and Ti, obtainable or obtained or prepa-rable or prepared by a process described herein above.
  • the molar ratio Y: B calculated as elemental Y: B, is preferably in the range of from 20: 1 to 110: 1.
  • the zeolitic material has an NH 3 adsorption capacity in the range of from 0.09 to 0.45 mmol/g, more preferably in the range of from 0.095 to 0.25 mmol/g, more preferably in the range of from 0.1 to 0.15 mmol/g, more preferably in the range of from 0.105 to 0.12 mmol/g, wherein the NH 3 ad-sorption capacity is defined as the NH 3 adsorption capacity per mass of the zeolitic material determined according to reference example 1.4.
  • the zeolitic material preferably exhibits the molar ratio Al: Y, calculated as elemental Al: Y, in the range of from 0: 1 to 0.001: 1, more prefera-bly in the range of from 0: 1 to 0.0001: 1, more preferably in the range of from 0: 1 to 0.00001: 1.
  • the zeolitic material exhibits an alkali metal content, calculated as molar ratio of the alkali metal AM relative to Y, AM: Y, in the range of from 0: 1 to 0.001: 1, more preferably in the range of from 0: 1 to 0.0001: 1, more preferably in the range of from 0: 1 to 0.00001: 1.
  • the zeolitic material of the present invention can be used for any conceivable purpose, includ-ing, but not limited to, a catalytically active material, as a catalyst, or as a catalyst component.
  • the zeolitic material of the present invention is used for the selective catalytic reduc-tion of nitrogen oxides in an exhaust gas stream, preferably an exhaust gas stream from a die-sel engine.
  • the zeolitic material of the present invention is used for the conversion of a C1 compound to one or more olefins, preferably for the conversion of methanol to one or more olefins or the conversion of a synthetic gas comprising carbon monoxide and hydrogen to one or more olefins.
  • the zeolitic material for said use described above is the zeolitic material comprising a metal M described above, more preferably the zeolitic material comprising a metal M obtainable or obtained or preparable or prepared by a process described herein above.
  • the present invention further relates to a method for selectively catalytically reducing nitrogen oxides in an exhaust gas stream, preferably an exhaust gas stream from a diesel engine, said method comprising bringing said exhaust gas stream in contact with a catalyst comprising the zeolitic material according to the present invention.
  • the zeolitic material employed in said method is the zeolitic material comprising a metal M described above, more preferably the zeolitic material comprising a metal M obtainable or obtained or preparable or prepared by a process described herein above.
  • the present invention yet further relates to a method for catalytically converting a C1 compound to one or more olefins, preferably converting methanol to one or more olefins or converting a synthetic gas comprising carbon monoxide and hydrogen to one or more olefins, said method comprising bringing said C1 compound in contact with a catalyst comprising the zeolitic material according to the present invention.
  • the zeolitic material employed in said method is the zeolitic material comprising a metal M described above, more preferably the zeolitic material comprising a metal M obtainable or obtained or preparable or prepared by a process described herein above.
  • the present invention relates to a catalyst, preferably a catalyst for selectively catalyti-cally reducing nitrogen oxides in an exhaust gas stream, preferably an exhaust gas stream from a diesel engine, or for catalytically converting a C1 compound to one or more olefins, preferably converting methanol to one or more olefins or converting a synthetic gas comprising carbon monoxide and hydrogen to one or more olefins, said catalyst comprising the zeolitic material of the present invention, preferably the zeolitic material comprising a metal M described above, more preferably the zeolitic material comprising a metal M obtainable or obtained or preparable or prepared by a process described herein above.
  • the molar ratio Y: B is in the range of from 20: 1 to 50: 1, preferably in the range of from 20: 1 to 40: 1, more preferably in the range of from 20: 1 to 35: 1.
  • the molar ratio Y: B is in the range of from 85: 1 to 110: 1, more preferably in the range of from 90: 1 to 110: 1, more preferably in the range of from 95: 1 to 110: 1, more preferably in the range of from 100: 1 to 110: 1.
  • the molar ratio Y: B is in the range of from 65: 1 to 80: 1, preferably in the range of from 70: 1 to 80: 1, more preferably in the range of from 75: 1 to 80: 1.
  • M is one or more of Fe, Co, Ni, Cu, and Zn, preferably one or more of Fe and Cu, wherein more preferably, the metal M compris-es, more preferably is Cu.
  • the zeolitic material of embodiment 9 or 10, preferably embodiment 10, comprising M in an amount in the range of from 0.25 to 6 weight-%, preferably in the range of from 0.5 to 5 weight-%, more preferably in the range of from 0.75 to 4 weight-%, more preferably in the range of from 1 to 3 weight-%, calculated as metal oxide MO and based on the total weight of the zeolitic material.
  • Y is one or more of Si, Ge, Zr, Zn and Ti;
  • Al: Y calculated as elemental Al: Y, is in the range of from 0: 1 to 0.001: 1.
  • CHA framework structure directing agent comprises one or more quaternary phosphonium cation containing com-pounds and/or one or more quaternary ammonium cation containing compounds, prefera-bly one or more quaternary ammonium cation containing compounds;
  • the one or more phosphonium cation containing compounds comprise one or more R 1 R 2 R 3 R 4 P + -containing compounds, wherein R 1 , R 2 , R 3 , and R 4 independently from one another stand for optionally substituted and/or optionally branched (C 1 -C 6 ) alkyl, pref-erably (C 1 -C 5 ) alkyl, more preferably (C 1 -C 4 ) alkyl, more preferably (C 2 -C 3 ) alkyl, more pref-erably for optionally substituted methyl or ethyl, wherein more preferably R 1 , R 2 , R 3 , and R 4 stand for optionally substituted ethyl, preferably unsubstituted ethyl;
  • the one or more quaternary ammonium cation containing compounds comprise one or more N, N-dialkyl-dialkylpiperidinium cation containing compounds, preferably one or more N, N- (C 1 -C 3 ) dialkyl- (C 1 -C 3 ) dialkylpiperidinium cation containing compounds, more preferably one or more N, N- (C 1 -C 2 ) dialkyl- (C 1 -C 2 ) dialkylpiperidinium cation containing compounds, wherein more preferably, the one or more quaternary ammonium cation con-taining compounds are selected from the group consisting of N, N- (C 1 -C 2 ) dialkyl-2, 6- (C 1 -C 2 ) dialkylpiperidinium cation and N, N- (C 1 -C 2 ) dialkyl-3, 5- (C 1 -C 2 ) di-alkylpiperidinium cation containing compounds, more
  • the one or more quaternary ammonium cation containing com-pounds are selected from the group consisting of one or more N, N, N-trialkyl-1-adamantylammonium cation containing compounds, preferably one or more N, N, N- (C1-C3) trialkyl-1-adamantylammonium cation containing compounds, more preferably one or more N, N, N- (C1-C2) trialkyl-1-adamantylammonium cation containing compounds;
  • the one or more quaternary phosphonium cation containing compounds and/or the one or more quaternary ammonium cation containing compounds, preferably the one or more quaternary ammonium cation containing compounds are salts, preferably select-ed from the group consisting of halides, preferably chloride and/or bromide, more prefera-bly chloride; hydroxide; sulfate; nitrate; phosphate; acetate; and mixtures of two or more thereof, more preferably from the group consisting of chloride, hydroxide, sulfate, and mix-tures of two or more thereof, wherein more preferably the one or more quaternary phos-phonium cation containing compounds and/or the one or more quaternary ammonium cat-ion containing compounds are hydroxides and/or chlorides, and more preferably hydrox-ides.
  • CHA framework structure directing agent comprises, preferably is N, N, N-trimethyl-1-adamantylammonium hydrox-ide.
  • hydrothermal synthesis according to (ii) comprise a hydrothermal synthesis time in the range of from 2 to 9 d, preferably in the range of from 3 to 8 d, more preferably in the range of from 4 to 7 d.
  • separating comprises subjecting the mother liq-uor comprising the zeolitic material having framework type CHA to a solid-liquid separa-tion method, preferably comprising a filtration method or a spraying method; preferably washing the obtained zeolitic material obtained; drying the preferably washed zeolitic ma-terial.
  • the acid according to (iii. 1) is one or more inorganic acids, or one or more organic acids, or a mixture of one or more inorganic acids and one or more organic acids, wherein the acid is preferably selected from the group consisting of nitric acid, sulfuric acid, perchloric acid, hydrochloric acid, hy-drobromic acid, acetic acid, trifluoroacetic acid, oxalic acid, and mixtures of two or more thereof, wherein more preferably, the inorganic acid comprises, more preferably is nitric acid.
  • the aqueous liquid phase con-tains the acid at a concentration in the range of from 0.05 to 0.4 mol/L, more preferably in the range of from 0.05 to 0.3 mol/L, more preferably in the range of from 0.05 to 0.2 mol/L.
  • the aqueous liquid phase contains the acid at a concentration in the range of from 0.1 to 1 mol/L, more preferably in the range of from 0.2 to 0.8 mol/L, more preferably in the range of from 0.3 to 0.7 mol/L, more preferably in the range of from 0.4 to 0.6 mol/L.
  • (iii. 2) keeping the mixture obtained from (iii. 1) at a temperature of the mixture in the range of from 15 to 90 °C for a period of time, preferably for a period of time in the range of 0.25 to 5 hours, more preferably in the range of from 0.5 to 4 hours, more preferably in the range of from 1 to 3 hours.
  • the molar ratio Y: B is in the range of from 65: 1 to 110: 1, preferably in the range of from 75: 1 to 110: 1, more preferably in the range of from 85: 1 to 110: 1, more preferably in the range of from 90: 1 to 100: 1, more preferably in the range of from 95: 1 to 110: 1, more preferably in the range of from 100: 1 to 110: 1.
  • the molar ratio Y: B is in the range of from 60: 1 to 95: 1, preferably in the range of from 65: 1 to 90: 1, more preferably in the range of from 70: 1 to 85: 1, more prefer-ably in the range of from 75: 1 to 80: 1.
  • (v. 3) preferably drying the zeolitic material obtained from (v. 1) or (v. 2) , preferably from (v. 2) .
  • the zeolitic material is dried in a gas atmosphere having a temperature in the range of from 30 to 140 °C, preferably in the range of from 35 to 120 °C, more preferably in the range of from 40 to 80 °C.
  • the zeolitic material is calcined in a gas atmosphere having a temperature in the range of from 500 to 660 °C, preferably in the range of from 550 to 610 °C.
  • the zeolitic material is calcined in a gas atmosphere having a temperature in the range of from 300 to 700 °C, preferably in the range of from 350 to 600 °C, more preferably in the range of from 400 to 600 °C, more preferably in the range of from 450 to 550 °C.
  • (ix. 2) preferably heating the mixture prepared in (ix. 1) to a temperature in the range of from 15 to 90 °C, preferably in the range of from 40 to 80 °C;
  • (ix. 5) preferably drying the zeolitic material comprising the metal M obtained from (ix. 4) in a gas atmosphere, preferably at a temperature of the gas atmosphere in the range of from 75 to 170 °C, more preferably in the range of from 80 to 150 °C, more preferably in the range of from 85 to 130 °C, more preferably in the range of from 90 to 110 °C; wherein the gas atmosphere preferably comprises oxygen;
  • (ix. 6) preferably calcining the zeolitic material comprising the metal M obtained from (ix. 4) or (ix. 5) , preferably (ix. 5) , in a gas atmosphere, preferably at a temperature of the gas atmosphere in the range of from 350 to 600 °C, more preferably in the range of from 400 to 550 °C, wherein the gas atmosphere preferably comprises oxygen.
  • the metal M is comprised in the zeolitic material in an amount in the range of from 0.25 to 6 weight-%, preferably in the range of from 0.5 to 5 weight-%, more preferably in the range of from 0.75 to 4 weight-%, more preferably in the range of from 1 to 3 weight-%, calculated as MO and based on the total weight of the zeolitic material.
  • any one of embodiments 13 to 94 preferably of any one of embodiments 13 to 49, more preferably of any one of embodiments 50 to 76, more preferably of any one of embodiments 77 to 86, more preferably of any one of embodiments 87 to 94, wherein the zeolitic material having framework type CHA obtained in (ii) or (iii) , preferably in (ix) has a crystal size of at least 0.5 micrometer, preferably in the range of from 0.5 to 1.5 mi-crometer, more preferably in the range of from 0.6 to 1.0 micrometer, more preferably in the range of from 0.6 to 0.8 micrometer, determined according to SEM as described in reference example 1.2 herein.
  • a zeolitic material comprising a metal M, having framework type CHA and having a framework structure which comprises a tetravalent element Y, B, and O, wherein Y is one or more of Si, Ge, Zr, Zn and Ti, obtainable or obtained or preparable or prepared by a process according to any one of embodiments 87 to 95.
  • zeolitic material of any one of embodiments 96 to 98 wherein the zeolitic material has an NH 3 adsorption capacity in the range of from 0.09 to 0.45 mmol/g, preferably in the range of from 0.095 to 0.25 mmol/g, more preferably in the range of from 0.1 to 0.15 mmol/g, more preferably in the range of from 0.105 to 0.12 mmol/g, wherein the NH 3 ad-sorption capacity is defined as the NH 3 adsorption capacity per mass of the zeolitic mate-rial determined according to reference example 1.4.
  • the zeolitic material of any one of embodiments 96 to 99 exhibiting the molar ratio Al: Y, calculated as elemental Al: Y, in the range of from 0: 1 to 0.001: 1, preferably in the range of from 0: 1 to 0.0001: 1, more preferably in the range of from 0: 1 to 0.00001: 1.
  • the zeolitic material of any one of embodiments 96 to 100 exhibiting an alkali metal con-tent, calculated as molar ratio of the alkali metal AM relative to Y, AM: Y, in the range of from 0: 1 to 0.001: 1, preferably in the range of from 0: 1 to 0.0001: 1, more preferably in the range of from 0: 1 to 0.00001: 1.
  • a zeolitic material according to any one of embodiments 1 to 12, preferably of any one of embodiments 9 to 12, more preferably of embodiment 10, or according to any one of embodiments 96 to 101, preferably embodiment 96 or 97, more preferably embodiment 97, as a catalytically active material, as a catalyst, or as a catalyst component.
  • embodiment 102 for the selective catalytic reduction of nitrogen oxides in an exhaust gas stream, preferably an exhaust gas stream from a diesel engine.
  • embodiment 102 for the conversion of a C1 compound to one or more olefins, preferably for the conversion of methanol to one or more olefins or the conversion of a synthetic gas comprising carbon monoxide and hydrogen to one or more olefins.
  • a method for catalytically converting a C1 compound to one or more olefins preferably converting methanol to one or more olefins or converting a synthetic gas comprising car-bon monoxide and hydrogen to one or more olefins, said method comprising bringing said C1 compound in contact with a catalyst comprising the zeolitic material according to any one of embodiments 1 to 12, preferably of any one of embodiments 9 to 12, more prefera-bly embodiment 10, or according to any one of embodiments 96 to 101, preferably em-bodiment 96 or 97, more preferably embodiment 97.
  • a catalyst preferably a catalyst for selectively catalytically reducing nitrogen oxides in an exhaust gas stream, preferably an exhaust gas stream from a diesel engine, or for catalyt-ically converting a C1 compound to one or more olefins, preferably converting methanol to one or more olefins or converting a synthetic gas comprising carbon monoxide and hydro-gen to one or more olefins, said catalyst comprising the zeolitic material according to any one of embodiments 1 to 12, preferably of any one of embodiments 9 to 12, more prefera-bly embodiment 10, or according to any one of embodiments 96 to 101, preferably em-bodiment 96 or 97, more preferably embodiment 97.
  • the present invention is further illustrated by the following reference examples, comparative examples, and examples.
  • the XRD diffraction patterns of the zeolitic materials according to the present invention was determined by XRD analysis.
  • the data were collected using a standard Bragg-Brentano diffrac-tometer with a Cu-X-ray source and an energy dispersive point detector.
  • the angular range of 2 ° to 70 ° (2 theta) was scanned with a step size of 0.02 °, while the variable divergence slit was set to a constant opening angle of 0.3 °.
  • the data were then analysed using TOPAS V5 soft-ware, wherein the sharp diffraction peaks were modelled using PONKCS phases for the crystal structure for CHA.
  • the model was prepared as described in Madsen, I. C. et al. This was re-fined to fit the data.
  • the SEM (Scanning Electron Microscopy) pictures (secondary electron (SE) picture at 15 kV (kiloVolt) ) were made using a Philips XL30 SEM FEG microscope.
  • the NH 3 breakthrough testing was carried out by using the SCR set-up (see example 5) by fol-lowing the NH 3 concentration at the outlet of the reactor, in which the hydrated zeolite sample (200 mg) is exposed to a flow of 545 ppm NH 3 and 5 % H 2 O in N 2 (total flow 275 mL/min) at 150 °C.
  • the NH 3 adsorption capacity was determined from the NH 3 breakthrough testing results as follows. From the breakthrough testing data, the NH 3 adsorption capacity in an atmosphere containing 5 volume % H 2 O in N 2 for hydrated samples at 150 °C was determined. The amount of ammonia adsorbed at break-through was determined using the NH 3 concentration at the reactor outlet vs. time plot. Specifi-cally, the area between the blank curve (recorded in an experiment without catalyst in the reac-tor tube) and the corresponding breakthrough curve for the material under study, loaded into the reactor tube, was integrated. Using the flow rate and the NH 3 concentration (545 ppm) , this al-lows to calculate the number of mmoles of ammonia that is withheld on the catalyst under study.
  • Example 1 Preparation of a zeolitic material having framework type CHA with an acid treatment step
  • N,N, N-trimethyl-1-adamantylammonium hydroxide (aqueous solution 30 wt. %; BASF) 46.44 g
  • N, N, N-trimethyl-1-adamantylammonium hydroxide (TMAdaOH) , H 3 BO 3 , fumed silica and deionized water were mixed for around 10 minutes at around 23 °C to form a gel, having the composition:
  • the obtained gel was transferred to an autoclave and the autoclave sealed.
  • the gel in the auto-clave was heated to a temperature of 150 °C and kept at this temperature for a time of 7 days, wherein during said time the autoclave and its contents were not perturbed by stirring or rota-tion.
  • the obtained suspension was filtered and the material was thoroughly washed with water, followed by drying at 60 °C.
  • the thus dried material was then heated at a heating rate of 1 °C/min to a temperature of 580 °C and calcined at this temperature for 4 h.
  • the resulting product had an atomic Si/B ratio of 14.5: 1.
  • the SEM picture, determined as described in Reference Example 1.2, is shown in Fig. 1. As one can see from the SEM, the obtained zeolitic material has a crystal size of 0.5 microns or more.
  • the XRD analysis of the product showed that it had a CHA framework structure. No other side phases were detected.
  • the pH was determined of the aqueous suspension compris-ing the zeolitic material having framework type CHA obtained in (ii) , water, and x M HNO 3 .
  • the pH was in the range of from 1.2 to 1.6; for Experiment b2) the pH was in the range of from 0.5 to 1;
  • the XRD analysis of each of the b1) , b2) and b3) products showed that each had a CHA framework structure.
  • the XRD pattern of the b1) , b2) and b3) products, determined as de-scribed in Reference Example 1.1, is shown in figure 2.
  • the SEM pictures, of each of the b1) , b2) and b3) products is shown in figures 3, 4 and 5 respectively. As one can see from the SEM, most of the obtained zeolitic materials have a crystal size of 0.5 microns or more.
  • Example 2 Preparation of a zeolitic material having framework type CHA with an acid treatment step
  • N,N, N-trimethyl-1-adamantylammonium hydroxide (aqueous solution 20 wt. %, BASF) 29.37 g
  • N, N, N-trimethyl-1-adamantylammonium hydroxide (TMAdaOH) , H 3 BO 3 , fumed silica and deionized water were mixed for around 10 minutes at around 23 °C to form a gel, having the composition:
  • the obtained gel was transferred to an autoclave and the autoclave sealed.
  • the gel in the auto-clave was heated to a temperature of 160 °C and kept at this temperature for a time of 5 days, wherein during said time the autoclave and its contents were not perturbed by stirring or rota-tion.
  • the obtained suspension was filtered and the material was thoroughly washed with water, followed by drying at 60 °C.
  • the thus dried material was then heated at a heating rate of 1 °C/min to a temperature of 580 °C and calcined at this temperature for 4 h.
  • the resulting product had an atomic Si/B ratio of 22: 1.
  • the SEM picture, determined as described in Reference Example 1.2, is shown in Fig. 6. As one can see from the SEM, the obtained zeolitic material has a crystal size of 0.5 microns or more.
  • the XRD analysis of the product showed that it had a CHA framework structure..
  • the pH was determined of the aqueous suspension compris-ing the zeolitic material having framework type CHA obtained in (ii) , water, and x M HNO 3 .
  • the pH was in the range of from 1.2 to 1.6; for Experiment b2) the pH was in the range of from 0.5 to 1;
  • the XRD analysis of each of the b1) , b2) and b3) products showed that each had a CHA framework structure.
  • the XRD pattern of the Example 2, b1) , b2) and b3) products, determined as described in Reference Example 1.1, is shown in figure 7.
  • the SEM pictures, of each of the Example 2, b1) , b2) and b3) products is shown in figures 8, 9 and 10 respectively. As one can see from the SEM, most of the obtained zeolitic materials have a crystal size of 0.5 microns or more.
  • N,N, N-trimethyl-1-adamantylammonium hydroxide (aqueous solution 20 wt. %, BASF) 9.86 g
  • N, N, N-trimethyl-1-adamantylammonium hydroxide (TMAdaOH) , H 3 BO 3 , fumed silica and deionized water were mixed for around 10 minutes at around 23 °C to form a uniform suspen-sion, having the composition:
  • the obtained uniform suspension was transferred to an autoclave and the autoclave sealed.
  • the uniform suspension in the autoclave was heated to a temperature of 160 °C over a time of 8 hours, then kept at this temperature for a time of 3 days. After pressure release and cooling to around 23 °C, the obtained suspension was filtered and the material was thoroughly washed with water, followed by drying at 60 °C to 80 °C. The thus dried material was then heated at a heating rate of 1 °C/min to a temperature of 580 °C and calcined at this temperature for 4 h. The resulting product had an atomic Si/B ratio of 100: 1.
  • the XRD analysis of the product showed that it had a CHA framework structure.
  • N,N, N-trimethyl-1-adamantylammonium hydroxide (aqueous solution 20 wt. %, BASF) 9.86 g
  • N, N, N-trimethyl-1-adamantylammonium hydroxide (TMAdaOH) , H 3 BO 3 , fumed silica and deionized water were mixed for around 10 minutes at around 23 °C to form a uniform suspen-sion, having the composition:
  • the obtained uniform suspension was transferred to an autoclave and the autoclave sealed .
  • the uniform suspension in the autoclave was heated to a temperature of 160 °C over a time of 8 hours, then kept at this temperature for a time of 3 days. After pressure release and cooling to around 23 °C, the obtained suspension was filtered and the material was thoroughly washed with water, followed by drying at 60 °C to 80 °C. The thus dried material was then heated at a heating rate of 1 °C/min to a temperature of 580 °C and calcined at this temperature for 4 h.
  • the resulting product had an atomic Si/B ratio of 50: 1.
  • the XRD pattern of the comparative example 2 product, determined as described in Reference Example 1.1, is shown in Fig. 13.
  • the SEM picture, determined as described in Reference Example 1.2, is shown in Fig. 14.
  • the XRD anal-ysis of the product showed that it had a CHA framework structure
  • Example 3 NH 3 Breakthrough Testing of the zeolitic material having framework type CHA of example 1 against other materials, and determination of the NH 3 adsorption capacity
  • the CHA zeolitic material according to the present invention, with an acid treatment step (Ex-ample 1, b1) was subjected to NH 3 breakthrough testing and compared against materials ob-tained without an acid treatment step (comparative examples 1 and 2) .
  • the protocol for said NH 3 breakthrough testing was carried out according to reference example 1.3.
  • Example 4 Preparation of a zeolitic material having framework type CHA and comprising a metal M (Cu) with an acid treatment step
  • Comparative Example 3 Preparation of a zeolitic material having framework type CHA and comprising a metal M (Cu) , with 2.5 wt. -% Cu
  • Comparative Example 4 Preparation of a zeolitic material having framework type CHA and comprising a metal M (Cu) , with 2.5 wt. -% Cu
  • Example 5 Use of the zeolitic material having framework type CHA of Example 3 as SCR catalysts–NO conversions and N 2 O make
  • the zeolitic materials obtained from example 3 and comparative examples 3 and 4 were sub-jected to a selective catalytic reduction test.
  • catalytic testing of the samples was performed in a quartz fixed bed tube reactor with downstream flow and an internal diameter of 4 mm at atmospheric pressure.
  • 200 mg granulated catalyst (mesh size 0.250 -0.500 mm) was fixed in the middle of the reactor bed using quartz wool.
  • a thermocouple was placed inside the catalyst bed to control the reactor temperature.
  • the catalyst was pre-treated by heating at 5 °C/min in a flow of O 2 (30 mL/min) to 450 °C and remaining at 450 °C for 0.5 h.
  • the reactor was cooled down in a flow of O 2 (30 mL/min) to 150°C.
  • a gas mixture consisting of 500 ppm NH 3 , 500 ppm NO , 10 % O 2 , 10 % CO 2 and 5 % H 2 O in N 2 was prepared by diluting 0.5 % NH 3 in N 2 (30 ml/min) , 0.5 % NO in N 2 (30 ml/min) , O 2 (30 ml/min) and CO 2 (30 ml/min) in N 2 (150 ml/min) .
  • H 2 O was added to the N 2 stream prior to mixing with NH 3 , NO, O 2 and CO 2 .
  • This gas mix-ture was passed over the catalyst at 150 °C using a space velocity of 17 500 h -1 .
  • the catalyst was tested at 150 °C, 200 °C, 250 °C, 350 °C, and 450 °C by remaining 1 h at each tempera-ture step and heating at 5 °C/min in between two temperature steps (Table 4) .
  • the reactor out-let was analysed using a GASMET FT-IR Gas analyser (Model DX4000) .
  • the NO conversion (%) As can be see from Figure 16 and Figure 17, as a conse-quence of the acid treatment, as the amount of boron in the zeolitic material decreases, the ac-tivity decreases. This shows that the NO conversion (%) catalytic activity may be tailored ac-cordingly by the acid treatment step, allowing the amount of boron in the zeolitic material to be reduced as desired.
  • the N 2 O make as can be seen from tables 5 and 6, the acid treated samples of the present invention according to example 3, a1) , a2) and a3) and example 3, b1) , b2) and b3) respectively each permit to obtain a great balance between the NO conver-sion and the N 2 O make.
  • the ratio of nitrous oxide make to NO conversion for exam-ple 3, a1) , a2) and a3) and example 3, b1) , b2) and b3) is always less than the ratio obtained with their respective comparative example 3 or 4, hence showing an improved catalytic perfor-mance compared to the comparative catalysts.
  • Fig. 1 shows the SEM pictures of the zeolitic material according to Example 1 a) .
  • Fig. 2 shows the XRD pattern of the zeolitic material according to Example 1 a) superim-posed with the XRD patterns of the deboronated materials according to Example 1 -b1) , b2) and b3) .
  • Fig. 3 shows the SEM pictures of the zeolitic material according to Example 1, b1) .
  • Fig. 4 shows the SEM pictures of the zeolitic material according to Example 1, b2) .
  • Fig. 5 shows the SEM pictures of the zeolitic material according to Example 1, b3) .
  • Fig. 6 shows the SEM pictures of the zeolitic material according to Example 2 a) .
  • Fig. 7 shows the XRD pattern of the zeolitic material according to Example 2 a) superim-posed with the XRD patterns of the deboronated materials according to Example 2 -b1) , b2) and b3) .
  • Fig. 8 shows the SEM pictures of the zeolitic material according to Example 2, b1) .
  • Fig. 9 shows the SEM pictures of the zeolitic material according to Example 2, b2) .
  • Fig. 10 shows the SEM pictures of the zeolitic material according to Example 2, b3) .
  • Fig. 15 shows the NH 3 breakthrough testing of the zeolitic material of Example 1, b1) , Com-parative Example 1 and Comparative Example 2.
  • the y axis cout/cin is the ammonia concentration detected after the reactor divided by the inlet concentration of ammonia. Blanc is a run without any material added, i. e. the reference of an empty reactor.
  • Fig. 16 shows on the left hand y axis the NO Conversion (%) in relation to temperature for the zeolitic materials in Table 5 tested in Example 5 –wherein the data measured thereto is shown by a solid line connecting the symbols.
  • Figure 16 shows on the right hand y axis the N 2 O make (ppm) in relation to temperature for the zeolitic materials in Table 5 tested in Example 5 –wherein the data measured thereto is shown by a broken line connecting the symbols.
  • Fig. 17 shows on the left hand y axis the NO Conversion (%) in relation to temperature for the zeolitic materials in Table 6 tested in Example 5 –wherein the data measured thereto is shown by a solid line connecting the symbols.
  • Figure 16 shows on the right hand y axis the N 2 O make (ppm) in relation to temperature for the zeolitic materials in Table 6 tested in Example 5 –wherein the data measured thereto is shown by a broken line connecting the symbols.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Life Sciences & Earth Sciences (AREA)
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  • Geology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
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  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

L'invention concerne un processus de préparation d'un matériau zéolithique ayant un CHA de type charpente et ayant une structure charpentée qui comprend un élément tétravalent Y, B et O, comprenant la préparation d'un mélange de synthèse comprenant de l'eau, une source de l'élément tétravalent Y, une source de B, et un agent directeur de structure de structure CHA, et à chauffer le mélange de synthèse à une température dans la plage de 100 à 200 °C et à maintenir le mélange de synthèse à une température dans cette plage sous pression autogène, et à soumettre le matériau zéolithique obtenu à un traitement acide.
PCT/CN2020/074094 2019-01-31 2020-01-31 Matériau zéolithique ayant un type de structure cha WO2020156506A1 (fr)

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CN114031092A (zh) * 2021-12-16 2022-02-11 中节能万润股份有限公司 一种sapo-20分子筛的制备方法
WO2023036238A1 (fr) * 2021-09-09 2023-03-16 Basf Corporation Synthèse de matériaux zéolitiques cha, matériaux zéolitiques cha pouvant être ainsi obtenus et catalyseurs scr les comprenant

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CN1890178A (zh) * 2003-12-23 2007-01-03 埃克森美孚化学专利公司 菱沸石型分子筛、其合成及其在含氧化合物转化成烯烃中的应用
US20110142755A1 (en) * 2009-11-24 2011-06-16 Basf Se Process for the preparation of zeolites having b-cha structure
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CN107108242A (zh) * 2014-12-17 2017-08-29 康斯乔最高科学研究公司 具有cha晶体结构的沸石的合成，其合成方法及其在催化应用中的用途
CN107673366A (zh) * 2012-06-04 2018-02-09 巴斯夫欧洲公司 Cha型沸石材料及其使用环烷基铵化合物的制备
CN108602056A (zh) * 2015-12-09 2018-09-28 巴斯夫公司 Cha型沸石材料和使用环烷基-和乙基三甲基铵化合物的组合制备它们的方法

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CN1890178A (zh) * 2003-12-23 2007-01-03 埃克森美孚化学专利公司 菱沸石型分子筛、其合成及其在含氧化合物转化成烯烃中的应用
US20110142755A1 (en) * 2009-11-24 2011-06-16 Basf Se Process for the preparation of zeolites having b-cha structure
CN107673366A (zh) * 2012-06-04 2018-02-09 巴斯夫欧洲公司 Cha型沸石材料及其使用环烷基铵化合物的制备
CN107108242A (zh) * 2014-12-17 2017-08-29 康斯乔最高科学研究公司 具有cha晶体结构的沸石的合成，其合成方法及其在催化应用中的用途
US20160243531A1 (en) * 2015-02-24 2016-08-25 California Institute Of Technology Processes for preparing zincoaluminosilicates with aei, cha, and gme topologies and compositions derived therefrom
CN108602056A (zh) * 2015-12-09 2018-09-28 巴斯夫公司 Cha型沸石材料和使用环烷基-和乙基三甲基铵化合物的组合制备它们的方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023036238A1 (fr) * 2021-09-09 2023-03-16 Basf Corporation Synthèse de matériaux zéolitiques cha, matériaux zéolitiques cha pouvant être ainsi obtenus et catalyseurs scr les comprenant
CN114031092A (zh) * 2021-12-16 2022-02-11 中节能万润股份有限公司 一种sapo-20分子筛的制备方法

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