WO2017211236A1 - Copper-promoted zeolitic materials of the cha framework structure from organotemplate-free synthesis and use thereof in the selective catalytic reduction of nox - Google Patents

Copper-promoted zeolitic materials of the cha framework structure from organotemplate-free synthesis and use thereof in the selective catalytic reduction of nox Download PDF

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WO2017211236A1
WO2017211236A1 PCT/CN2017/087035 CN2017087035W WO2017211236A1 WO 2017211236 A1 WO2017211236 A1 WO 2017211236A1 CN 2017087035 W CN2017087035 W CN 2017087035W WO 2017211236 A1 WO2017211236 A1 WO 2017211236A1
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zeolitic material
framework structure
cha framework
copper
cha
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PCT/CN2017/087035
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English (en)
French (fr)
Inventor
Stefan Maurer
Mathias Feyen
Natalia Trukhan
Ulrich Mueller
Faruk Oezkirim
Susanne Stiebels
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Basf Corporation
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Priority to BR112018073870-0A priority Critical patent/BR112018073870B1/pt
Priority to EP17809675.6A priority patent/EP3481549A4/en
Priority to CA3026817A priority patent/CA3026817C/en
Priority to CN201780034580.8A priority patent/CN109219481A/zh
Publication of WO2017211236A1 publication Critical patent/WO2017211236A1/en

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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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates (SAPO compounds)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9409—Nitrogen oxides
    • B01D53/9413—Processes characterised by a specific catalyst
    • B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
    • 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
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B01J29/763—CHA-type, e.g. Chabazite, LZ-218
    • B01J35/30—
    • 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
    • C01B39/026—After-treatment
    • 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
    • C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
    • 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
    • C01B39/54—Phosphates, e.g. APO or SAPO compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • B01D2251/2062—Ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • B01D2251/2067—Urea
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20738—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20761—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/50—Zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/92—Dimensions
    • B01D2255/9207—Specific surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/01—Engine exhaust gases
    • B01D2258/012—Diesel engines and lean burn gasoline engines
    • 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
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions

Definitions

  • the present invention relates to an organotemplate-free synthetic process for the production of a zeolitic material having a CHA framework structure ion-exchanged with high levels of copper and/or iron and to the copper and/or iron exchanged zeolitic material as obtained or obtainable according to the inventive method as well as to the synthetic copper and/or iron containing zeo-litic material per se and to its use in a method for the treatment of NO x by selective catalytic re-duction (SCR) . Furthermore, the present invention relates to the use of the synthetic copper and/or iron containing zeolitic material, in particular as a catalyst in the treatment of NO x con-taining automotive or industrial exhaust gas by SCR.
  • Zeolites containing copper and/or iron have found wide use in the field of selective catalytic re-duction of nitrogen oxides (NO x ) contained in exhaust gases, and in particular in exhaust gas stemming from diesel engines and lean burn gasoline engines.
  • NO x nitrogen oxides
  • a particularly prominent exam-ple of the zeolites which find use in these applications are copper containing zeolites of the CHA structure type, and in particular chabazite ion-exchanged with copper.
  • WO 2009/141324 A1 relates to a process for the direct synthesis of Cu con-taining zeolites having CHA structure and to their use in the selective catalytic reduction of NO x in exhaust gas.
  • WO 2013/068976 A1 concerns an organotemplate-free synthetic process for the production of a zeolitic material of the CHA-type framework structure.
  • the present invention aims at providing a zeolite catalyst displaying higher activities under prolonged conditions of use, in particular with respect to applications in selective catalytic reduction (SCR) , i.e. for the conversion of nitrogen oxide with a reducing agent to environmentally inoffensive compounds such as in particular to nitrogen and oxygen.
  • SCR selective catalytic reduction
  • zeolitic materials supporting copper and/or iron wherein said zeolitic materials have a CHA-type framework structure as may be obtained from organotemplate-free synthesis display an improved performance as a catalyst compared to conventional zeolitic materials having the CHA-type framework structure obtained from or-ganotemplate-mediated synthesis, wherein this improved performance is particularly apparent in the selective catalytic reduction reaction.
  • zeolitic materials having a CHA-type framework structure obtainable from organotemplate-free synthetic procedures may not only display a higher catalytic activity at comparable loadings relative to the known catalysts from the prior art wherein the zeolitic material is obtained from templated synthesis, it has furthermore quite unexpectedly been found that said improved cata-lytic activity observed for the zeolitic materials obtainable from organotemplate-free synthesis may actually be improved towards higher loadings compared to the general decrease of cata-lytic activity towards higher loadings observed for the prior art materials.
  • the present invention relates to an organotemplate-free synthetic process for the production of a copper and/or iron containing zeolitic material having a CHA framework struc-ture comprising YO 2 , X 2 O 3 , and optionally comprising Z 2 O 5 , wherein said process comprises:
  • the zeolitic material obtained in (2) to one or more ion exchange procedures for obtaining a zeolitic material ion exchanged with Cu and/or Fe, preferably with Cu; wherein Y is a tetravalent element, X is a trivalent element, and Z is a pentavalent element, wherein the ion exchanged zeolitic material obtained in (3) contains from 3.8 to 12 wt. -%of Cu and/or Fe calculated as the respective element and based on 100 wt-%of YO 2 contained in the zeolitic material having a CHA framework structure.
  • the mixture prepared in (1) and crys-tallized in (2) contain more than an impurity of an organic structure directing agent specifically used in the synthesis of zeolitic materials having a CHA-type framework structure, in particular specific tetraalkylammonium compounds, dialkyl amines, heterocyclic amines, and combina-tions of two or more thereof.
  • the mixture prepared in (1) and crystallized in (2) contain more than an impurity of one or more organic structure direct-ing agents selected from the group consisting of tetra (C 1 –C 5 ) alkylammonium compounds, di(C 1 –C 5 ) alkyl amines, oxygen containing heteroxyclic amines with 5 to 8 ring members, and combinations of two or more thereof, more preferably from the group consisting of tetra (C 2 –C 4 )alkylammonium compounds, di (C 2 –C 4 ) alkyl amines, oxygen containing heteroxyclic amines with 5 to 7 ring members, and combinations of two or more thereof, more preferably from the group consisting of tetra (C 2 –C 3 ) alkylammonium compounds, di (C 2 –C 3 ) alkyl amines, oxygen containing heteroxyclic amines with 5 or 6 ring members, and combinations of two
  • Such an impurity can, for example, be caused by organic structure directing agents still present in seed crystals used in the inventive process.
  • Organic structure directing agents eventually contained in seed crystals may not, however, participate in the crystallization process since they are trapped within the seed crystal framework and therefore may not act as structure directing agents within the mean-ing of the present invention.
  • an “organotemplate-free” synthetic process relates to a synthetic process wherein the materials used therein are substantially free of organic struc-ture directing agents, wherein “substantially” as employed in the present invention with respect to the amount of one or more organic structure directing agents contained in the one or more materials used in a synthetic process indicates an amount of 0.1 wt. -%or less of one or more organic structure directing agents based on 100 wt. -%of the mixture prepared in (1) , preferably 0.05 wt. -%or less, more preferably 0.001 wt. -%or less, more preferably 0.0005 wt. -%or less, and even more preferably 0.0001 wt.
  • organic structure directing agents if at all present in any one of the materials used in the synthetic proc-ess, may also be denoted as “impurities” or “trace amounts” within the meaning of the present invention.
  • impurities or “trace amounts” within the meaning of the present invention.
  • trace amounts within the meaning of the present invention.
  • organotemplate and “organic structure direct-ing agent” are synonymously used in the present application.
  • organotemplate designates any con-ceivable organic material which is suitable for template-mediated synthesis of a zeolite material, preferably of a zeolite material having a CHA-type framework-structure, and even more prefera-bly which is suitable for the synthesis of Chabazite.
  • organotemplates include e.g.
  • the preparation of a zeolitic material according to the process defined in (1) and (2) and preferably according to the inventive process as defined in particular and preferred embodiments of the present application is conducted in the absence of an organic structure directing agent and is thus an organotemplate-free synthetic process within the meaning of the present invention.
  • YO 2 , X 2 O 3 , and optionally Z 2 O 5 are comprised in the CHA framework structure as structure building elements, as opposed to non-framework elements which can be present in the pores and cavities formed by the framework structure and typical for zeolitic materials in general.
  • a zeolitic material having a CHA framework structure is crys-tallized in (2) , wherein said material comprises YO 2 .
  • one or more sources for YO 2 and seed crystals comprising YO 2 are provided in (1) for the crystallization thereof.
  • Y stands for any conceivable tetravalent element, Y standing for either or several tetravalent elements.
  • Preferred tetravalent elements according to the present invention include Si, Sn, Ti, Zr, and Ge, and combinations thereof. More preferably, Y stands for Si, Ti, or Zr, or any combi-nation of said tetravalent elements, even more preferably for Si, and/or Sn. According to the present invention, it is particularly preferred that Y stands for Si.
  • Y comprised in the seed crys-tals and/or, preferably and, that Y provided in (1) in the one or more sources for YO 2 are, inde-pendently from one another, selected from the group consisting of Si, Sn, Ti, Zr, Ge, and mix-tures of two or more thereof, Y preferably being Si.
  • one or more sources for YO 2 are provided in (1) , wherein said one or more sources may be provided in any conceivable form provided that a zeolitic ma-terial having a CHA framework structure comprising YO 2 and X 2 O 3 can be crystallized in (2) .
  • YO 2 is provided as such and/or as a compound which comprises YO 2 as a chemical moiety and/or as a compound which (partly or entirely) is chemically transformed to YO 2 during the inventive process.
  • the source for SiO 2 preferably provided in (1) can also be any conceivable source.
  • any type of silicas and/or silicates may be used, wherein preferably the one or more sources for YO 2 comprises one or more silicates.
  • the one or more silicates any conceivable silicate or a combination of silicates may be used wherein it is preferred that said one or more silicates comprise one or more alkaline metal silicates, the alkaline metal being preferably selected from the group consisting of Li, Na, K, and combinations of two or more thereof.
  • the one or more silicates comprise one or more sodium and/or one or more potassium silicates, wherein even more preferably the one or more silicates comprise one or more sodium silicates.
  • silicate as a preferred source for YO 2 generally refers to any conceivable silicates, provided that an organotemplate-free zeolitic ma-terial having a CHA framework structure may be crystallized in (2) of the inventive process.
  • silicate refers to the [SiO 3 ] 2- anion comprised in the particularly preferrred silicate compounds comprised in the one or more sources for YO 2 .
  • the one or more sources for YO 2 comprises one or more silicates, preferably one or more alkali metal silicates, wherein the alkali metal is preferably selected from the group consisting of Li, Na, K, and combinations of two or more thereof, wherein more preferably the alkali metal is Na and/or K, and wherein even more preferably the alkali metal is Na.
  • the one or more sources for YO 2 provided in (1) comprises one or more silicates
  • said one or more silicates comprise water glass.
  • any type of water glass or combi-nations thereof may be used in the present invention as the one or more sources for YO 2 pro-vided that a zeolitic material having a CHA framework structure may be obtained, wherein pre-ferably sodium and/or potassium silicate is employed as water glass, more preferably sodium silicate.
  • the mixture prepared in (1) comprises water glass, preferably sodium and/or potassium silicate, and even more preferably sodium silicate.
  • the one or more sources for YO 2 comprises one or more silicates
  • one or more silicas are added to the mixture prepared in (1) in addition to the one or more silicates.
  • any conceivable source of silica may be employed, provided that a zeolitic material having the CHA-type framework structure may be crystallized in (2) .
  • any type of silica may be employed such as fumed silica, silica hydrosols, reactive amorphous silicas, silica gel, silicic acid, colloidal silica, pyrogenic silica, silicic acid esters, tetraalkoxy silanes, or mixtures of at least two of these compounds, wherein more preferably one or more silica hydrosols and/or one or more colloidal silicas are used, and even more preferably one or more colloidal silicas.
  • the mixture prepared in (1) of the inventive process further comprises one or more silicas in addition to the one or more sili-cates, preferably one or more silica hydrosols and/or one or more colloidal silicas, and even more preferably one or more colloidal silicas in addition to the one or more silicates.
  • X 2 O 3 is comprised in the zeolitic material having a CHA framework structure which is crystallized in (2) . Furthermore, one or more sources for X 2 O 3 and seed crystals comprising X 2 O 3 are provided in (1) for the crystallization thereof.
  • X stands for any conceivable trivalent element, X standing for either one or several trivalent ele-ments.
  • Preferred trivalent elements according to the present invention include Al, B, In, and Ga, and combinations thereof. More preferably, X stands for Al, B, or In, or any combination of said trivalent elements, even more preferably for Al and/or B. According to the present invention, it is particularly preferred that X stands for Al.
  • X comprised in the seed crys-tals and/or preferably and, that X provided in (1) in the one or more sources for X 2 O 3 are, inde-pendently from one another, selected from the group consisting of Al, B, In, Ga, and mixtures of two or more thereof, X preferably being Al and/or B, and more preferably being Al.
  • the one or more sources for X 2 O 3 provided in (1) may be provided in any conceivable form, provided that a zeolitic material having a CHA framework structure is crystallized in (2) .
  • X 2 O 3 is provided as such and/or as a compound which comprises X 2 O 3 as a chemical moiety and/or as a compound which (partly or entirely) is chemi-cally transformed to X 2 O 3 during the inventive process.
  • the source for Al 2 O 3 provided in (1) can be any conceivable source.
  • alumina and aluminates aluminum salts such as, for example, alkali metal aluminates, aluminum alcoholates, such as, for example, aluminum triisopropylate, or hydrated alumina such as, for example, alumina trihy-drate, or mixtures thereof.
  • the source for Al 2 O 3 comprises at least one compound selected from the group consisting of alumina and aluminates, preferably aluminates, more pre-ferably alkali metal aluminates, wherein even more preferably, the alkali metal of the aluminate comprises one or more of the alkali metals M.
  • the at least one source preferably comprises sodium and/or potassium aluminate, more preferably sodium aluminate.
  • the source for Al 2 O 3 is sodium aluminate.
  • the one or more sources for X 2 O 3 comprises one or more aluminate salts, preferably one or more alkali metal aluminates, wherein the alkali metal is preferably selected from the group consisting of Li, Na, K, and combinations of two or more thereof, wherein more preferably the alkali metal is Na and/or K, and wherein even more preferably the alkali metal is Na.
  • the mixture according to (1) comprises one or more silicates as a source for YO 2 and one or more aluminates as a source for X 2 O 3 , more preferably one or more alkali metal silicates and one or more alkali metal aluminates, more preferably a sodium and/or potassium silicate and a sodium and/or potassium aluminate, more preferably a sodium silicate and sodium aluminate, wherein even more prefer-ably the one or more sources for YO 2 comprises sodium waterglass (Na 2 SiO 3 ) and the one or more sources for X 2 O 3 comprises sodium aluminate.
  • the mixture according to (1) comprises one or more silicas in addition to one or more silicates as a source for YO 2 and one or more aluminates as a source for X 2 O 3 , more preferably one or more colloidal silicas in addition to one or more alkali metal silicates and one or more alkali metal aluminates, more preferably one or more col-loidal silicas in addition to a sodium and/or a potassium silicate and sodium and/or potassium aluminate, more preferably one or more colloidal silicas in addition to a sodium silicate and so-dium aluminate, wherein even more preferably the one or more sources for YO 2 comprises one or more colloidal silicas in addition to sodium waterglass (Na 2 SiO 3 ) and the one or more sources for X 2 O 3 comprises sodium aluminate.
  • the mixture prepared in (1) optionally comprises one or more sources for Z 2 O 5 , wherein Z stands for any conceivable pentavalent element, Z standing for either one or several pentavalent elements.
  • Z 2 O 5 is provided as such and/or as a compound which comprises Z 2 O 5 as a chemical moiety and/or as a compound which (partly or entirely) is chemically transformed to Z 2 O 5 during the inventive process.
  • any con-ceivable source may be provided as the one or more sources for Z 2 O 5 , provided that in (2) of the inventive process, a zeolitic material having a CHA framework structure is crystallized.
  • the zeolitic material having a CHA framework structure crystallized in (2) as well as the seed crystals provided in (1) for the crystallization thereof may respectively comprise Z 2 O 5 .
  • Preferred pentavalent elements Z according to the present invention include P, As, Sb, Bi, V, Nb, Ta, and combinations of two or more thereof. More preferably, Z stands for P, As, V, and combinations of two or more thereof, wherein even more preferably Z comprises P or As. Ac-cording to particularly preferred embodiments, Z comprises P, wherein it is particularly preferred that Z stands for P.
  • Z optionally comprised in the seed crystals and/or, preferably and, that Z in the one or more sources for Z 2 O 5 optionally fur-ther provided in (1) are, independently from one another, selected from the group consisting of P, As, Sb, Bi, V, Nb, Ta, and combinations of two or more thereof, preferably from the group consisting of P, As, V, and combinations of two or more thereof, wherein more preferably Z comprises P or As, preferably P, and wherein even more preferably Z is P.
  • one or more sources for Z 2 O 5 may optionally be pro-vided in (1) .
  • the one or more sources for Z 2 O 5 which may be provided to this effect, no particular restrictions apply provided that a zeolitic material having a CHA framework struc-ture is crystallized in (2) .
  • the one or more sources for Z 2 O 5 is provided as such and/or as a compound which comprises Z 2 O 5 as a chemical moiety and/or as a compound which (partly or entirely) is chemically transformed to Z 2 O 5 during the inventive process.
  • the source for P 2 O 5 provided in (1) can be any conceivable source.
  • phosphoric acid is employed that the source for Z 2 O 5 optionally provided in step (1) .
  • the mixture prepared in (1) comprises seed crystals having a CHA framework structure, wherein the CHA framework structure of the seed crystals compris-es YO 2 and X 2 O 3 , wherein if the CHA framework structure of the seed crystals does not contain Z 2 O 5 , said seed crystals then preferably display a YO 2 : X 2 O 3 molar ratio of 5 or greater than 5.
  • an organotemplate-free synthetic process may be provided for obtaining a zeolitic material having a CHA frame-work structure comprising YO 2 and X 2 O 3 , in particular in instances in which the CHA framework structure of the seed crystals does not contain Z 2 O 5 .
  • the process of the present invention preferably allows for the use of seed crystals displaying intermediate and high YO 2 : X 2 O 3 molar ratios.
  • intermediate and high YO 2 : X 2 O 3 molar ratios generally refers to molar ratios having a value of 5 or greater than 5, and in particular to YO 2 : X 2 O 3 molar ratios according to particular and preferred embodiments of the present invention.
  • the YO 2 : X 2 O 3 molar ratio of the seed crystals having a CHA framework structure provided in (1) of the inventive process may display any conceivable YO 2 : X 2 O 3 molar ratio provided that a zeolitic material having a CHA framework structure may be crystallized in (2) of the inventive process, wherein the value of the YO 2 : X 2 O 3 molar ratio is preferably either 5 or a value greater than 5.
  • the seed crystals provided in (1) of the inventive process may display a YO 2 : X 2 O 3 molar ratio in the range of anywhere from 5 to 200 wherein it is preferred that the molar ratio displayed by the seed crystals is comprised in the range of from 6 to 150, more preferably of from 8 to 100, more preferably of from 12 to 70, more preferably of from 20 to 50, more prefera-bly of from 25 to 40, and even more preferably of from 28 to 35. According to the inventive process it is particularly preferred that the YO 2 : X 2 O 3 molar ratio of the seed crystals is in the range of from 29 to 33.
  • optionally one or more sources for Z 2 O 5 are further provided in (1) , and that if the CHA framework structure of the seed crystals does not contain Z 2 O 5 , the seed crystals then have a YO 2 : X 2 O 3 molar ratio of 5 or greater than 5.
  • the seed crystals having a CHA framework structure pro-vided in (1) of the inventive process may optionally comprise Z 2 O 5 .
  • the seed crystals having a CHA framework structure provided in (1) of the inventive process display a YO 2 : nX 2 O 3 : pZ 2 O 5 molar ratio
  • said crystals are not necessarily characterized by a YO 2 : X 2 O 3 molar ratio but rather by a YO 2 : nX 2 O 3 : pZ 2 O 5 molar ratio wherein the value for the ratio (1+2p) : (n-p) is characteristic for the CHA framework structure of said seed crystals.
  • the CHA framework structure of the seed crystals further comprises Z 2 O 5
  • the YO 2 : X 2 O 3 molar ratio which the seed crystals further comprising Z 2 O 5 may display there is no particular restriction as to the YO 2 : X 2 O 3 molar ratio which the seed crystals further comprising Z 2 O 5 may display.
  • said ratio may have any suitable value, provided that an organotemplate-free zeolitic material may be crystallized in (2) .
  • the value for the ratio (1+2p) : (n-p) may be 1 or greater than 1, wherein it is preferred that said value is 2 or greater than 2, more preferably 3 or greater than 3, and even more preferably 5 or greater than 5.
  • the value for the ratio (1+2p) : (n-p) of seed crystals further comprising Z 2 O 5 may range anywhere from 1 to 500, more preferably from 2 to 400, more preferably from 3 to 300, more preferably from 5 to 200, more preferably from 6 to 150, more preferably from 8 to 100, more preferably from 12 to 70, more preferably from 20 to 50, more preferably from 25 to 40, and even more preferably from 28 to 35. and even more preferably from 29 to 33.
  • the value for the ratio (1+2p) : (n-p) relative to the YO 2 : nX 2 O 3 : pZ 2 O 5 molar ratio of the seed crystals is comprised in the range of from 29 to 33.
  • the seed crystals then have a YO 2 : nX 2 O 3 : pZ 2 O 5 molar ratio, wherein the value for the ratio (1+2p) : (n-p) is 5 or greater than 5, wherein the value for the ratio (1+2p) : (n-p) preferably ranges from 5 to 200, more preferably from 6 to 150, more preferably from 8 to 100, more preferably from 12 to 70, more preferably from 20 to 50, more preferably from 25 to 40, more preferably from 28 to 35, and even more preferably from 29 to 33.
  • composition of the seed crystals having a CHA framework structure there is no particular restriction as to their composition, provided that they comprise YO 2 and X 2 O 3 , wherein Y is a tetravalent element and X is a trivalent element, and provided that they are suitable for crystallizing an organotemplate-free zeolitic material having a CHA framework structure in (2) of the inventive process.
  • YO 2 and X 2 O 3 comprised in the framework structure of the seed crystals having a CHA framework structure is contained therein as structure building elements, as opposed to non-framework elements which can be present in the pores and/or cavities formed by the CHA framework structure and typical for zeolitic materials in general.
  • the seed crystals having a CHA framework structure may comprise any conceivable tetravalent element Y, wherein Y stands for one or several tetravalent elements.
  • Preferred te-travalent elements comprised in the seed crystals according to the present invention include Si, Sn, Ti, Zr, and Ge, and combinations of two or more thereof. More preferably, Y stands for Si, Ti, or Zr, or any combination of said tetravalent elements, even more preferably for Si and/or Sn. According to the present invention, it is particularly preferred that Y stands for Si.
  • both said one or more sources for YO 2 and the seed crystals having a CHA framework structure provided in (1) comprise the same one or more tetravalent elements, wherein even more preferably Y comprised in the one or more sources for YO 2 and Y comprised in the seed crystals having a CHA framework structure stand for the same one or more tetravalent elements according to particular and preferred em-bodiments of the present invention.
  • the seed crystals having a CHA framework structure may comprise any suitable trivalent element X, wherein again X stands for either one or several trivalent elements.
  • Pre-ferred trivalent elements according to the present invention include Al, B, In, and Ga, and com-binations thereof. More preferably, X comprises Al or Ga, wherein more preferably X comprises Al, and wherein even more preferably X is Al.
  • both said one or more sources for X 2 O 3 and the seed crystals having a CHA framework structure provided in (1) comprise the same one or more trivalent elements X, wherein even more preferably X comprised in the one or more sources for X 2 O 3 and X com-prised in the seed crystals having a CHA framework structure stand for the same one or more trivalent elements according to particular and preferred embodiments of the present invention.
  • the CHA framework structure may accordingly comprise any suitable pentavalent element Z, wherein Z stands for either one of several pentavalent elements.
  • Preferred pentavalent ele-ments according to the present invention include P, As, Sb, Bi, V, Nb, Ta, and combinations of two or more thereof. More preferably Z comprises one or more pentavalent elements selected from the group consisting of P, As, V, and combinations of two or more thereof, wherein more preferably Z comprises P or As, preferably P, and wherein even more preferably Z is P
  • both said one or more sources for YO 2 and said one or more sources for X 2 O 3 as well as the seed crystals having a CHA framework struc-ture provided in (1) comprise the same one or more tetravalent elements Y in addition to the same one or more trivalent elements X, wherein even more preferably Y comprised in the one or more sources for YO 2 and Y comprised in the seed crystals as well as X comprised in the one or more sources for X 2 O 3 and X comprised in the seed crystals stand for the same one or more tetravalent elements and the same one or more trivalent elements, respectively, according to particular and preferred embodiments of the present invention.
  • a zeolitic material having a CHA framework struc-ture comprising YO 2 and X 2 O 3 may be crystallized in (2) .
  • any conceivable YO 2 : X 2 O 3 molar ratio may be provided in the mixture prepared in (1) , wherein, by way of ex-ample, said molar ratio may range anywhere from 1 to 150.
  • the YO 2 : X 2 O 3 molar ratio of the mixture prepared in (1) is comprised in the range of from 2 to 100, more preferably from 5 to 70, more preferably from 10 to 50, more preferably from 13 to 30, and more preferably from 16 to 25. According to particularly preferred embodiments of the present invention, the YO 2 : X 2 O 3 molar ratio of the mixture prepared in (1) ranges from 18 to 22.
  • the mixture prepared in (1) preferably comprises one or more alkaline metals M.
  • said one or more alkaline metals M may be provided from any suitable compounds or compounds comprising one or more alkaline metals M, wherein pre-ferably the one or more alkaline metals M are provided as one or more alkaline metal salts.
  • the one or more alkaline metals M are provided as one or more alkaline metal compounds being the one or more sources for YO 2 and/or the one or more sources for X 2 O 3 , even more preferably as one or more alkaline metal compounds being the respective sources for YO 2 and X 2 O 3 .
  • the one or more alkaline metal compounds used as sources for YO 2 and/or X 2 O 3 preferably comprise one or more alkaline metal salts used as the one or more sources for YO 2 and/or X 2 O 3 wherein according to a particularly preferred embodiment one or more alkaline metal salts are used as the one or more sources for YO 2 and/or X 2 O 3 , and prefer-ably as the one or more sources for both YO 2 and X 2 O 3 .
  • any suitable alkaline metal M or combination of alkaline metals M may be used, wherein preferably the one or more alkaline metals M are selected from the group consisting of Li, Na, K, and combinations of two or more thereof.
  • the one or more alkaline metals M comprise Li and/or Na, and preferably Na, wherein even more preferably the one or more alkaline metal is Li and/or Na, and preferably Na.
  • the M 2 O : YO 2 molar ratio of the mixture prepared in (1) may range anywhere from 0.01 to 5, wherein preferably said ratio ranges from 0.05 to 2, more preferably from 0.1 to 1.5, more preferably from 0.15 to 1, and even more pre-ferably from 0.2 to 0.5.
  • the M 2 O : YO 2 molar ratio of the mixture prepared in (1) ranges from 0.25 to 0.35.
  • the mixture prepared in (1) comprises one or more alkaline metals M
  • the M 2 O : X 2 O 3 molar ratio of the mixture again provided that a zeolitic material having a CHA framework structure is crystallized in (2) .
  • the YO 2 : X 2 O 3 : M 2 O 3 molar ratios of said preferred mixtures may range anywhere from (5 -70) : 1 : (0.5 -20) , wherein preferably the molar ratios are in the range of from (10 -50) : 1 : (1 -15) , more preferably from (13 -30) : 1 : (2 -10) , and more pre-ferably from (16 -25) : 1 : (4 -8) .
  • the YO 2 : X 2 O 3 : M 2 O 3 molar ratios of the mixture prepared in (1) range from (18 -22) : 1 : (5 -7) .
  • a mixture defined as not containing potassium and/or strontium relates to a mixture wherein the amount of potassium and/or strontium contained therein is 0.001 wt. -%or less of potassium and/or strontium, prefer-ably of 0.0005 wt. -%or less, more preferably of 0.00001 wt. -%or less, more preferably of 0.000005 wt. -%or less, and even more preferably 0.000001 wt. -%or less thereof.
  • Said amounts of potassium and/or strontium, if at all present in the mixture prepared in (1) may also be denoted as “impurities” or “trace amounts” within the meaning of the present invention.
  • impurities or “trace amounts” within the meaning of the present invention.
  • the mixture prepared in (1) does not contain potassium.
  • the mixture prepared in (1) contains no K and/or Sr, preferably no K.
  • the CHA framework structure displayed by the seed crystals there is no particular restriction as to the CHA framework structure displayed by the seed crystals provided that said seed crystals display an X-ray dif- fraction pattern typical of a CHA framework structure in particular with respect to the reflections and their 2 ⁇ degree positions relative to one another.
  • the dif-fraction pattern is typical of a CHA framework structure
  • the first reflection in the X-ray diffraction pattern of the seed crystals i.e.
  • the reflection having the lowest angle 2 ⁇ value is the reflection having highest intensity among all measured reflections, i.e. the reflection measured at the lowest dif-fraction angle 2 ⁇ has an intensity of 100 %.
  • the diffraction angle 2 ⁇ having an intensity of 100 % is comprised in the range of from 5 to 15 °2 ⁇ , wherein more preferably, said most intense reflection is comprised in the range of from 8 to 12 °2 ⁇ , more preferably of from 9 to 10.5 °2 ⁇ , more preferably of from 9.2 to 10 °2 ⁇ , more preferably of from 9.5 to 9.7 °2 ⁇ , and even more preferably of from 9.55 to 9.65 °2 ⁇ .
  • the most intense reflection in the diffraction pattern of the seed crystals having a CHA framework struc-ture when using Cu K (alpha 1) radiation is comprised in the range of from 9.58 to 9.62 °2 ⁇ .
  • seed crystals are provided in (1) , wherein said seed crystals comprise a zeolitic material having a CHA framework structure.
  • said seed crystals can comprise any zeolitic material having a CHA framework structure pro-vided that a zeolitic material having a CHA framework structure is crystallized in (2) , wherein if the CHA framework structure of the seed crystals does not contain Z 2 O 5 , the framework struc-ture preferably has a YO 2 : X 2 O 3 molar ratio of 5 or greater than 5.
  • the zeolitic ma-terial having a CHA framework structure comprised in the seed crystals is a zeolitic material as obtained in or obtainable from (2) of the inventive process, and in particular according to any of the particular or preferred embodiments thereof described in the present application. More pre-ferably, the zeolitic material having a CHA framework structure comprised in the seed crystals is the same as the zeolitic material having a CHA framework structure which is crystallized in (2) .
  • seed crystals comprising one ore more zeolites selected from the group consisting of (Ni (deta) 2 ) -UT-6, Chabazite,
  • any suitable amount of seed crystals can be provided in the mixture according to (1) , provided that a zeolitic material having a CHA framework structure is crystallized in (2) .
  • an amount of seed crystals may be provided in the mixture according to (1) ranging anywhere from 0.1 to 35 wt. -%based on 100 wt. -%of YO 2 in the one or more sources for YO 2 provided in (1) for obtaining a zeolitic material with a CHA framework structure in (2) .
  • the amount of seed crystals in the mixture according to (1) ranges from 12 to 14 wt. -%based on 100 wt. -%of YO 2 in the one ore more sources for YO 2 .
  • the mixture according to (1) of the inventive process prefer-ably further comprises one or more solvents.
  • any conceivable solvents may be used in any suitable amount, provided that a zeolitic material having a CHA framework structure comprising YO 2 , X 2 O 3 , and optionally comprising Z 2 O 5 can be obtained from crystallization in (2) .
  • the one or more solvents may be chosen from water, organic solvents, and mixtures thereof, preferably from the group consisting of distilled water, alcohols, and mix-tures thereof. More preferably from the group consisting of distilled water, methanol, ethanol, propanol, and mixtures thereof.
  • only water and preferably only distilled water is contained in the mixture according to (1) as the solvent.
  • the mixture prepared in (1) further comprises one or more solvents, wherein said one or more solvents preferably compris-es water, more preferably distilled water.
  • the H 2 O : YO 2 molar ratio of the mixture prepared in (1) may range anywhere from 1 to 25.
  • the H 2 O : YO 2 molar ratio ranges from 2 to 20, more preferably from 4 to 18, more preferably from 6 to 16, and more pre-ferably from 8 to 14.
  • the mixture according to (1) comprises water as a solvent, and even more preferably wherein distilled water is the only solvent present in said mixture, it is preferred that the H 2 O : YO 2 molar ratio of the mixture according to (1) ranges from 10 to 12.
  • (2) according to the inventive process can be conducted in any conceivable manner, provided that a zeolitic material having a CHA framework structure is crystallized from the mix-ture according to (1) .
  • the mixture can be crystallized in any type of vessel, wherein a means of agitation is preferably employed, preferably by rotation of the vessel and/or stirring, and more preferably by stirring the mixture.
  • the mixture is preferably heated during at least a portion of the crystallization process in (2) .
  • the mixture can be heated to any conceivable tem-perature of crystallization, provided that a zeolitic material having a CHA framework structure is crystallized from the mixture.
  • the mixture is heated in (2) to a temperature of crystal-lization ranging from 80 to 200°C, more preferably from 90 to 180°C, more preferably from 100 to 160°C, more preferably from 110 to 140°C, and even more preferably from 115 to 130°C.
  • the mixture according to (1) is subjected in (2) to a pressure which is elevated with regard to normal pressure.
  • normal pressure as used in the context of the present invention relates to a pressure of 101, 325 Pa in the ideal case.
  • this pressure may vary within boundaries known to the person skilled in the art.
  • this pressure can be in the range of from 95,000 to 106,000 or of from 96,000 to 105,000 or of from 97,000 to 104,000 or of from 98,000 to 103,000 or of from 99,000 to 102,000 Pa.
  • heating in (2) is conducted under solvothermal conditions, meaning that the mixture is crystallized under autogenous pressure of the solvent which is used, for example by conducting heating in an autoclave or other crystallization vessel suited for generating solvothermal conditions.
  • the solvent comprises water, preferably distilled water
  • heating in (2) is accordingly preferably con-ducted under hydrothermal conditions.
  • the apparatus which can be used in the present invention for crystallization is not particularly restricted, provided that the desired parameters for the crystallization process can be realized, in particular with respect to the preferred embodiments requiring particular crystallization condi-tions.
  • any type of au-toclave or digestion vessel can be used.
  • heating may be conducted during the entire crystallization process or dur-ing only one or more portions thereof, provided that a zeolitic material having the CHA frame-work structure is crystallized.
  • heating is conducted during the entire duration of crys-tallization.
  • the duration of the crystallization process in (2) of the inventive process is not partic-ularly limited.
  • said crystallization process is conducted for a period ranging from 2 to 36 h, more preferably from 6 to 24 h, more preferably from 12 to 20 h, and more preferably from 14 to 18 h.
  • the process of the present invention can optionally comprise further steps for the work-up and/or further physical and/or chemical transformation of the zeolitic material having an CHA framework structure crystallized in (2) from the mixture prepared in (1) .
  • the crystallized material can for example be subject to any sequence of isolation and/or washing procedures, wherein the zeolitic material obtained from crystallization in (2) is preferably subject to at least one isolation and at least one washing procedure.
  • the inventive process preferably further comprises one or more of the following
  • steps (2a) and/or (2b) and/or (2c) can be conducted in any order, and
  • one or more of said steps is preferably repeated one or more times.
  • Isolation of the crystallized product in (2a) can be achieved by any conceivable means.
  • isolation of the crystallized product in (2a) is achieved by means of filtration, ultrafiltration, diafiltration, centrifugation and/or decantation methods, wherein filtration methods can involve suction and/or pressure filtration steps.
  • washing agents which may be used are, for example, water, alcohols, such as metha-nol, ethanol or propanol, or mixtures of two or more thereof.
  • mixtures are mixtures of two or more alcohols, such as methanol and ethanol or methanol and propanol or ethanol and propanol or methanol and ethanol and propanol, or mixtures of water and at least one alco-hol, such as water and methanol or water and ethanol or water and propanol or water and methanol and ethanol or water and methanol and propanol or water and ethanol and propanol or water and methanol and ethanol and propanol.
  • Water or a mixture of water and at least one alcohol, preferably water and ethanol, is preferred, distilled water being very particularly pre-ferred as the only washing agent in (2b) .
  • the separated zeolitic material is washed in (2b) until the pH of the washing agent, preferably the washwater, is in the range of from 6 to 8, preferably from 6.5 to 7.5, as deter-mined via a standard glass electrode.
  • any conceivable means of drying can be used in (2c) .
  • Drying procedures preferably include heating and/or applying vacuum to the zeolitic material having a CHA framework struc-ture.
  • the one or more drying steps in (2c) involve spray drying and/or spray granulation, and preferably spray drying of the zeolitic material.
  • the drying temperatures are preferably in the range of from 25°C to 150°C, more pre-ferably of from 60 to 140°C, more preferably of from 70 to 130°C and even more preferably in the range of from 75 to 125°C.
  • the durations of drying are preferably in the range of from 2 to 60 h, more preferably in the range of 6 to 48 hours, more preferably of from 12 to 36 h, and even more preferably of from 18 to 30 h.
  • the zeolitic material crystallized in (2) is subject to at least one ion-exchange procedure in (3) , wherein the term "ion-exchange"according to the present invention generally refers to non-framework ionic elements and/or molecules contained in the zeolitic material.
  • the non-framework ionic element comprises one or more of the one or more alkali metals M preferably comprised in the zeolitic material having a CHA framework structure, more preferably Na and/or K, and even more preferably Na which is accordingly ion-exchanged against against Cu and/or Fe, and preferably against Cu.
  • any conceiva-ble ion-exchange procedure with all possible ionic elements and/or molecules can be conducted on the zeolitic material, with the exception of organic structure directing agents specifically used in the synthesis of zeolitic materials having an CHA framework structure, in particular specific tetraalkylammonium compounds, dialkyl amines, heterocyclic amines, including combinations of two or more thereof, and/or related organotemplates such as any suitable N-alkyl-3-quinuclidinol compound, N, N, N-trialkyl-exoaminonorbornane compound, N, N, N-trimethyl-1-adamantylammonium compound, N, N, N-trimethyl-2-adamantylammonium compound, N, N, N-trimethylcyclohexylammonium compound, N, N-dimethyl-3, 3-dimethylpiperidinium compound, N, N-methylethyl-3, 3-dimethylpiperidinium compound, N, N-
  • At least one ionic non-framework element contained in the zeolitic material having a CHA framework is ion exchanged against Cu and/or Fe, and preferably against Cu, wherein said at least one ionic non-framework element is preferably one or more alkali metals, more preferably Na and/or K, and more prefer-ably Na.
  • the zeolitic material obtained in (2) is subject to an ion-exchange procedure, wherein it is ion-exchanged against copper and/or iron, preferably against copper.
  • any conceivable ion-exchange procedure can be conducted on the zeolitic material to this effect, provided that a copper and/or iron ion-exchanged zeolitic material is ob-tained.
  • the zeolitic material ob-tained in (2) is first converted to the H-form, preferably via the ammonium form and subsequent calcination thereof for obtaining the H-form, prior to ion change with copper and/or iron.
  • the amount of copper and/or iron is ion exchanged into the zeolitic material accord-ing to the inventive process, no particular restrictions apply provided that the amount of copper and/or iron may exchanged therein is in the range of from from 3.8 to 12 wt. -%of Cu and/or Fe calculated as the respective element and based on 100 wt-%of YO 2 contained in the zeolitic material having a CHA framework structure.
  • refer-ence to the amounts of copper and/or iron as such or in relation to other materials indicates the total amount of copper and/or iron or refers to the totality of copper and/or iron contained in the zeolitic material.
  • the term "copper and/or iron” as used in the present application accordingly indicates the total amount or the to-tality of both copper and iron contained in the inventive zeolitic material or in the zeolitic material obtained according to the inventive process.
  • the zeolitic material is ion exchanged in (3) such as to obtain a loading in the zeolitic material ranging from 4.5 to 10 wt. -%of Cu and/or Fe calculated as the respective element and based on 100 wt-%of YO 2 contained in the zeolitic material having a CHA framework structure.
  • the zeolitic material is ion exchanged such as to obtain a loading of copper and/or iron ranging from 5.2 to 9.5 wt. -%, more preferably from 5.5 to 9 wt. -%, more preferably from 6 to 8.5 wt. -%, and more preferably from 6.5 to 8 wt. -%.
  • the zeolitic material is ion exchanged in (3) such as to obtain a loading of copper and/or iron ranging from 7 to 7.5 wt. -%calculated as the respective element and based on 100 wt-%of YO 2 contained in the zeolitic material having a CHA framework structure.
  • copper and/or iron may be ion exchanged as Cu + , Cu 2+ , Fe 2+ , and/or Fe 3+ , respectively, wherein it is however preferred according to the present invention that independently from one another copper is ion exchanged as Cu 2+ and iron is ion exchanged as Fe 2+ .
  • the ion-exchange step (3) may comprise one or more ion-exchange procedures.
  • the zeolitic material obtained in step (2) of the inventive process is first ion-exchanged with H + and/or ammonium, preferably with H + , prior to one or more ion-exchange procedures with copper and/or iron.
  • the zeolitic material obtained in step (3a) of the inventive process may also be subject to a step of calcina-tion in (3b) , is effected by heating of the zeolitic material, prior to ion-exchange with copper and/or iron in step (3c) .
  • said calcination may be effected in (3b) by heating of the zeolitic material to any suitable temperature for any conceivable dura-tion provided that the resulting material may be ion-exchanged with copper and/or iron for ob-taining an ion-exchanged material wherein the loading with copper and/or iron is comprised in the range of from 3.8 to 12 wt. -%of Cu and/or Fe calculated as the respective element and based on 100 wt-%of YO 2 contained in the zeolitic material having a CHA framework structure.
  • the calcination temperature may range anywhere from 200 to 850°C, wherein the calcination temperature is preferably comprised in the range of from 250 to 750°C, more preferably from 300 to 700°C, more preferably from 350 to 650 °C, more preferably from 400 to 600°C, and more preferably from 450 to 550°C.
  • the zeolitic material obtained in step (3a) is calcined in (3b) at a temperature comprised in the range of from 475 to 525°C prior to ion-exchange with copper and/or iron in (3c) .
  • the calcination may be conducted for a period ranging anywhere from 0.5 to 36 h, wherein pre-ferably the duration of the calcination ranges from 1 to 24 h, more preferably from 2 to 20 h, more preferably from 3 to 16 h, more preferably from 3.5 to 12 h, more preferably from 4 to 10 h, more preferably from 4.5 to 8 h, more preferably from 5 to 7 h.
  • the calcination procedure performed to ion-exchange with copper and/or iron is performed for a duration of from 5.5 to 6.5 h.
  • the zeolitic material obtained from crystallization in (3a) and/or (3c) is subject to at least one isolating step prior to being subject to at least one ion-exchange procedure, preferably to at least one isolating step followed by at least one washing step, and more preferably to at least one isolating step followed by at least one washing step followed by at least one drying step.
  • the preferred washing and/or isolation and/or ion-exchange procedures comprised in the inventive process can be conducted in any conceivably order and repeated as often as desired.
  • (3a) further comprises one or more of the following
  • steps (3a. i) and/or (3a. ii) and/or (3a. iii) can be conducted in any order, and
  • one or more of said steps is preferably repeated one or more times.
  • (3c) further comprises one or more of the following
  • steps (3c. i) and/or (3c. ii) and/or (3c. iii) can be conducted in any order, and
  • isolation of the crystallized product in (3a. i) and (3c. i) can be achieved by any conceivable means.
  • isolation of the crystallized product in (3a. i) and/or (3c. i) is achieved by means of filtration, ultrafiltration, diafiltration, centrifugation and/or decantation methods, wherein filtration methods can involve suction and/or pressure filtration steps.
  • any conceiva-ble solvent can be used.
  • Washing agents which may be used are, for example, water, alcohols, such as methanol, ethanol or propanol, or mixtures of two or more thereof.
  • mix-tures are mixtures of two or more alcohols, such as methanol and ethanol or methanol and pro-panol or ethanol and propanol or methanol and ethanol and propanol, or mixtures of water and at least one alcohol, such as water and methanol or water and ethanol or water and propanol or water and methanol and ethanol or water and methanol and propanol or water and ethanol and propanol or water and methanol and ethanol and propanol.
  • Water or a mixture of water and at least one alcohol, preferably water and ethanol, is preferred, distilled water being very particu-larly preferred as the only washing agent in (3a. i) and/or (3c. i) .
  • the separated zeolitic material is washed in (3a. ii) and/or (3c. ii) until the pH of the washing agent, preferably the washwater, is in the range of from 6 to 8, preferably from 6.5 to 7.5, as determined via a standard glass electrode.
  • drying pro-cedures preferably include heating and/or applying vacuum to the zeolitic material having a CHA framework structure.
  • the one or more drying steps in (3a. iii) and/or (3c. iii) involve spray drying and/or spray granulation, and preferably spray drying of the zeolitic material.
  • the drying temperatures are preferably in the range of from 25°C to 150°C, more preferably of from 60 to 140°C, more preferably of from 70 to 130°C and even more preferably in the range of from 75 to 125°C.
  • the durations of drying are preferably in the range of from 2 to 60 h, more preferably in the range of 6 to 48 hours, more preferably of from 12 to 36 h, and even more preferably of from 18 to 30 h.
  • a calcination step is not employed prior to the one or more ion exchange procedures of the inventive process.
  • a calci-nation step involves the heating of the zeolitic material crystallized according to (2) above a temperature of 500°C.
  • a process according to the present invention for the production of a zeolitic material having a CHA framework structure which does not comprise a calcination step prior to the one or more ion exchange procedures refers to processes, wherein the zeolitic material crystallized according to (2) is not subject in a subsequent step prior to ion exchange in (3) according to any of the particular and preferred embodiments of the inventive process to a temperature exceeding 450°C, more preferably 350°C, more preferably 300°C, more preferably 250°C, more preferably 200°C, and even more preferably 150°C.
  • zeolitic material which is “non-calcined” is one which has not been subject to any one of the aforementioned calcination procedures.
  • the zeolitic material having a CHA framework structure obtained according to the inventive process may be any conceivable zeolite of the CHA framework type comprising YO 2 , X 2 O 3 , and optionally comprising Z 2 O 5 , wherein Y is a tetravalent element, X is a trivalent ele-ment, and Z is a pentavalent element.
  • the present invention furthermore relates to a synthetic copper and/or iron containing zeolitic material having a CHA framework structure which is either obtained by the process according to the present invention or by any conceivable process which leads to a copper and/or iron con-taining zeolitic material having a CHA framework structure as obtainable according to the inven-tive process.
  • the synthetic copper and/or iron containing zeolitic material having a CHA framework structure is a non-calcined zeolitic material which is either obtained by the process according to the present invention or by any conceivable process which leads to a zeolitic material having a copper and/or iron containing CHA frame-work structure as obtainable according to the inventive process.
  • a material which is designated as a “synthetic” material does not signify that the designated material as such may not naturally occur in nature.
  • a “synthetic” material only indicates that it is manmade but by no means excludes that the material as such may occur naturally.
  • the term “organotemplate-free zeolitic material” is synonymous to “synthetic organotemplate-free zeolitic material” .
  • the present invention also relates to a synthetic copper and/or iron containing zeolitic material having a CHA framework structure, optionally obtainable and/or obtained according to the process of any of the particular and preferred embodiments of the inventive process, where-in the CHA framework structure comprises SiO 2 , X 2 O 3 , and optionally comprises Z 2 O 5 , wherein X is a trivalent element, and Z is a pentavalent element,
  • the zeolitic material contains from 3.8 to 12 wt. -%of Cu and/or Fe calculated as the respective element and based on 100 wt-%of SiO 2 contained in the zeolitic material having a CHA framework structure, and
  • the 29 Si MAS NMR of the zeolitic material comprises:
  • the 29 Si MAS NMR of the inventive zeolitic material there is no particular restriction as to the number and/or respective ppm values and/or relative intensities of the signals dis-played in the NMR spectrum provided that the 29 Si MAS NMR comprises a first peak (P1) com-prised in the range of from -96 to -98.8 ppm, a second peak (P2) comprised in the range of from -102 to -104.5 ppm, and a third peak (P3) comprised in the range of from -107.5 to -111 ppm, wherein the integration of the first, second, and third peaks in the 29 Si MAS NMR of the zeolitic material offers a ratio of the integration values P1 : P2 : P3 of (0.35 –0.7) : 1 : (0.1 –1.6) .
  • the signal at -109 ppm of the 29 Si MAS NMR corresponds to Q4 structures, wherein the respective signals at -103 and -98 pp
  • the first peak (P1) in the 29 Si MAS NMR of the inventive zeolitic material is comprised in the range of from -96.5 to -98.5 ppm, more preferably of from -96.8 to -98.2 ppm, more preferably of from -97 to -98 ppm, and more preferably of from -97.3 to -97.9 ppm. It is however particularly preferred according to the present invention that the first peak (P1) in the 29 Si MAS NMR is comprised in the range of from -97.5 to -97.7 ppm.
  • the second peak (P2) in the 29 Si MAS NMR of the inventive zeolitic material is preferably comprised in the range of from -102.5 to -104 ppm, more preferably of from -102.8 to -103.7 ppm, and more preferably of from -103 to -103.5 ppm, wherein according to particu-larly preferred embodiments the second peak (P2) is comprised in the range of from -103.2 to -103.4 ppm.
  • the third peak (P3) in the 29 Si MAS NMR of the inventive zeolitic material is comprised in the range of from -108 to -110.5 ppm, more prefera-bly of from -108.5 to -110 ppm, more preferably of from -108.8 to -109.5 ppm, and more pre-ferably of from -109 to -109.4 ppm. According to particularly preferred embodiments, however, the third peak (P3) in the 29 Si MAS NMR is comprised in the range of from -109.1 to -109.3 ppm.
  • the ratio of the integration values P1 : P2 : P3 ranges from preferably from (0.4 –0.65) : 1 : (0.15 –1.3) , more preferably from (0.42 –0.62) : 1 : (0.2 –1) , more preferably from (0.45 –0.6) : 1 : (0.3 –0.7) , more preferably from (0.48 –0.58) : 1 : (0.35 –0.5) , and more preferably from (0.5 –0.56) : 1 : (0.4 –0.45) , .
  • the ratio of the integration values P1 : P2 : P3 ranges from (0.52 –0.54) : 1 : (0.42 –0.44) .
  • the standard used in the 29 Si MAS NMR experiments for obtaining the respective values for the chemical shift in ppm in the 29 Si MAS NMR spectra according to particular and preferred embodiments of the present invention, wherein preferably an external standard is used.
  • the external standard used in the 29 Si MAS NMR experiment is the polymer Q8M8, wherein the resonance of the trimethylsilyl M group is set to 12.5 ppm.
  • the chemical shift values in ppm defined in the present application rela-tive to the 29 Si MAS NMR spectra of the inventive zeolitic materials having a CHA framework structure are preferably based on the use of the polymer Q8M8 as an external secondary stan-dard in the 29 Si MAS NMR experiment, wherein the resonance of the trimethylsilyl M group is set to 12.5 ppm.
  • the ppm and integration values respectively defined for the 29 Si MAS NMR of the inventive zeolitic material according to any of the particular and preferred embodiments of the present invention refers to the values obtained as described in the experimental section of the present application.
  • the amount of copper and/or iron which is contained in the zeolitic material accord-ing to the present invention is in the range of from from 3.8 to 12 wt. -%of Cu and/or Fe calculated as the re-spective element and based on 100 wt-%of SiO 2 contained in the zeolitic material having a CHA framework structure.
  • the total loading of copper and/or iron in the zeolitic ma-terial ranges from 4.5 to 10 wt.
  • the zeolitic material contains copper and/or iron in an amount ranging from 7 to 7.5 wt. -%calculated as the respective element and based on 100 wt-%of SiO 2 contained in the zeolitic material having a CHA framework structure.
  • the state in which cop-per and/or iron is contained in the zeolitic material there is no particular restriction as to the state in which cop-per and/or iron is contained in the zeolitic material. It is, however, preferred according to the present invention that copper and/or iron is contained in the inventive zeolitic material at least in part and preferably entirely as extra-framework ions, wherein preferably copper is contained therein as Cu 2+ , and iron is contained therein as Fe 2+ and/or Fe 3+ , and preferably at least in part as Fe 2+ . Furthermore, it is preferred according to the present invention that the copper and/or iron contained in the zeolitic material has at least in part been introduced therein via ion ex-change.
  • extra-framework ions desig-nates ions which are located at the ion exchange sites of the zeolitic material and thus serve to compensate the charge of the zeolite framework structure, and in particular the negative charge thereof.
  • non-framework ionic elements and “extra-framework ions” are preferably employed synonymously.
  • the inventive copper and/or iron containing zeolitic material having a CHA framework structure comprises X 2 O 3 .
  • X stands for any conceivable trivalent element, X standing for one or several trivalent elements.
  • Preferred trivalent elements according to the present invention include Al, B, In, and Ga, and combinations thereof. More preferably, X stands for Al, B, or In, or any combination of said trivalent elements, even more preferably for Al and/or B. According to the present invention, it is particularly preferred that X stands for Al.
  • the inventive copper and/or iron containing zeolitic material having a CHA framework structure optionally comprises Z 2 O 5 , wherein Z stands for any conceivable pentavalent element, Z standing for either one or several pentavalent ele-ments.
  • Preferred pentavalent elements Z according to the present invention include P, As, Sb, Bi, V, Nb, Ta, and combinations of two or more thereof. More preferably, Z stands for P, As, V, and combinations of two or more thereof, wherein even more preferably Z comprises P or As.
  • Z comprises P, wherein it is particularly pre-ferred that Z stands for P
  • the CHA framework structure does not contain P 2 O 5 , and preferably does not contain Z 2 O 5 , in an amount greater than 1 wt. -%based on 100 wt. -%of SiO 2 contained in the zeolitic material having a CHA framework structure, the CHA framework structure may have an SiO 2 : X 2 O 3 molar ratio of 7 or greater than 7.
  • the CHA framework structure does not contain P 2 O 5 , and pre-ferably does not contain Z 2 O 5 , in an amount greater than 1 wt. -%
  • the CHA framework structure has an SiO 2 : X 2 O 3 molar ratio ranging from 7.2 to 12, more preferably from 7.4 to 10, more pre-ferably from 7.6 to 9.5, more preferably from 7.8 to 9, more preferably from 7.9 to 8.5, and more preferably from 8 to 8.2.
  • the CHA framework structure does not contain P 2 O 5 , and pre-ferably does not contain Z 2 O 5 , in an amount greater than 1 wt.
  • the CHA framework structure contains P 2 O 5 , and preferably contains Z 2 O 5 , in an amount of 0.5 wt. -%or less, more preferably of 0.1 wt. -%or less, more preferably of 0.05 wt. -%or less, more preferably of 0.01 wt. -%or less, more preferably of 0.005 wt. -%or less, more preferably of 0.001 wt. -%or less, more preferably of 0.0005 wt. -%or less, more preferably of 0.0005 wt. -%or less, more preferably of 0.00005 wt. -%or less, and more preferably of 0.00001 wt. -%or less.
  • the CHA framework structure of the synthetic copper and/or iron containing zeolitic material further com-prises Z 2 O 5 in addition to SiO 2 and X 2 O 3 , there is, in general, no particular restriction as to the YO 2 : X 2 O 3 molar ratios displayed, such that the YO 2 : X 2 O 3 molar ratio in such inventive mate-rials may have any conceivable value.
  • the CHA framework structure further comprises Z 2 O 5 in addition SiO 2 and X 2 O 3
  • the CHA framework structure then has a YO 2 : nX 2 O 3 : pZ 2 O 5 molar ratio, wherein the value for the ratio (1+2p) : (n-p) may have any conceivable value.
  • the value for the ratio (1+2p) : (n-p) may be 1 or greater than 1, wherein it is preferred that said value is 2 or greater than 2, more preferably 3 or greater than 3, more preferably 5 or greater than 5, and even more preferably 7 or greater than 7.
  • the value for the ratio (1+2p) : (n-p) of the synthetic copper and/or iron con-taining zeolitic material having a CHA framework structure further comprising Z 2 O 5 may range anywhere from 1 to 500, more preferably from 2 to 400, more preferably from 3 to 300, more preferably from 5 to 250, more preferably from 7 to 200, more preferably from 7.5 to 100, more preferably from 8 to 50, more preferably from 8.5 to 30, more preferably from 9 to 20, more pre-ferably from 9.3 to 17, and even more preferably from 9.5 to 15.
  • the CHA framework structure comprises Z 2 O 5 in addition to SiO 2 and X 2 O 3
  • the CHA framework structure has a SiO 2 : nX 2 O 3 : pZ 2 O 5 molar ratio, wherein the value for the ratio (1+2p) : (n-p) is 7 or greater than 7, wherein the value for the ratio (1+2p) : (n-p) ranges from 7.2 to 12, and preferably ranges from 7.4 to 10, more preferably from 7.6 to 9.5, more preferably from 7.8 to 9, more preferably from 7.9 to 8.5, and more preferably from 8 to 8.2.
  • the copper and/or iron containing zeolitic material having a CHA framework structure displays an X-ray diffraction pattern typical of a CHA framework structure in particular with respect to the reflections and their 2 ⁇ degree positions relative to one another.
  • the diffraction pattern is typical of a CHA framework structure, there is no particular restriction neither with respect to the actual position of the reflections measured as angle 2 ⁇ , nor with respect to the intensities of the indi-vidual reflections relative to one another.
  • the first reflection in the X-ray diffraction pattern of the copper and/or iron containing zeolitic material having a CHA framework structure i.e. the reflection having the low-est angle 2 ⁇ value is the reflection having highest intensity among all measured reflections, i.e. the reflection measured at the lowest diffraction angle 2 ⁇ , has an intensity of 100 %.
  • the diffraction angle 2 ⁇ having an intensity of 100 %is comprised in the range of from 5 to 15 °2 ⁇ , wherein more pre-ferably, said most intense reflection is comprised in the range of from 8 to 12 °2 ⁇ , more prefera-bly of from 9 to 10.5 °2 ⁇ , more preferably of from 9.2 to 10 °2 ⁇ , more preferably of from 9.5 to 9.7 °2 ⁇ , and even more preferably of from 9.55 to 9.65 °2 ⁇ .
  • the most intense reflection in the diffraction pattern of the copper and/or iron containing zeolitic material having a CHA framework structure when using Cu K (alpha 1) radiation is comprised in the range of from 9.58 to 9.62 °2 ⁇ .
  • the material may display any conceivable molar ratio (Cu and/or Fe) : X 2 O 3 of Cu and/or Fe to X 2 O 3 , provided that the zeolitic material contains from 3.8 to 12 wt. -%of Cu and/or Fe calculated as the respective element and based on 100 wt-%of SiO 2 contained in the zeolitic material having a CHA framework structure.
  • the molar ratio (Cu and/or Fe) : X 2 O 3 of Cu and/or Fe to X 2 O 3 of the framework structure may range anywhere from 0.05 to 10, wherein preferably the molar ratio ranges from 0.1 to 7, more preferably from 0.5 to 5, more preferably from 1 to 3.5, and more preferably from 1.5 to 3.
  • the molar ratio (Cu and/or Fe) : X 2 O 3 of Cu and/or Fe to X 2 O 3 of the framework structure ranges from 1.8 to 2.8.
  • the copper and/or iron containing zeolitic material may com-prise one or more of any zeolites having a CHA framework structure, provided that said frame-work structure comprises SiO 2 and X 2 O 3 .
  • the copper and/or iron containing zeolitic material comprises one or more zeolites selected from the group consisting of (Ni (deta) 2 ) -UT-6, Chabazite,
  • the present invention further relates to a method for the treatment of NO x by selective catalytic reduction (SCR) comprising:
  • step (b) contacting a gas stream comprising NOx with the catalyst provided in step (a) .
  • the gas stream treated by contacting with the catalyst in (b) comprises one or more reducing agents for selective catalytic reduction of NOx.
  • any suitable reducing agent or combination of reducing agents may be em-ployed, provided that they may reduce NOx to nitrogen gas under the catalytic conditions pro- vided by the inventive method.
  • urea and/or ammonia is comprised among the reducing agents used, wherein more preferably urea and/or ammonia is employed as the reducing agent in the inventive method, preferably ammonia.
  • the gas stream further comprises one or more reducing agents, the one or more reducing agents preferably comprising urea and/or ammonia, preferably ammonia.
  • the gas stream com-prises a NO x containing waste gas stream from an internal combustion engine, preferably from an internal combustion engine which operates under lean-burn conditions, and more preferably from a lean-burn gasoline engine or from a diesel engine.
  • the gas stream comprises one or more NOx containing waste gases from one or more industrial processes, wherein more pre-ferably the NOx containing waste gas stream comprises one or more waste gas streams ob-tained in processes for producing adipic acid, nitric acid, hydroxylamine derivatives, caprolac-tame, glyoxal, methyl-glyoxal, glyoxylic acid or in processes for burning nitrogeneous materials, including mixtures of waste gas streams from two or more of said processes.
  • the present invention also relates to the use of the inventive copper and/or iron contain-ing zeolitic material having a CHA framework structure according to any of the particular and preferred embodiments of the present invention, in particular in the field of catalysis and/or in the treatment of exhaust gas, wherein said exhaust gas treatment comprises industrial and au-tomotive exhaust gas treatment.
  • inventive copper and/or iron containing zeolitic material having a CHA framework structure is used as a catalyst for the selective catalytic reduction of NOx, and preferably in the treatment of NOx containing exhaust gas by SCR, wherein more preferably the zeolitic material is used in the treatment of industrial or automotive exhaust gas.
  • inventive copper and/or iron containing zeolitic material having a CHA framework structure according to any of the particular and preferred embodiments defined in the present application is used in the treatment of automotive exhaust gas.
  • Y is a tetravalent element
  • X is a trivalent element
  • Z is a pentavalent ele-ment
  • the ion exchanged zeolitic material obtained in (3) contains from 3.8 to 12 wt. -%of Cu and/or Fe calculated as the respective element and based on 100 wt-%of YO 2 con-tained in the zeolitic material having a CHA framework structure.
  • the metal ion exchanged zeolitic material obtained in (3) contains from 4.5 to 10 wt. -%of Cu and/or Fe calculated as the respective element and based on 100 wt-%of YO 2 contained in the zeolitic material having a CHA framework structure, preferably from 5.2 to 9.5 wt. -%, more preferably from 5.5 to 9 wt. -%, more pre-ferably from 6 to 8.5 wt. -%, more preferably from 6.5 to 8 wt. -%, and more preferably from 7 to 7.5 wt. -%.
  • the seed crystals then have a YO 2 : X 2 O 3 molar ratio of 5 or greater than 5.
  • the mixture prepared in (1) comprises one or more alkali metals M, wherein the one or more alkali metals M are preferably se-lected from the group consisting of Li, Na, K, and combinations of two or more thereof, wherein more preferably the one or more alkali metals are Li and/or Na, and preferably Na.
  • Y provided in (1) in the one or more sources for YO 2 are, independently from one another, selected from the group consisting of Si, Sn, Ti, Zr, Ge, and mixtures of two or more thereof, Y preferably being Si.
  • the one or more sources for YO 2 comprises one or more silicates, preferably one or more alkali metal silicates, wherein the alkali metal is preferably selected from the group consisting of Li, Na, K, and combinations of two or more thereof, wherein more preferably the alkali metal is Na and/or K, and wherein even more preferably the alkali metal is Na.
  • the mixture prepared in (1) preferably further comprises silica in addition to the one or more silicates, preferably one or more silica hy-drosols and/or one or more colloidal silicas, and even more preferably one or more col-loidal silicas in addition to the one or more silicates.
  • X provided in (1) in the one or more sources for X 2 O 3 are, independently from one another, selected from the group consisting of Al, B, In, Ga, and mixtures of two or more thereof, X preferably being Al and/or B, and more preferably being Al.
  • the one or more sources for X 2 O 3 comprises one or more aluminate salts, preferably on or more alkali metal aluminates, wherein the alkali metal is preferably selected from the group consisting of Li, Na, K, and combinations of two or more thereof, wherein more preferably the alkali metal is Na and/or K, and wherein even more preferably the alkali metal is Na.
  • Z in the one or more sources for Z 2 O 5 optionally further provided in (1) are, inde-pendently from one another, selected from the group consisting of P, As, Sb, Bi, V, Nb, Ta, and combinations of two or more thereof, preferably from the group consisting of P, As, V, and combinations of two or more thereof, wherein more preferably Z comprises P or As, preferably P, and wherein even more preferably Z is P.
  • the one or more sources for Z 2 O 5 comprises one or more phosphates and/or one or more oxides and/or one or more acids of phosphorous, preferably one or more acids of phosphorous, more preferably phosphor-ic acid, and wherein even more preferably the source for Z 2 O 5 is phosphoric acid.
  • the seed crystals having a CHA framework structure comprise one or more zeolites selected from the group consisting of (Ni (deta) 2 ) -UT-6, Chabazite,
  • the seed crystals having a CHA framework structure com-prise Na-Chabazite and/or SAPO-34, and preferably Na-Chabazite.
  • steps (2a) and/or (2b) and/or (2c) can be conducted in any order, and
  • one or more of said steps is preferably repeated one or more times.
  • steps (3a. i) and/or (3a. ii) and/or (3a. iii) can be conducted in any order, and
  • one or more of said steps is preferably repeated one or more times.
  • steps (3c. i) and/or (3c. ii) and/or (3c. iii) can be conducted in any order, and
  • one or more of said steps is preferably repeated one or more times.
  • said at least one ionic non-framework element is preferably one or more alkali metals, more preferably Na and/or K, and more preferably Na.
  • a synthetic copper and/or iron containing zeolitic material having a CHA framework struc-ture obtainable and/or obtained according to the process of any of embodiments 1 to 34.
  • a synthetic copper and/or iron containing zeolitic material having a CHA framework struc-ture optionally obtainable and/or obtained according to the process of any of embodi-ments 1 to 34, wherein the CHA framework structure comprises SiO 2 , X 2 O 3 , and optionally comprises Z 2 O 5 , wherein X is a trivalent element, and Z is a pentavalent element,
  • the zeolitic material contains from 3.8 to 12 wt. -%of Cu and/or Fe calculated as the respective element and based on 100 wt-%of SiO 2 contained in the zeolitic material having a CHA framework structure, and
  • the 29 Si MAS NMR of the zeolitic material comprises:
  • a third peak (P3) in the range of from -107.5 to -111 ppm, preferably of from -108 to -110.5 ppm, more preferably of from -108.5 to -110 ppm, more preferably of from -108.8 to -109.5 ppm, more preferably of from -109 to -109.4 ppm, and even more preferably of from -109.1 to -109.3 ppm;
  • the integration of the first, second, and third peaks in the 29 Si MAS NMR of the zeolitic material offers a ratio of the integration values P1 : P2 : P3 ranging from (0.35 –0.7) : 1 : (0.1 –1.6) , preferably from (0.4 –0.65) : 1 : (0.15 –1.3) , more preferably from (0.42 –0.62) : 1 : (0.2 –1) , more preferably from (0.45 –0.6) : 1 : (0.3 –0.7) , more prefer-ably from (0.48 –0.58) : 1 : (0.35 –0.5) , more preferably from (0.5 –0.56) : 1 : (0.4 –0.45) , and even more preferably from (0.52 –0.54) : 1 : (0.42 –0.44) .
  • zeolitic material of embodiment 36 wherein the zeolitic material contains from 4.5 to 10 wt. -%of Cu and/or Fe calculated as the respective element and based on 100 wt-%of SiO 2 contained in the zeolitic material having a CHA framework structure, preferably from 5.2 to 9.5 wt. -%, more preferably from 5.5 to 9 wt. -%, more preferably from 6 to 8.5 wt. -%, more preferably from 6.5 to 8 wt. -%, and more preferably from 7 to 7.5 wt. -%.
  • zeolitic material of embodiment 36 or 37 wherein X is selected from the group con-sisting of Al, B, In, Ga, and mixtures of two or more thereof, X preferably being Al and/or B, and more preferably being Al.
  • zeolitic material of any of embodiments 36 to 40 wherein Z is selected from the group consisting of P, As, Sb, Bi, V, Nb, Ta, and combinations of two or more thereof, preferably from the group consisting of P, As, V, and combinations of two or more thereof, wherein more preferably Z comprises P or As, preferably P, and wherein even more preferably Z is P.
  • the zeolitic material of embodiment 44 wherein the molar ratio (Cu and/or Fe) : X 2 O 3 of Cu and/or Fe to X 2 O 3 of the framework structure ranges from 0.05 to 10, preferably from 0.1 to 7, more preferably from 0.5 to 5, more preferably from 1 to 3.5, more preferably from 1.5 to 3, and even more preferably from 1.8 to 2.8.
  • zeolitic material of any of embodiments 36 to 45 wherein the zeolitic material com-prises one or more zeolites selected from the group consisting of (Ni (deta) 2 ) -UT-6, Cha-bazite,
  • Chabazite preferably from the group consisting of Chabazite,
  • Chabazite More preferably from the group consisting of Chabazite,
  • the seed crystals having a CHA framework structure com-prise Na-Chabazite and/or SAPO-34, and preferably Na-Chabazite.
  • the gas stream further comprises one or more reducing agents, the one or more reducing agents preferably comprising urea and/or ammonia, preferably ammonia.
  • the gas stream comprises one or more NO x containing waste gases, preferably one or more NO x containing waste gases from one or more industrial processes, wherein more preferably the NO x containing waste gas stream comprises one or more waste gas streams obtained in processes for producing adipic acid, nitric acid, hydroxylamine derivatives, caprolactame, glyoxal, methyl-glyoxal, glyoxylic acid or in processes for burning nitrogeneous materials, in-cluding mixtures of waste gas streams from two or more of said processes.
  • gas stream comprises a NO x containing waste gas stream from an internal combustion engine, preferably from an internal combustion engine which operates under lean-burn conditions, and more preferably from a lean-burn gasoline engine or from a diesel engine.
  • a synthetic organotemplate-free zeolitic material having a CHA framework struc-ture according to any of embodiments 35 to 46 as a molecular sieve, as an adsorbent, for ion exchange, as a catalyst and/or as a catalyst support, preferably as a catalyst, more preferably as a catalyst in the selective catalytic reduction (SCR) of NO x , more prefer-ably as a catalyst in the treatment of exhaust gas by SCR, more preferably in the treatment of NO x containing automotive or industrial exhaust gas by SCR, preferably of automotive exhaust gas.
  • SCR selective catalytic reduction
  • X-ray diffraction (XRD) patterns shown in the Figures were respectively measured using Cu K alpha-1 radiation.
  • the diffraction angle 2 theta in ° is shown along the abscissa and the intensities are plotted along the ordinate.
  • Figure 1a shows the X-ray diffraction pattern of the zeolitic material obtained from Refer-ence Example 1.
  • the line pattern of the CHA type framework structure is indicated in the diffractogram.
  • Figures 1b and 2a show the 29 Si MAS NMR spectrum obtained for the zeolitic materials of Ref-erence Examples 1 and 2, respectively.
  • Figures 1c and 2b show the 27 Si MAS NMR spectrum obtained for the zeolitic materials of Ref-erence Examples 1 and 2, respectively.
  • FIG. 3 shows the results from SCR catalytic testing obtained for the zeolitic materials of Example 1 and Comparative Example 1 at different copper loadings.
  • the copper loading in wt. -% (of Cu calculated as the element) of the zeolitic ma-terial for the different samples is shown along the abscissa and the NOx conver-sion rate in %is plotted along the ordinate.
  • Figure 4 shows the results from SCR catalytic testing obtained for the zeolitic materials of Example 1 and Comparative Example 1 at different copper loadings after aging for 5 h at 750°C.
  • the copper loading in wt. -% (of Cu calculated as the element) of the zeolitic material for the different samples is shown along the abscissa and the NOx conversion rate in %is plotted along the ordinate.
  • the re-sults for the aged samples from Example 1 tested at 200°C are indicated by “ ⁇ ”
  • the aged samples from Comparative Example 1 tested at 200°C are indicated by “ ⁇ ”
  • the aged samples from Example 1 tested at 575°C are indicated by “ ⁇ ”
  • the aged samples from Comparative Example 1 tested at 575°C are indicated by “X” .
  • reaction mixture is then transferred into a static autoclave and is heated for 60 h to 120°C. Afterwards the dispersion is cooled down and the solid is separated from the supernatant by filtration and subsequent wash-ing with H 2 O (DI) until a conductivity of 200 ⁇ S is reached. In order to fully remove residual H 2 O, the sample was dried for 16 h at 120°C in a static oven under air. 27 kg of a white powder were obtained.
  • DI H 2 O
  • the product reveals a zeolitic material having CHA framework structure.
  • the 29 Si MAS NMR of the crystalline product obtained from the synthetic procedure is shown.
  • three major peaks are observed at -97.6 ppm (P1) , -103.3 ppm (P2) , and -109.2 ppm (P3) , respectively, wherein the relative in-stensity of the peaks afford a P1 : P2 : P3 ratio of 0.268 : 0.515 : 0.216.
  • the signal at -109 ppm of the 29 Si MAS NMR corresponds to Q4 structures, wherein the respective signals at -103 and -98 ppm are attributed to the Q3 or to Q4 structures.
  • reaction mixture is stirred for 30 min before it is placed into an autoclave, which is heated to 170°C for 20 hours.
  • the resulting dispersion was adjusted by means of a 10wt-%HNO 3 solution in H 2 O to a pH-value of 7.
  • the resulting solid was filtered and washed with H 2 O until a con-ductivity of below 200 ⁇ S is reached.
  • the solid was first dried at 120°C for 10h and then calcined under air at 600°C for 6h.
  • the 29 Si MAS NMR of the crystalline product obtained from the synthetic procedure is shown.
  • three major peaks are observed at -98.8 ppm (P1) , -104.1 ppm (P2) , and -109.9 ppm (P3) , respectively, wherein the relative in-stensity of the peaks afford a P1 : P2 : P3 ratio of 0.137 : 0.412 : 0.442.
  • the signal at -110 ppm of the 29 Si MAS NMR corresponds to Q4 structures, wherein the respective signals at -104 and -99 ppm are attributed to the Q3 or to Q4 structures.
  • Example 1 Loading of Reference Example 1 with copper
  • Respective samples of the H-form as obtained after calcination were then loaded via incipient wetness impregnation with various Cu (NO 3 ) 2 solutions for obtaining copper loadings ranging from 1.0 wt-%to 7.5 wt-%Cu calculated as the element.
  • the impregnated powders were placed in sealed beakers for 20 hours at 50°C. Afterwards, the materials were calcined at 5h for 450°Cunder air.
  • Comparative Example 1 Loading of Reference Example 2 with copper
  • Example 1 The procedure of Example 1 was repeated with Reference Example 2 for affording a copper loaded comparative example displaying a copper loading ranging from 1.0 wt-%to 7.5 wt-%Cu calculated as the element.
  • Example 1 and Comparative Example 1 were re-spectively dispersed in H 2 O in which 5 wt-%of Zr (acetate) 2 based on the amount of zeolite is added.
  • the slurrys were then dried under stirring and calcined afterwards at 600°C for 1 hour under air.
  • the obtained solids were crushed and sieved to a particle size of 250 –500 ⁇ m for catalytic testing.
  • the respective samples were subsequently tested under selective catalytic reduction conditions relative to their NOx conversion capacity. To this effect the samples were contacted at 200°Cand 575°C with a gas stream containing 500 ppm nitrogen oxide, 500 ppm ammonia, 5 volume percent water, 10 volume percent oxygen (as air) and balance nitrogen at a weight hourly space velocity (WHSV) of 80,000 h -1 . The samples were then aged at 750°C for 5 hours in an atmos-phere containing 10 volume percent of water, and then tested anew. The results of said testing are displayed in Figures 3 and 4.
PCT/CN2017/087035 2016-06-08 2017-06-02 Copper-promoted zeolitic materials of the cha framework structure from organotemplate-free synthesis and use thereof in the selective catalytic reduction of nox WO2017211236A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BR112018073870-0A BR112018073870B1 (pt) 2016-06-08 2017-06-02 Processo sintético isento de modelos orgânicos, materiais zeolíticos contendo cobre e/ ou ferro sintético, método para o tratamento de nox por redução catalítica seletiva e uso de um material zeolítico
EP17809675.6A EP3481549A4 (en) 2016-06-08 2017-06-02 ZEOLITIC MATERIALS ACTIVATED BY COPPER OF THE CHA FRAME STRUCTURE DERIVED FROM SYNTHESIS WITHOUT ORGANIC MODEL, AND THEIR USE IN SELECTIVE CATALYTIC NOx REDUCTION
CA3026817A CA3026817C (en) 2016-06-08 2017-06-02 Copper-promoted zeolitic materials of the cha framework structure from organotemplate-free synthesis and use thereof in the selective catalytic reduction of nox
CN201780034580.8A CN109219481A (zh) 2016-06-08 2017-06-02 来自无有机模板的合成的CHA骨架结构的铜助催化沸石材料及其在NOx的选择性催化还原中的用途

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GB2580521A (en) * 2018-11-30 2020-07-22 Johnson Matthey Plc Enhanced introduction of extra-frame work metal into aluminosilicate zeolites
US11091425B2 (en) 2016-11-30 2021-08-17 Basf Se Process for the conversion of ethylene glycol to ethylenediamine employing a zeolite catalyst
US11104637B2 (en) 2016-11-30 2021-08-31 Basf Se Process for the conversion of monoethanolamine to ethylenediamine employing a copper-modified zeolite of the MOR framework structure
RU2778875C1 (ru) * 2018-11-30 2022-08-26 Джонсон Мэттей Паблик Лимитед Компани Улучшенное введение внекаркасного металла в алюминосиликатные цеолиты
US11529618B2 (en) 2016-11-28 2022-12-20 Basf Se Catalyst composite comprising an alkaline earth metal containing CHA zeolite and use thereof in a process for the conversion of oxygenates to olefins

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US11529618B2 (en) 2016-11-28 2022-12-20 Basf Se Catalyst composite comprising an alkaline earth metal containing CHA zeolite and use thereof in a process for the conversion of oxygenates to olefins
US11091425B2 (en) 2016-11-30 2021-08-17 Basf Se Process for the conversion of ethylene glycol to ethylenediamine employing a zeolite catalyst
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GB2580521A (en) * 2018-11-30 2020-07-22 Johnson Matthey Plc Enhanced introduction of extra-frame work metal into aluminosilicate zeolites
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