WO2020164545A1 - Matériau zéolithique contenant de l'aluminium et du gallium et son utilisation en scr - Google Patents

Matériau zéolithique contenant de l'aluminium et du gallium et son utilisation en scr Download PDF

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WO2020164545A1
WO2020164545A1 PCT/CN2020/075095 CN2020075095W WO2020164545A1 WO 2020164545 A1 WO2020164545 A1 WO 2020164545A1 CN 2020075095 W CN2020075095 W CN 2020075095W WO 2020164545 A1 WO2020164545 A1 WO 2020164545A1
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zeolitic material
framework structure
sio
range
alkyl
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PCT/CN2020/075095
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Andrei-Nicolae PARVULESCU
Ulrich Mueller
Dirk De Vos
Trees De Baerdemaeker
Patrick Tomkins
Bernd Marler
Weiping Zhang
Toshiyuki Yokoi
Feng-Shou Xiao
Ute KOLB
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Basf Se
Basf (China) Company Limited
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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
    • B01J29/04—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
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/182—Phosphorus; Compounds thereof with silicon
    • 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
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J29/088—Y-type faujasite
    • 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
    • B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • 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
    • B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J29/7065—CHA-type, e.g. Chabazite, LZ-218
    • 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
    • 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
    • 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
    • B01D53/02—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 by adsorption, e.g. preparative gas chromatography
    • 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
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties

Definitions

  • the present invention relates to a zeolitic material comprising SiO 2 , Al 2 O 3 and Ga 2 O 3 in its framework structure, as well as to a method for its production. Furthermore, the present inven-tion relates to a zeolitic material comprising SiO 2 , Al 2 O 3 and Ga 2 O 3 in its framework structure and comprising one or more metal cations M at the ion exchange sites of the framework struc-ture.
  • the present invention relates to a zeolitic material as obtained or obtainable according to the inventive method for the production of a zeolitic material, as well as to a process for the treatment of NO x using the inventive zeolitic materials, to an apparatus for the treatment of a gas stream containing NO x , the apparatus containing the inventive zeolitic mate-rials, and to the use of the zeolitic materials according to the present invention.
  • NH 3 -SCR ammonia
  • N 2 O is typically formed as a side product during SCR and catalysts that minimize this reaction are essential.
  • a broad range of catalysts have been tested for this reaction, for example manganese oxides, titania supported vanadia or transition metal containing zeolites.
  • the VO x /TiO 2 type systems have been thorough-ly investigated and are produced on a commercial scale, mainly for stationary emission treat-ment.
  • Transition metal containing zeolites have emerged as the most prom-ising for application in automotive exhaust treatment.
  • a major challenge for these automotive applications remains improving the low temperature activity, which is of particular importance during the cold start-up of the vehicle.
  • iron zeolites are more active for high tempera-ture application and copper zeolites are more active for low temperature application. Poor per-formance at low temperature can be caused by a simple Arrhenius type relationship between rates and temperature at the active site.
  • the amounts of adsorbed ammonia and water change drastically during start-up. For instance, adsorbed water can be problematic for reactivity at low temperatures due to competitive adsorption.
  • Other key challenges for mobile applications are the hydrothermal stability of the catalyst and the selectivity of the reaction, es-pecially with regard to N 2 O formation.
  • Cu-ZSM-5 was identified as a promising SCR catalyst, although many other catalysts were tested (Cu-*BEA, Cu-FAU, Cu-MOR and others) . Later, small pore zeolites, especially Cu-SSZ-13 (CHA) and SSZ-39 (AEI) were found to have remarkable activity and stability. Cu-SSZ-13 is highly resistant against dealumination, which allows for stability un-der the harsh conditions of SCR, during which high temperatures are reached in the presence of water and where repeated cycles of dehydration and rehydration during start-up and cool-down occur.
  • zeolite catalysts for instance, Cu-*BEA and Cu-MFI, loose (mostly low- temperature) activity and selectivity through dealumination, ensuing structural degradation, and through the formation of CuO x and Cu-aluminate species.
  • Cu-SSZ-13 the reason for its high stability, as the pores are too narrow to allow extensive removal of Al species from the zeolite and the structure remains stable even when a large part of the Al is no longer in the framework itself.
  • Cu-SSZ-13 exhibits stable, highly dispersed Cu species, which is crucial for optimal SCR performance.
  • the Si/Al ratio plays an important role in the performance of Cu-SSZ-13. On the one hand, it has been suggested that the Si/Al ratio needs to be low enough to allow introduction of suffi-cient copper to have a reasonable activity at low temperatures. Further, the location, speciation and stability of that copper also depend on the Si/Al ratio and the copper loading. Additionally, both the Si/Al and Cu/Al affect the number and strength of residual acid sites that can serve as a reservoir for ammonia species.
  • Fickel D. W. et al. Appl. Catal. B Environ. 2011, 102, 441-448 discuss differences be-tween Al-SSZ-13 and SSZ-13 isomorphously substituted with Ga, wherein Ga-SSZ-13 was found to be unstable after steaming.
  • table 1 discloses the characteristics of the obtained products, where samples 6, 7, 8, and 9 show a Si to Ga molar ratio of 49, 89, 139, and 262, respectively.
  • table 4 the characteristics of the Cu-loaded samples are dis-closed, where the respective samples show a Si to Ga molar ratio of 37, 68, 110, and 200.
  • JP 2018 083745 discloses a crystalline aluminosilicate for the use in selective catalytic reduc-tion.
  • the crystalline aluminosilicate has a CHA framework structure and is characterized by fur-ther comprising gallium and having a molar ratio of silica to gallium oxide of 75 or more.
  • the crystaline aluminosilicate may further contain copper and/or iron. It has been found that a cata-lyst comprising said crystalline aluminosilicate is useful for nitrogen oxide reduction and ammo-nia conversion.
  • inventive zeolitic materials comprising gallium and aluminum as framework element, a far higher conversion of NO is achieved as observed as for conventional SCR catalysts having gallium but essentially no aluminum as framework ele-ment, especially after hydrothermal aging thereof, wherein furthermore the inventive zeolitic materials display a far lower N 2 O make.
  • the present invention relates to a zeolitic material comprising SiO 2 , Al 2 O 3 and Ga 2 O 3 in its framework structure, wherein the SiO 2 : Ga 2 O 3 molar ratio of the framework structure of the zeolitic material is equal to or less than 69: 1, and wherein the SiO 2 : Al 2 O 3 molar ratio of the framework structure of the zeolitic material is equal to or less than 750: 1.
  • the present invention relates to a process for the preparation of a zeolitic ma-terial comprising SiO 2 , Ga 2 O 3 , and Al 2 O 3 in its framework structure, preferably of a zeolitic ma-terial according to any one of the embodiments disclosed herein, the process comprising
  • the molar ratio Si: Ga of the silicon to the gallium, calculated as the element, respective- ly, in the mixture prepared according to (1) is in the range of from 1: 1 to 34.5: 1, and wherein the molar ratio Si: Al of the silicon to the aluminum, calculated as the element, respec-tively, in the mixture prepared according to (1) is equal to or less than 375: 1.
  • the present invention relates to a zeolitic material obtainable from the process of any one of the embodiments disclosed herein.
  • the present invention relates to a process for the treatment of NO x by selective cata-lytic reduction comprising
  • step (B) contacting the gas stream provided in step (A) with a zeolitic material according to any one of the embodiments disclosed herein.
  • the present invention relates to an apparatus for the treatment of a gas stream con-taining NO x , the apparatus comprising a catalyst bed provided in fluid contact with the gas stream to be treated, wherein the catalyst bed comprises a zeolitic material according to any one of the embodiments disclosed herein.
  • the present invention relates to a use of a zeolitic material according to any one of the embodiments disclosed herein as a molecular sieve, as an adsorbent, for ion-exchange, as a catalyst or a precursor thereof, and/or as a catalyst support or a precursor thereof, more pre-ferably as a catalyst or a precursor thereof and/or as a catalyst support or a precursor thereof, more preferably as a catalyst or a precursor thereof, more preferably as a catalyst for the selec-tive catalytic reduction (SCR) of nitrogen oxides NO x ; for the storage and/or adsorption of CO 2 ; for the oxidation of NH 3 , in particular for the oxidation of NH 3 slip in diesel systems; for the de-composition of N 2 O; as an additive in fluid catalytic cracking (FCC) processes; and/or as a cata-lyst in organic conversion reactions, preferably in the conversion of alcohols to olefins,
  • the SiO 2 : Ga 2 O 3 molar ratio of the framework structure of the zeolitic material is in the range of from 1: 1 to 69: 1, more preferably in the range of from 10: 1 to 69: 1, more preferably in the range of from 30: 1 to 68: 1, more preferably in the range of from 40: 1 to 68: 1, more preferably in the range of from 48: 1 to 67: 1, more preferably in the range of from 55: 1 to 67: 1, more preferably in the range of from 60: 1 to 67: 1, more prefera-bly in the range of from 63: 1 to 67: 1, and more preferably in the range of from 65: 1 to 67: 1.
  • the SiO 2 : Al 2 O 3 molar ratio of the framework structure of the zeolitic material is in the range of from 1: 1 to 500: 1, more preferably of from 5: 1 to 250: 1, more prefera-bly of from 10: 1 to 150: 1, more preferably of from 15: 1 to 125: 1, more preferably of from 20: 1 to 80:1, more preferably of from 30: 1 to 60: 1, more preferably of from 35: 1 to 55: 1, more prefera-bly of from 40: 1 to 48: 1, and more preferably of from 42: 1 to 46: 1.
  • the SiO 2 : (Al 2 O 3 +Ga 2 O 3 ) molar ratio of the framework structure of the zeolitic material is in the range of from 1: 1 to 75: 1, more preferably of from 5: 1 to 50: 1, more preferably of from 10: 1 to 43: 1, more preferably of from 15: 1 to 38: 1, more preferably of from 20:1 to 33: 1, more preferably of from 23: 1 to 29: 1, and more preferably of from 25: 1 to 28: 1.
  • the zeolitic materi-al has a framework structure type selected from the group consisting of AEI, BEA, BEC, CHA, EUO, FAU, FER, GIS, HEU, ITH, ITW, LEV, MEL, MFI, MOR, MTN, MWW, AFT, AFV, AFX, AVL, EMT, GME, KFI, LEV, LTN, SFW, and TON, including mixed structures of two or more thereof, more preferably from the group consisting of AEI, AFT, AFV, AFX, AVL, EMT, GIS, GME, KFI, LEV, LTN, MTN, SFW, BEA, CHA, FAU, FER, MFI, MOR, and MWW, including mixed structures of two or more thereof, more preferably from the group consisting of AEI, AFT, AFV, AFX, AVL, EMT, GIS, GME, KFI, LEV, LTN, MTN, S
  • 95 or more weight-%of the framework of the zeolitic material consists of Si, Al, Ga, O, and H, calculated based on the total weight of the framework of the zeolitic material, more preferably 95 to 100 weight-%, more preferably 97 to 100 weight-%, more preferably 99 to 100 weight-%.
  • the zeolitic material may comprise one or more further elements of the periodic system of elements. It is preferred that the zeolitic material comprises one or more metal cations M se-lected from the group consisting of Sr, Zr, Cr, Mo, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, Sc, and mixtures of two or more thereof, more preferably selected from the group consisting of Sr, Zr, Cr, Mo, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, and mixtures of two or more thereof, more preferably from the group consisting of Sr, Cr, Mo, Fe, Co, Ni, Cu, Zn, Ag, and mixtures of two or more thereof, more preferably from the group consisting of Cr, Mo, Fe, Ni,
  • the zeolitic material comprises the one or more metal cations M in an amount in the range of from 0.01 to 5 weight-%based on 100 weight-%of Si in the zeolitic material calculated as SiO 2 , more preferably in the range of from 0.05 to 4 weight-%, more preferably in the range of from 0.1 to 3 weight-%, more preferably in the range of from 0.2 to 2.5 weight-%, more preferably in the range of from 0.4 to 2 weight-%, more pre-ferably in the range of from 0.6 to 1.5 weight-%, and more preferably in the range of from 0.8 to 1.2 weight-%.
  • the zeolitic material comprises one or more metal cations as disclosed herein, it is preferred that 95 or more weight-%of the zeolitic material consists of Si, Al, Ga, O, H, and the one or more metal cations M, calculated based on the total weight of the zeolitic material, more preferably 95 to 100 weight-%, more preferably 97 to 100 weight-%, more preferably 99 to 100 weight-%.
  • the zeolitic material may comprise one or more further elements of the pe-riodic system of elements. It is preferred that the zeolitic material further contains one or more of Li + , Na + , K + , Mg 2+ , Ca 2+ , more preferably one or more of K + and Na + , more preferably Na + , at the ion-exchange sites of the framework structure.
  • the zeolitic material may comprise one or more further elements of the pe-riodic system of elements. It is preferred that the zeolitic material further comprises phosphor-ous, more preferably in an amount in the range of from 0.1 to 10 weight-%, more preferably in the range of from 0.5 to 7.0 weight-%, more preferably in the range of from 1.0 to 5.0 weight-%, more preferably in the range of from 1.1 to 2.0 weight-%.
  • the mean particle size D50 by volume of the zeolitic material as determined accord-ing to ISO 13320: 2009 is of at least 0.3 micrometer, and is more preferably in the range of from 0.3 to 6.0 micrometer, more preferably in the range of from 1.5 to 4.5 micrometer, and more preferably in the range of from 2.5 to 3.6 micrometer.
  • the mean particle size of the primary crystals of the zeolitic material as determined by SEM is in the range of from 100 to 3000 nanometer, more preferably in the range of from 110 to 1000 nanometer, more preferably in the range of from 120 to 500 nanome-ter, and more preferably in the range of from 130 to 250 nanometer.
  • the zeolitic material has a crystal size of at least 0.5 micrometer, more preferably in the range of from 0.5 to 1.5 micrometer, more preferably in the range of from 0.6 to 1.0 micrometer, more preferably in the range of from 0.6 to 0.8 micrometer.
  • the zeolitic material has a CHA-type frame-work structure. More particular, it is preferred that the zeolitic material has a CHA-type frame-work structure, wherein more preferably the zeolitic material having a CHA-type framework structure is selected from the group consisting of Willhendersonite, ZYT-6, SAPO-47, Na-Chabazite, Chabazite, LZ-218, Linde D, Linde R, SAPO-34, ZK-14, K-Chabazite, MeAPSO-47, Phi, DAF-5, UiO-21,
  • the zeolitic material has an AEI-type framework structure. More particular, it is preferred that the zeolitic material has an AEI-type framework structure, wherein more preferably the zeolitic material having an AEI-type frame-work structure is selected from the group consisting of SSZ-39, SAPO-18, SIZ-8, including mix-tures of two or more thereof, wherein more preferably the zeolitic material comprises SSZ-39, and wherein more preferably the zeolitic material is SSZ-39.
  • the zeolitic material has an AEI-type framework structure
  • it is preferred that the zeolitic material has a crystal size in the range of from 0.1 to 5 micrometer, more preferably in the range of from 0.5 to 2.5 micrometer.
  • the present invention relates to a process for the preparation of a zeolitic material comprising SiO 2 , Ga 2 O 3 , and Al 2 O 3 in its framework structure, preferably of a zeolitic material according to any one of the embodiments disclosed herein, the process comprising
  • the molar ratio Si: Ga of the silicon to the gallium, calculated as the element, respective-ly, in the mixture prepared according to (1) is in the range of from 1: 1 to 34.5: 1, and wherein the molar ratio Si: Al of the silicon to the aluminum, calculated as the element, respec-tively, in the mixture prepared according to (1) is equal to or less than 375: 1.
  • the molar ratio of Si: Ga in the mixture prepared according to (1) is in the range of from 1: 1 to 110: 1, more preferably in the range of from 1: 1 to 32: 1, preferably in the range of from 2: 1 to 30: 1, more preferably in the range of from 3: 1 to 27: 1, more preferably of from 5: 1 to 25: 1, more preferably of from 7: 1 to 25: 1, more preferably of from 9: 1 to 23: 1, more preferably of from 11 to 23: 1, more preferably of from 13: 1 to 22: 1, preferably of from 15: 1 to 22:1, more preferably of from 17: 1 to 21: 1, more preferably of from 19: 1 to 21: 1.
  • the molar ratio of Si: Al in the mixture prepared according to (1) is in the range of from 1: 1 to 375: 1, more preferably of from 5: 1 to 250: 1, more preferably of from
  • the molar ratio SiO 2 : organotemplate of the one or more sources for SiO 2 to the one or more organotemplates in the mixture prepared in (1) or (1a) is in the range of from 1: 20 to 100: 1, more preferably of from 1: 10 to 50: 1, more preferably of from 1: 6 to 50: 1, more preferably of from 1: 1 to 50: 1, preferably of from 2: 1 to 20: 1, more preferably of from 3: 1 to 10: 1, more preferably of from 4: 1 to 7: 1, and more preferably of from 4.5: 1 to 5.5: 1.
  • the one or more organotemplates comprise one or more tetraalkylammonium cation R 1 R 2 R 3 R 4 N + -containing compounds, wherein R 1 , R 2 , and R 3 inde-pendently from one another stand for alkyl, and wherein R 4 stands for adamantyl and/or benzyl, preferably for 1-adamantyl.
  • R 1 , R 2 , R 3 , and R 4 of the one or more organotemplates no particular restriction applies. It is preferred that R 1 , R 2 , and R 3 independently from one another stand for optionally branched (C 1 -C 6 ) alkyl, more preferably (C 1 -C 5 ) alkyl, more preferably (C 1 -C 4 ) alkyl, more prefera-bly (C 1 -C 3 ) alkyl, more preferably for methyl or ethyl, and more preferably for methyl. Further, it is preferred that R 4 stands for adamantyl and/or benzyl, more preferably for adamantyl, more pre-ferably for 1-adamantyl.
  • the one or more tetraalkylammonium cation R 1 R 2 R 3 R 4 N + -containing compounds comprise one or more N, N, N-tri (C 1 -C 4 ) alkyl-1-adamantammonium com-pounds, more preferably one or more N, N, N-tri (C 1 -C 3 ) alkyl-1-adamantammonium compounds, more preferably one or more N, N, N-tri (C 1 -C 2 ) alkyl-1-adamantammonium compounds, more preferably one or more N, N, N-tri (C 1 -C 2 ) alkyl-1-adamantammonium and/or one or more N, N, N-tri (C 1 -C 2 ) alkyl-1-adamantammonium compounds, more preferably one or more compounds se-lected from N, N, N-triethyl-1-adamantammonium, N, N-diethyl-N
  • the one or more organotemplates comprises one or more tetraalkylammonium cation R 1 R 2 R 3 R 4 N + -containing compounds, wherein R 1 , R 2 , and R 3 independently from one another stand for alkyl, and wherein R 4 stands for cycloalkyl.
  • the one or more organotemplates comprises one or more tetraalkylammo-nium cation R 1 R 2 R 3 R 4 N + -containing compounds, wherein R 1 , R 2 , and R 3 independently from one another stand for alkyl, and wherein R 4 stands for cycloalkyl
  • R 1 and R 2 inde-pendently from one another stand for optionally branched (C 1 -C 6 ) alkyl, more preferably (C 1 -C 5 ) alkyl, more preferably (C 1 -C 4 ) alkyl, more preferably (C 1 -C 3 ) alkyl, and more preferably for methyl or ethyl, wherein more preferably R 1 and R 2 independently from one another stand for methyl.
  • the one or more organotemplates comprises one or more tetraalky-lammonium cation R 1 R 2 R 3 R 4 N + -containing compounds, wherein R 1 , R 2 , and R 3 independently from one another stand for alkyl, and wherein R 4 stands for cycloalkyl
  • R 3 stands for optionally branched (C 1 -C 6 ) alkyl, more preferably (C 1 -C 5 ) alkyl, more prefera-bly (C 1 -C 4 ) alkyl, more preferably (C 1 -C 3 ) alkyl, and more preferably for methyl or ethyl, wherein more preferably R 3 stands for ethyl.
  • the one or more organotemplates comprises one or more tetraalky-lammonium cation R 1 R 2 R 3 R 4 N + -containing compounds, wherein R 1 , R 2 , and R 3 independently from one another stand for alkyl, and wherein R 4 stands for cycloalkyl
  • R 4 stands for optionally heterocyclic 5-to 8-membered cycloalkyl, more preferably for 5-to 7-membered cycloalkyl, more preferably for 5-or 6-membered cycloalkyl, wherein more prefer-ably R 4 stands for optionally heterocyclic 6-membered cycloalkyl, and more preferably for cyclo-hexyl.
  • the one or more organotemplates comprises one or more tetraalky-lammonium cation R 1 R 2 R 3 R 4 N + -containing compounds, wherein R 1 , R 2 , and R 3 independently from one another stand for alkyl, and wherein R 4 stands for cycloalkyl
  • the one or more tetraalkylammonium cation R 1 R 2 R 3 R 4 N + -containing compounds comprise one or more N, N, N-tri (C 1 -C 4 ) alkyl- (C 5 -C 7 ) cycloalkylammonium compounds, more preferably one or more N, N, N-tri (C 1 -C 3 ) alkyl- (C 5 -C 6 ) cycloalkylammonium compounds, more preferably one or more N, N, N-tri (C 1 -C 2 ) alkyl- (C 5 -C 6 ) cycloalkylammonium
  • the one or more organotemplates comprises one or more tetraalkylammonium cation R 1 R 2 R 3 R 4 N + -containing compounds, wherein R 1 , R 2 , R 3 and R 4 independently from one another stand for alkyl, and wherein R 3 and R 4 form a common alkyl chain.
  • the one or more organotemplates comprises one or more tetraalkylammo-nium cation R 1 R 2 R 3 R 4 N + -containing compounds, wherein R 1 , R 2 , R 3 and R 4 independently from one another stand for alkyl, and wherein R 3 and R 4 form a common alkyl chain
  • R 1 and R 2 independently from one another stand for optionally branched (C 1 -C 6 ) alkyl, more preferably (C 1 -C 5 ) alkyl, more preferably (C 1 -C 4 ) alkyl, more preferably (C 1 -C 3 ) alkyl, wherein more preferably R 1 and R 2 independently from one another stand for methyl or ethyl, and more pre-ferably for methyl.
  • the one or more organotemplates comprises one or more tetraalky-lammonium cation R 1 R 2 R 3 R 4 N + -containing compounds, wherein R 1 , R 2 , R 3 and R 4 independent-ly from one another stand for alkyl, and wherein R 3 and R 4 form a common alkyl chain
  • R 3 and R 4 form a common (C 4 -C 8 ) alkyl chain, more preferably a common (C 4 -C 7 ) alkyl chain, more preferably a common (C 4 -C 6 ) alkyl chain, wherein more preferably said common alkyl chain is a C 4 or C 5 alkyl chain, and more preferably a C 5 alkyl chain.
  • the one or more organotemplates comprises one or more tetraalky-lammonium cation R 1 R 2 R 3 R 4 N + -containing compounds, wherein R 1 , R 2 , R 3 and R 4 independent-ly from one another stand for alkyl, and wherein R 3 and R 4 form a common alkyl chain
  • the one or more tetraalkylammonium cation R 1 R 2 R 3 R 4 N + -containing com-pounds comprise one or more ammonium compounds selected from the group consisting of N,N-di (C 1 -C 4 ) alkyl-3, 5-di (C 1 -C 4 ) alkylpyrrolidinium compounds, N, N-di (C 1 -C 4 ) alkyl-3, 5-di (C 1 -C 4 ) alkylpiperidinium compounds, N, N-di (C 1 -C 4 ) alkyl-3, 5-d
  • R 1 R 2 R 3 R 4 N + -containing com-pounds comprise one or more ammonium compounds selected from the group consisting of N,N-di (C 1 -C 4 ) alkyl-3, 5-di (C 1 -C 4 ) alkylpyrrolidinium compounds, N, N-di (C 1 -C 4 ) alkyl-3, 5-di (C 1 - C 4 ) alkylpiperidinium compounds, N, N-di (C 1 -C 4 ) alkyl-3, 5-di (C 1 -C 4 ) alkylhexahydroazepinium compounds, N, N-di (C 1 -C 4 ) alkyl-2, 6-di (C 1 -C 4 ) alkylpyrrolidinium compounds, N, N-di (C 1 -C 4 ) alkyl-2,6-di (C 1 -C
  • the one or more organotemplates comprise one or more tetraalkyl-phosphonium cation R 1 R 2 R 3 R 4 P + -containing compounds, wherein R 1 , R 2 , R 3 , and R 4 indepen-dently from one another stand for optionally substituted and/or optionally branched (C 1 -C 6 ) alkyl, more preferably (C 1 -C 5 ) alkyl, more preferably (C 1 -C 4 ) alkyl, more preferably (C 2 -C 3 ) alkyl, and more preferably for optionally substituted methyl or ethyl, wherein more preferably R 1 , R 2 , R 3 , and R 4 stand for optionally substituted ethyl, preferably unsubstituted ethyl.
  • the one or more organotemplates are provided as salts, more preferably as one or more salts selected from the group consisting of halides, sulfate, nitrate, phosphate, acetate, and mixtures of two or more thereof, more preferably from the group con-sisting of bromide, chloride, hydroxide, sulfate, and mixtures of two or more thereof, wherein more preferably the one or more organotemplates are provided as hydroxides and/or bromides, and more preferably as hydroxides.
  • the mixture prepared in (1) comprises seed crystals, wherein the amount of seed crystals comprised in the mixture prepared in (1) is in the range of from 0.1 to 15 weight-%based on 100 weight-%of Si in the mixture calculated as SiO 2 , and more prefera-bly of from 0.5 to 11 weight-%, more preferably of from 0.8 to 8 weight-%, more preferably of from 1.2 to 5 weight-%, more preferably of from 1.5 to 3 weight-%, and more preferably of from 1.8 to 2.5 weight-%.
  • the mixture prepared in (1) comprises seed crystals, wherein the seed crystals comprise one or more zeolitic materials having a framework structure type se-lected from the group consisting of AEI, BEA, BEC, CHA, EUO, FAU, FER, GIS, HEU, ITH, ITW, LEV, MEL, MFI, MOR, MTN, MWW, AFT, AFV, AFX, AVL, EMT, GME, KFI, LEV, LTN, SFW, and TON, including mixed structures of two or more thereof, more preferably from the group consisting of AEI, AFT, AFV, AFX, AVL, EMT, GIS, GME, KFI, LEV, LTN, MTN, SFW, BEA, CHA, FAU, FER, MFI, MOR, and MWW, including mixed structures of two or more thereof, more preferably from the group consisting of AEI, AFT, AFV, AFX, AVL, EMT
  • the mixture prepared in (1) , (1a) , or (1 b) , more preferably in (1a) and (1b) comprises hydroxide salts.
  • the mixtures prepared in (1a) and (1 b) comprise hydroxide salts
  • the molar ratio of OH - in the first mixture prepared in (1a) to OH - in the second mix-ture prepared in (1 b) is in the range of from 0.01: 1 to 100: 1, more preferably of from 0.05: 1 to 20:1, more preferably of from 0.1: 1 to 10: 1, more preferably of from 0.2: 1 to 5: 1, more prefera-bly of from 0.4: 1 to 2.5: 1, more preferably of from 0.6: 1 to 1.7: 1, and more preferably of from 0.8: 1 to 1.25: 1.
  • the mixture prepared in (1) comprises hydroxide salts
  • the molar ratio OH - : organotemplate in the mixture prepared in (1) is in the range of from 0.01: 1 to 100: 1, more preferably of from 0.05: 1 to 20: 1, more preferably of from 0.25: 1 to 10: 1, more pre-ferably of from 0.5: 1 to 5: 1, more preferably of from 0.75: 1 to 2.5: 1, more preferably of from 1.0: 1 to 2.0: 1, and more preferably of from 1.25: 1 to 1.75: 1.
  • the mixture prepared in (1) or (1a) comprises one or more metals selected from the group consisting of alkali metals and alkaline earth metals, more preferably one or more metals selected from the group consisting of Li, Na, K, Rb, Cs, Mg, and Ca, more preferably from the group consisting of Li, Na, and K, wherein more preferably the mixture pre-pared in (1) or (1a) comprises K and/or Na, preferably Na.
  • the mixture prepared in (1) or (1a) comprises one or more metals selected from the group consisting of alkali metals and alkaline earth metals
  • the molar ratio of the one or more metals selected from the group consisting of alkali metals and alkaline earth metals to the one or more organotemplates in the mixture prepared in (1) is in the range of from 0.01: 1 to 100: 1, more preferably of from 0.05: 1 to 20: 1, more preferably of from 0.1: 1 to 10:1, more preferably of from 0.2: 1 to 5: 1, more preferably of from 0.4: 1 to 2.5: 1, more prefera-bly of from 0.6: 1 to 1.7: 1, and more preferably of from 0.8: 1 to 1.25: 1.
  • heating in (2) is conducted for a duration in the range of from 0.5 to 15 d, and more preferably from 1 to 10 d, more preferably from 2 to 8 d, more preferably from 3 to 7 d, more preferably from 3.5 to 6.5 d, more preferably from 4 to 6 d, preferably from 4.5 to 5.5 d.
  • heating in (2) is conducted at a temperature in the range of from 80 to 220 °C, more preferably of from 100 to 200 °C, more preferably of from 120 to 180 °C, more preferably of from 130 to 170 °C, more preferably of from 140 to 160 °C, and more preferably of from 145 to 155 °C.
  • heating in (2) is conducted under autogenous pressure, more pre-ferably under solvothermal conditions, more preferably under hydrothermal conditions, wherein preferably heating in (2) is performed in a pressure tight vessel, preferably in an autoclave.
  • the zeolitic material crystallized in (2) has a framework struc-ture type selected from the group consisting of AEI, BEA, BEC, CHA, EUO, FAU, FER, GIS, HEU, ITH, ITW, LEV, MEL, MFI, MOR, MTN, MWW, AFT, AFV, AFX, AVL, EMT, GME, KFI, LEV, LTN, SFW, and TON, including mixed structures of two or more thereof, more preferably from the group consisting of AEI, AFT, AFV, AFX, AVL, EMT, GIS, GME, KFI, LEV, LTN, MTN, SFW, BEA, CHA, FAU, FER, MFI, MOR, and MWW, including mixed structures of two or more thereof, more preferably from the group consisting of AEI, AFT, AFV, AFX, AVL, EMT, GIS, GME, KFI, LEV,
  • any one of the em-bodiments as disclosed herein further comprises
  • (3) subjecting the zeolitic material obtained in (2) to ion exchange with one or more metal cations M, it is preferred that (3) comprises
  • the zeolitic material obtained in (2) is directly subject to ion exchange with the one or more metal cations M, wherein no ion-exchange step is per-formed prior to ion exchange of the zeolitic material obtained in (2) with the one or more metal cations M.
  • the one or more metal cations M are selected from the group consisting of Sr, Zr, Cr, Mg, Mo, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, Sc, and mixtures of two or more the-reof, more preferably selected from the group consisting of Sr, Zr, Cr, Mg, Mo, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, and mixtures of two or more thereof, more prefera-bly from the group consisting of Sr, Cr, Mo, Fe, Co, Ni, Cu, Zn, Ag, and mixtures of two or more thereof, more preferably from the group consisting of Sr, Cr, Mo, Fe, Co, Ni, Cu, Zn, Ag, and mixtures of two or more thereof
  • the one or more metal cations M are provided as salts, pre-ferably as one or more salts selected from the group consisting of halides, sulfate, nitrate, phosphate, acetate, and mixtures of two or more thereof, more preferably from the group consisting of sulfate, nitrate, acetate, and mixtures of two or more thereof, wherein more preferably the one or more metal cations M used for preparing the mixture according to (1) or (1a) are provided as nitrates and/or acetates, and more preferably as acetates.
  • calcination in (iv) is conducted for a duration in the range of from 0.5 to 15 h, preferably of from 1 to 10 h, more preferably of from 1.5 to 8 h, more preferably of from 2 to 6 h, more preferably of from 2.5 to 5.5 h, more preferably of from 3 to 5 h, and more preferably of from 3.5 to 4.5 h.
  • calcination in (iv) is conducted at a temperature in the range of from 300 to 900 °C, more preferably of from 350 to 800 °C, more preferably of from 400 to 750 °C, more preferably of from 450 to 700 °C, more preferably of from 500 to 650 °C, and more preferably of from 560 to 600 °C.
  • the mixture prepared in (1) comprises seed crystals, wherein the seed crystals comprise one or more zeolitic materials having the framework structure of the zeo-litic material comprising SiO 2 , Ga 2 O 3 and Al 2 O 3 in its framework structure obtained according to the process of any one of the embodiments disclosed herein, wherein more preferably the one or more zeolitic materials of the seed crystals is obtainable and/or obtained according to the process of any one of the embodiments disclosed herein.
  • the seed crystals are prepared according to a process comprising
  • heating in (b) is conducted for a duration in the range of from 0.5 to 15 d, and more preferably from 1 to 10 d, more preferably from 2 to 8 d, more preferably from 3 to 7 d, more preferably from 3.5 to 6.5 d, more preferably from 4 to 6 d, preferably from 4.5 to 5.5 d.
  • heating in (b) is conducted at a temperature in the range of from 80 to 220 °C, more preferably of from 100 to 200 °C, more preferably of from 120 to 190 °C, more preferably of from 130 to 180 °C, more preferably of from 150 to 170 °C, and more preferably of from 155 to 165 °C. It is particularly preferred that heating in (b) is conducted under autogenous pressure, more preferably under solvothermal conditions, more preferably under hydrothermal conditions, wherein preferably heating in (2) is performed in a pressure tight vessel, preferably in an autoclave.
  • the acid employed in (c) is in aqueous solu-tion, wherein the concentration of the acid in the aqueous solution is in the range of from 0.01 to 0.5 mol/l, more preferably of from 0.03 to 0.3 mol/l, more preferably of from 0.05 to 0.2 mol/l, more preferably of from 0.07 to 0.15 mol/l, and more preferably of from 0.09 to 0.11 mol/l.
  • the acid employed in (c) is selected from the group consisting of HCl, HNO 3 , H 3 PO 4 , H 2 SO 4 , H 3 BO 3 , HF, HBr, HClO 4 , and mixtures of two or more thereof, more pre-ferably from the group consisting of HCl, HNO 3 , H 2 SO 4 , HBr, HClO 4 , and mixtures of two or more thereof, wherein more preferably the acid employed in (c) is HCl and/or HNO 3 , preferably HNO 3 .
  • the treatment in (c) is conducted for a duration in the range of from 0.1 to 6 h, more preferably of from 0.5 to 4 h, more preferably of from 1 to 3 h, more preferably of from 1.5 to 2.5 h, and more preferably of from 1.8 to 2.2 h. More particular, it is preferred that the treatment in (c) is conducted at a temperature in the range of from 20 to 95 °C, more preferably of from 30 to 85 °C, more preferably of from 40 to 80 °C, more preferably of from 45 to 75 °C, more preferably of from 50 to 70 °C, and more preferably of from 55 to 65 °C.
  • the one or more sources for B 2 O 3 is selected from the group consisting of boric acid, borates, boric esters, and mixtures of two or more the-reof, more preferably from the group consisting of boric acid, borates, triethyl borate, trimethyl borateboric esters, and mixtures of two or more thereof, wherein more preferably the one or more sources for B 2 O 3 comprises boric acid and/or borates, preferably boric acid, wherein more preferably the one or more sources for B 2 O 3 consists of boric acid and/or borates, preferably of boric acid.
  • the molar ratio SiO 2 : B 2 O 3 of the one or more sources for SiO 2 to the one or more sources for B 2 O 3 in the mixture prepared in (a) is in the range of from 0.5 to 50, more preferably of from 1 to 20, more preferably of from 2 to 10, more preferably of from 2.5 to 5, more preferably of from 3 to 4, and more preferably of from 3.3 to 3.4.
  • the molar ratio SiO 2 : organotemplate of the one or more sources for SiO 2 to the one or more organotemplates in the mixture prepared in (a) is in the range of from 0.1 to 50, more preferably of from 0.5 to 20, more preferably of from 1 to 10, more prefera-bly of from 1.4 to 5, more preferably of from 1.6 to 3, and more preferably of from 1.8 to 2.5. It is particularly preferred that the molar ratio H 2 O : SiO 2 of water to SiO 2 in the framework structure of the first zeolitic material in the mixture prepared according to (a) ranges from 5 to 30, prefer-ably of from 8 to 25, more preferably of from 10 to 20, more preferably of from 12 to 18, and more preferably of from 14 to 16.
  • the process for the preparation of the seed crystals further comprises
  • the process for the preparation of the seed crystals further comprises calcination in (iv) .
  • the calcination in (iv) it is preferred that it is conducted for a duration in the range of from 0.5 to 15 h, more preferably of from 1 to 10 h, more preferably of from 1.5 to 8 h, more preferably of from 2 to 6 h, more preferably of from 2.5 to 5.5 h, more preferably of from 3 to 5 h, and more preferably of from 3.5 to 4.5 h.
  • the process for the preparation of the seed crystals further comprises calcination in (iv) .
  • the calcination in (iv) it is preferred that it is conducted at a temperature in the range of from 300 to 900 °C, more preferably of from 350 to 800 °C, more preferably of from 400 to 750 °C, more preferably of from 450 to 700 °C, more preferably of from 500 to 650 °C, and more preferably of from 560 to 600 °C.
  • the zeolitic material crystallized in (b) has a framework structure type selected from the group consisting of AEI, BEA, BEC, CHA, EUO, FAU, FER, HEU, ITH, ITW, LEV, MEL, MFI, MOR, MTN, MWW, and TON, including mixed structures of two or more thereof, more preferably from the group consisting of AEI, BEA, CHA, FAU, FER, MFI, MOR, and MWW, including mixed structures of two or more thereof, more pre-ferably from the group consisting of AEI, BEA, CHA, MFI, MOR, and MWW, including mixed structures of two or more thereof, more preferably from the group consisting of AEI, CHA, and MWW, including mixed structures of two or more thereof, wherein more preferably the zeolitic material
  • the one or more sources of SiO 2 are selected from the group consisting of silicon containing zeolites having a FAU, FER, GIS, MOR, LTA, TON, MTT, BEA and/or MFI framework structure, silicas, silicates, silicic acid and combinations of two or more thereof, more preferably selected from the group consisting of silicon containing zeolites having a FAU, GIS, BEA and/or MFI framework structure, silicas, alkali metal silicates, silicic acid, and combinations of two or more thereof, more preferably selected from the group consisting of a silicon contain-ing zeolite having a FAU, BEA and/or MFI framework structure, fumed silica, colloidal silica, reactive amorphous solid silica, silica gel, pyrogenic silica, lithium silicates, sodium silicates, potassium silicates, silicic acid, and combinations of two or more thereof, more preferably se-lected from the group consisting of
  • the one or more sources of SiO 2 are selected from the group consisting of silicon containing zeolites having a FAU, FER, GIS, MOR, LTA, TON, MTT, BEA and/or MFI framework structure, silicas, silicates, silicic acid and combinations of two or more thereof
  • the zeolites having an FAU-type framework structure are selected from the group consisting of ZSM-3, Faujasite, [Al-Ge-O] -FAU, CSZ-1, ECR-30, Zeolite X, Zeolite Y, LZ-210, SAPO-37, ZSM-20, Na-X, US-Y, Na-Y, [Ga-Ge-O] -FAU, Li-LSX, [Ga-Al-Si-O] -FAU, and [Ga-Si-O] -FAU, including mixtures of two or more thereof, more preferably from the group consisting of ZSM-3, Faujasite,
  • the one or more sources of SiO 2 are selected from the group consisting of silicon containing zeolites having a FAU, FER, GIS, MOR, LTA, TON, MTT, BEA and/or MFI framework structure, silicas, silicates, silicic acid and combinations of two or more thereof
  • the zeolites having a BEA-type framework structure is selected from the group consisting of zeolite beta, Tschernichite, [B-Si-O] -*BEA, CIT-6, [Ga-Si-O] -*BEA, Beta polymorph B, SSZ-26, SSZ-33, Beta polymorph A, [Ti-Si-O] -*BEA, and pure silica beta, including mixtures of two or more thereof, more preferably from the group consisting of zeolite beta, CIT-6, Beta polymorph B, SSZ-26, SSZ-33, Beta polymorph A, and pure silica beta, and pure silica beta
  • the one or more sources of SiO 2 are selected from the group consisting of silicon containing zeolites having a FAU, FER, GIS, MOR, LTA, TON, MTT, BEA and/or MFI framework structure, silicas, silicates, silicic acid and combinations of two or more thereof
  • the zeolites having an MFI-type framework structure is selected from the group consisting of Silicalite, ZSM-5, [Fe-Si-O] -MFI, [Ga-Si-O] -MFI, [As-Si-O] -MFI, AMS-1 B, AZ-1, Bor-C, Encilite, Boralite C, FZ-1, LZ-105, Mutinaite, NU-4, NU-5, TS-1, TSZ, TSZ-III, TZ-01, USC-4, USI-108, ZBH, ZKQ-1 B, ZMQ-TB, MnS-1, and FeS-1, including mixture
  • the one or more sources of Ga 2 O 3 comprises one or more compounds selected from the group consisting of gallium containing zeolites having a FAU framework structure and gallium salts, wherein more preferably the one or more sources of Ga 2 O 3 comprises a gallium contain-ing zeolite having a FAU framework structure or gallium nitrate, wherein more preferably one or more sources of Ga 2 O 3 consists of a gallium containing zeolite having a FAU framework struc-ture or gallium nitrate.
  • the one or more sources of Al 2 O 3 comprises one or more compounds selected from the group consisting of aluminum containing zeolites having a FAU framework structure and aluminum salts, wherein more preferably the one or more sources of Al 2 O 3 comprises an aluminum con-taining zeolite having a FAU framework structure or aluminum nitrate, wherein more preferably the one or more sources of Al 2 O 3 consists of an aluminum containing zeolite having a FAU framework structure or aluminum nitrate.
  • the one or more sources of SiO 2 and the one or more sources of Al 2 O 3 comprise silicon, gallium and aluminum containing zeolites having a FAU framework structure, more preferably the one or more sources of SiO 2 and the one or more sources of Al 2 O 3 consist of a silicon, gallium and aluminum containing zeolite having a FAU framework structure, wherein more preferably the one or more sources of SiO 2 , the one or more sources of Ga 2 O 3 , and the one or more sources of Al 2 O 3 comprise silicon, gallium and aluminum containing zeolites having a FAU framework structure, more preferably the one or more sources of SiO 2 , the one or more sources of Ga 2 O 3 , and the one or more sources of Al 2 O 3 comprise a silicon, gallium and aluminum containing zeolite having a FAU framework structure.
  • the solvent system is selected from the group consisting of optionally branched (C1-C4) alcohols, distilled water, and mixtures thereof, more preferably from the group consisting of optionally branched (C1-C3) alcohols, distilled water, and mixtures thereof, more preferably from the group consisting of methanol, ethanol, distilled water, and mixtures thereof, wherein more preferably the solvent system comprises distilled water, wherein more preferably the solvent system consists of distilled water.
  • optionally branched (C1-C4) alcohols, distilled water, and mixtures thereof more preferably from the group consisting of optionally branched (C1-C3) alcohols, distilled water, and mixtures thereof, more preferably from the group consisting of methanol, ethanol, distilled water, and mixtures thereof, wherein more preferably the solvent system comprises distilled water, wherein more preferably the solvent system consists of distilled water.
  • the seed crystals comprise one or more zeolitic materials comprising SiO 2 , Al 2 O 3 , and Ga 2 O 3 in its framework structure as obtainable and or obtained according to the process of any one of the embodiments disclosed herein.
  • the present invention relates to a zeolitic material obtainable from the process of any one of the embodiments disclosed herein.
  • the present invention relates to a process for the treatment of NO x by selective cata-lytic reduction comprising
  • step (B) contacting the gas stream provided in step (A) with a zeolitic material according to any one of the embodiments disclosed herein.
  • the gas stream provided in (A) further comprises one or more reducing agents, wherein the reducing agent more preferably comprises ammonia and/or urea.
  • the gas stream provided in (A) comprises one or more waste gases, more preferably one or more waste gases from one or more industrial processes, wherein more preferably the waste gas stream comprises one or more waste gas streams obtained in processes for producing adipic acid, ni-tric acid, hydroxylamine derivatives, caprolactame, 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, wherein even more preferably the waste gas stream comprises one or more waste gas streams obtained in processes for producing adipic acid and/or nitric acid.
  • the gas stream provided in (A) comprises one or more waste gases from an internal combustion engine, preferably from a diesel engine or from a lean burn gaso-line engine.
  • the contacting of the gas stream with the zeolitic material in (B) is conducted at a temperature comprised in the range of from 250 to 550 °C, more preferably of from 300 to 500 °C, more preferably of from 325 to 450 °C, more preferably of from 350 to 425 °C, more preferably of from 380 to 420 °C, and even more preferably of from 390 to 410 °C.
  • the present invention relates to an apparatus for the treatment of a gas stream con-taining NO x , the apparatus comprising a catalyst bed provided in fluid contact with the gas stream to be treated, wherein the catalyst bed comprises a zeolitic material according to any one of the embodiments disclosed herein.
  • the catalyst bed is a fixed bed catalyst or a fluidized bed catalyst, more preferably a fixed bed catalyst.
  • the apparatus further comprises one or more devices pro-vided upstream of the catalyst bed for injecting one or more reducing agents into the gas stream, wherein the reducing agent preferably comprises ammonia and/or urea.
  • the present invention relates to a use of a zeolitic material according to any one of the embodiments disclosed herein as a molecular sieve, as an adsorbent, for ion-exchange, as a catalyst or a precursor thereof, and/or as a catalyst support or a precursor thereof, more pre-ferably as a catalyst or a precursor thereof and/or as a catalyst support or a precursor thereof, more preferably as a catalyst or a precursor thereof, more preferably as a catalyst for the selec-tive catalytic reduction (SCR) of nitrogen oxides NO x ; for the storage and/or adsorption of CO 2 ; for the oxidation of NH 3 , in particular for the oxidation of NH 3 slip in diesel systems; for the de-composition of N 2 O; as an additive in fluid catalytic cracking (FCC) processes; and/or as a cata-lyst in organic conversion reactions, preferably in the conversion of alcohols to olefins,
  • a zeolitic material comprising SiO 2 , Al 2 O 3 and Ga 2 O 3 in its framework structure, wherein the SiO 2 : Ga 2 O 3 molar ratio of the framework structure of the zeolitic material is equal to or less than 69: 1, and wherein the SiO 2 : Al 2 O 3 molar ratio of the framework structure of the zeolitic material is equal to or less than 750: 1.
  • the zeolitic material of embodiment 1, wherein the SiO 2 : Ga 2 O 3 molar ratio of the frame-work structure of the zeolitic material is in the range of from 1: 1 to 69: 1, preferably in the range of from 10: 1 to 69: 1, more preferably in the range of from 30: 1 to 68: 1, more prefer-ably in the range of from 40: 1 to 68: 1, more preferably in the range of from 48: 1 to 67: 1, more preferably in the range of from 55: 1 to 67: 1, more preferably in the range of from 60:1 to 67: 1, more preferably in the range of from 63: 1 to 67: 1, and more preferably in the range of from 65: 1 to 67: 1.
  • the zeolitic material of embodiment 1 or 2, wherein the SiO 2 : Al 2 O 3 molar ratio of the framework structure of the zeolitic material is in the range of from 1: 1 to 500: 1, preferably of from 5: 1 to 250: 1, more preferably of from 10: 1 to 150: 1, more preferably of from 15: 1 to 125: 1, more preferably of from 20: 1 to 80: 1, more preferably of from 30: 1 to 60: 1, more preferably of from 35: 1 to 55: 1, more preferably of from 40: 1 to 48: 1, and more preferably of from 42: 1 to 46: 1.
  • the zeolitic material of any one of embodiments 1 to 11, wherein the mean particle size D50 by volume of the zeolitic material as determined according to ISO 13320: 2009 is of at least 0.3 micrometer, and is preferably in the range of from 0.3 to 6.0 micrometer, more preferably in the range of from 1.5 to 4.5 micrometer, and more preferably in the range of from 2.5 to 3.6 micrometer.
  • the zeolitic material of any one of embodiments 1 to 12, wherein the mean particle size of the primary crystals of the zeolitic material as determined by SEM is in the range of from 100 to 3000 nanometer, preferably in the range of from 110 to 1000 nanometer, more pre-ferably in the range of from 120 to 500 nanometer, and more preferably in the range of from 130 to 250 nanometer.
  • zeolitic material of embodiment 16 wherein the zeolitic material has a crystal size in the range of from 0.1 to 5 micrometer, preferably in the range of from 0.5 to 2.5 micrometer.
  • a process for the preparation of a zeolitic material comprising SiO 2 , Ga 2 O 3 , and Al 2 O 3 in its framework structure, preferably of a zeolitic material according to any one of embodi-ments 1 to 17, the process comprising
  • R 1 , R 2 , and R 3 independently from one another stand for optionally branched (C 1 -C 6 ) alkyl, preferably (C 1 -C 5 ) alkyl, more preferably (C 1 -C 4 ) alkyl, more preferably (C 1 -C 3 ) alkyl, more preferably for methyl or ethyl, and more pre-ferably for methyl.
  • R 4 stands for adamantyl and/or benzyl, preferably for adamantyl, more preferably for 1-adamantyl.
  • any one of embodiments 22 to 24, wherein the one or more tetraalkylam-monium cation R 1 R 2 R 3 R 4 N + -containing compounds comprise one or more N, N, N-tri (C 1 -C 4 ) alkyl-1-adamantammonium compounds, preferably one or more N, N, N-tri (C 1 -C 3 ) alkyl-1-adamantammonium compounds, more preferably one or more N, N, N-tri (C 1 -C 2 ) alkyl-1-adamantammonium compounds, more preferably one or more N, N, N-tri (C 1 -C 2 ) alkyl-1-adamantammonium and/or one or more N, N, N-tri (C 1 -C 2 ) alkyl-1-adamantammonium com-pounds, more preferably one or more compounds selected from N, N, N-triethyl-1-adamantammonium, N, N-die
  • R 3 stands for optionally branched (C 1 -C 6 ) alkyl, preferably (C 1 -C 5 ) alkyl, more preferably (C 1 -C 4 ) alkyl, more preferably (C 1 -C 3 ) alkyl, and more preferably for methyl or ethyl, wherein more preferably R 3 stands for ethyl.
  • R 4 stands for optionally hetero-cyclic 5-to 8-membered cycloalkyl, preferably for 5-to 7-membered cycloalkyl, more pre-ferably for 5-or 6-membered cycloalkyl, wherein more preferably R 4 stands for optionally heterocyclic 6-membered cycloalkyl, and more preferably for cyclohexyl.
  • any one of embodiments 26 to 29, wherein the one or more tetraalkylam-monium cation R 1 R 2 R 3 R 4 N + -containing compounds comprise one or more N, N, N-tri (C 1 -C 4 ) alkyl- (C 5 -C 7 ) cycloalkylammonium compounds, preferably one or more N, N, N-tri (C 1 -C 3 ) alkyl- (C 5 -C 6 ) cycloalkylammonium compounds, more preferably one or more N, N, N-tr i(C 1 -C 2 ) alkyl- (C 5 -C 6 ) cycloalkylammonium compounds, more preferably one or more N, N, N-tri (C 1 -C 2 ) alkyl-cyclopentylammonium and/or one or more N, N, N-tri (C 1 -C 2 ) alkyl-cyclohexylammonium compounds
  • the one or more organotem-plates comprises one or more tetraalkylammonium cation R 1 R 2 R 3 R 4 N + -containing com-pounds, wherein R 1 , R 2 , R 3 and R 4 independently from one another stand for alkyl, and wherein R 3 and R 4 form a common alkyl chain.
  • N, N-dialkyl-2, 6-dialkylpyrrolidinium com-pounds, N, N-dialkyl-2, 6-dialkylpiperidinium compounds, and/or N, N-dialkyl-2, 6-dialkylhexahydroazepinium compounds display the cis configuration, the trans configura-tion, or contain a mixture of the cis and trans isomers, wherein preferably the N, N-dialkyl-2, 6-dialkylpyrrolidinium compounds, N, N-dialkyl-2, 6-dialkylpiperidinium compounds, and/or N, N-dialkyl-2, 6-dialkylhexahydroazepinium com-pounds display the cis configuration, wherein more preferably the one or more tetraalkylammonium cation R 1 R 2 R 3 R 4 N + -containing compounds comprise one or more ammonium compounds selected from the group consisting of N, N-di (C 1 -C 2 ).
  • the one or more organotem-plates comprise one or more tetraalkylphosphonium cation R 1 R 2 R 3 R 4 P + -containing com-pounds, wherein R 1 , R 2 , R 3 , and R 4 independently from one another stand for optionally substituted and/or optionally branched (C 1 -C 6 ) alkyl, preferably (C 1 -C 5 ) alkyl, more prefera-bly (C 1 -C 4 ) alkyl, more preferably (C 2 -C 3 ) alkyl, and more preferably for optionally substi-tuted methyl or ethyl, wherein more preferably R 1 , R 2 , R 3 , and R 4 stand for optionally subs-tituted ethyl, preferably unsubstituted ethyl.
  • the mixture prepared in (1) comprises seed crystals, wherein the amount of seed crystals comprised in the mixture prepared in (1) is in the range of from 0.1 to 15 weight-%based on 100 weight-%of Si in the mixture calculated as SiO 2 , and preferably of from 0.5 to 11 weight-%, more preferably of from 0.8 to 8 weight-%, more preferably of from 1.2 to 5 weight-%, more preferably of from 1.5 to 3 weight-%, and more preferably of from 1.8 to 2.5 weight-%.
  • the mixture prepared in (1) comprises seed crystals, wherein the seed crystals comprise one or more zeolitic mate-rials having a framework structure type selected from the group consisting of AEI, BEA, BEC, CHA, EUO, FAU, FER, GIS, HEU, ITH, ITW, LEV, MEL, MFI, MOR, MTN, MWW, AFT, AFV, AFX, AVL, EMT, GME, KFI, LEV, LTN, SFW, and TON, including mixed struc-tures of two or more thereof, more preferably from the group consisting of AEI, AFT, AFV, AFX, AVL, EMT, GIS, GME, KFI, LEV, LTN, MTN, SFW, BEA, CHA, FAU, FER, MFI, MOR, and MWW, including mixed structures of two or more thereof, more preferably from the group consisting of AEI, BEA, BEC, CHA, EUO,
  • the mixture prepared in (1) or (1a) comprises one or more metals selected from the group consisting of alkali metals and alkaline earth metals, preferably one or more metals selected from the group consisting of Li, Na, K, Rb, Cs, Mg, and Ca, more preferably from the group consisting of Li, Na, and K, wherein more preferably the mixture prepared in (1) or (1a) comprises K and/or Na, pre-ferably Na.
  • heating in (2) is conducted for a duration in the range of from 0.5 to 15 d, and more preferably from 1 to 10 d, more pre-ferably from 2 to 8 d, more preferably from 3 to 7 d, more preferably from 3.5 to 6.5 d, more preferably from 4 to 6 d, preferably from 4.5 to 5.5 d.
  • heating in (2) is conducted at a temperature in the range of from 80 to 220 °C, preferably of from 100 to 200 °C, more pre- ferably of from 120 to 180 °C, more preferably of from 130 to 170 °C, more preferably of from 140 to 160 °C, and more preferably of from 145 to 155 °C.
  • heating in (2) is conducted under autogenous pressure, preferably under solvothermal conditions, more preferably under hydrothermal conditions, wherein preferably heating in (2) is performed in a pres-sure tight vessel, preferably in an autoclave.
  • any one of embodiments 18 to 48, wherein the zeolitic material crystallized in (2) has a framework structure type selected from the group consisting of AEI, BEA, BEC, CHA, EUO, FAU, FER, GIS, HEU, ITH, ITW, LEV, MEL, MFI, MOR, MTN, MWW, AFT, AFV, AFX, AVL, EMT, GME, KFI, LEV, LTN, SFW, and TON, including mixed struc-tures of two or more thereof, more preferably from the group consisting of AEI, AFT, AFV, AFX, AVL, EMT, GIS, GME, KFI, LEV, LTN, MTN, SFW, BEA, CHA, FAU, FER, MFI, MOR, and MWW, including mixed structures of two or more thereof, more preferably from the group consisting of AEI, AFT, AFV, AFX, AVL, EUO, F
  • any one of embodiments 50 to 52, wherein the one or more metal cations M are selected from the group consisting of Sr, Zr, Cr, Mg, Mo, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, Sc, and mixtures of two or more thereof, preferably selected from the group consisting of Sr, Zr, Cr, Mg, Mo, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, and mixtures of two or more thereof, more preferably from the group consisting of Sr, Cr, Mo, Fe, Co, Ni, Cu, Zn, Ag, and mixtures of two or more thereof, more preferably from the group consisting of Cr, Mg, Mo, Fe, Ni, Cu, Zn, Ag, and mixtures of two or
  • the mixture prepared in (1) comprises seed crystals, wherein the seed crystals comprise one or more zeolitic mate-rials having the framework structure of the zeolitic material comprising SiO 2 , Ga 2 O 3 and Al 2 O 3 in its framework structure obtained according to the process of any one of embodi-ments 18 to 57, wherein preferably the one or more zeolitic materials of the seed crystals is obtainable and/or obtained according to the process of any one of embodiments 18 to 57.
  • heating in (b) is conducted for a duration in the range of from 0.5 to 15 d, and more preferably from 1 to 10 d, more preferably from 2 to 8 d, more preferably from 3 to 7 d, more preferably from 3.5 to 6.5 d, more preferably from 4 to 6 d, preferably from 4.5 to 5.5 d.
  • thermoforming in (b) is conducted at a tempera-ture in the range of from 80 to 220 °C, preferably of from 100 to 200 °C, more preferably of from 120 to 190 °C, more preferably of from 130 to 180 °C, more preferably of from 150 to 170 °C, and more preferably of from 155 to 165 °C.
  • heating in (b) is conducted under autogenous pressure, preferably under solvothermal conditions, more preferably under hydrothermal conditions, wherein preferably heating in (2) is performed in a pres-sure tight vessel, preferably in an autoclave.
  • any one of embodiments 59 to 66 wherein the one or more sources for B 2 O 3 is selected from the group consisting of boric acid, borates, boric esters, and mix-tures of two or more thereof, preferably from the group consisting of boric acid, borates, triethyl borate, trimethyl borateboric esters, and mixtures of two or more thereof, wherein more preferably the one or more sources for B 2 O 3 comprises boric acid and/or borates, preferably boric acid, wherein more preferably the one or more sources for B 2 O 3 consists of boric acid and/or borates, preferably of boric acid.
  • the zeolitic material crystallized in (b) has a framework structure type selected from the group consisting of AEI, BEA, BEC, CHA, EUO, FAU, FER, HEU, ITH, ITW, LEV, MEL, MFI, MOR, MTN, MWW, and TON, including mixed structures of two or more thereof, preferably from the group consist-ing of AEI, BEA, CHA, FAU, FER, MFI, MOR, and MWW, including mixed structures of two or more thereof, more preferably from the group consisting of AEI, BEA, CHA, MFI, MOR, and MWW, including mixed structures of two or more thereof, more preferably from the group consisting of AEI, CHA, and MWW, including mixed structures of two or more thereof, wherein more preferably the zeolitic material crystallized in (b) has a CHA-and/or AEI-type framework
  • zeolites having an FAU-type framework structure are selected from the group consisting of ZSM-3, Faujasite, [Al-Ge-O] -FAU, CSZ-1, ECR-30, Zeolite X, Zeolite Y, LZ-210, SAPO-37, ZSM-20, Na-X, US-Y, Na-Y, [Ga-Ge-O] -FAU, Li-LSX, [Ga-Al-Si-O] -FAU, and [Ga-Si-O] -FAU, including mixtures of two or more thereof, preferably from the group consisting of ZSM-3, Faujasite, CSZ-1, ECR-30, Zeolite X, Zeo-lite Y, LZ-210, ZSM-20, Na-X, US-Y, Na-Y, and Li-LSX, including mixtures of two or more thereof, more preferably from the group consisting of Faujasite, Zeolite Y, CSZ-1, ECR-30,
  • the first zeolitic material having a BEA-type framework structure is selected from the group consisting of zeolite beta, Tschernichite, [B-Si-O] -*BEA, CIT-6, [Ga-Si-O] -*BEA, Beta polymorph B, SSZ-26, SSZ-33, Beta poly-morph A, [Ti-Si-O] -*BEA, and pure silica beta, including mixtures of two or more thereof, preferably from the group consisting of zeolite beta, CIT-6, Beta polymorph B, SSZ-26, SSZ-33, Beta polymorph A, and pure silica beta, including mixtures of two or more thereof, wherein more preferably the first zeolitic material having a BEA-type framework structure comprises zeolite beta, preferably zeolite beta obtained from organotemplate-free synthe-sis, wherein more preferably the first zeolitic material having a
  • the first zeolitic material having an MFI-type framework structure is selected from the group consisting of Silicalite, ZSM-5, [Fe-Si-O] -MFI, [Ga-Si-O] -MFI, [As-Si-O] -MFI, AMS-1 B, AZ-1, Bor-C, Encilite, Boralite C, FZ-1, LZ-105, Mutinaite, NU-4, NU-5, TS-1, TSZ, TSZ-III, TZ-01, USC-4, USI-108, ZBH, ZKQ-1 B, ZMQ-TB, MnS-1, and FeS-1, including mixtures of two or more thereof, preferably from the group consisting of Silicalite, ZSM-5, AMS-1 B, AZ-1, Encilite, FZ-1, LZ-105, Mutinaite, NU-4, NU-5, TS-1, TSZ, TSZ-III,
  • the one or more sources of Ga 2 O 3 comprises one or more compounds selected from the group consisting of gallium containing zeolites having a FAU framework structure and gallium salts, wherein prefera-bly the one or more sources of Ga 2 O 3 comprises a gallium containing zeolite having a FAU framework structure or gallium nitrate, wherein more preferably one or more sources of Ga 2 O 3 consists of a gallium containing zeolite having a FAU framework structure or gal-lium nitrate.
  • the one or more sources of Al 2 O 3 comprises one or more compounds selected from the group consisting of aluminum containing zeolites having a FAU framework structure and aluminum salts, wherein pre-ferably the one or more sources of Al 2 O 3 comprises an aluminum containing zeolite hav-ing a FAU framework structure or aluminum nitrate, wherein more preferably the one or more sources of Al 2 O 3 consists of an aluminum containing zeolite having a FAU frame-work structure or aluminum nitrate.
  • the solvent system is selected from the group consisting of optionally branched (C1-C4) alcohols, distilled water, and mix-tures thereof, preferably from the group consisting of optionally branched (C1-C3) alcohols, distilled water, and mixtures thereof, more preferably from the group consisting of metha-nol, ethanol, distilled water, and mixtures thereof, wherein more preferably the solvent system comprises distilled water, wherein more preferably the solvent system consists
  • a zeolitic material obtainable from the process of any one of embodiments 18 to 83.
  • a process for the treatment of NO x by selective catalytic reduction comprising
  • step (B) contacting the gas stream provided in step (A) with a zeolitic material according to any one of embodiments 1 to 17 and 84.
  • gas stream provided in (A) further comprises one or more reducing agents, wherein the reducing agent preferably comprises ammonia and/or urea.
  • the gas stream provided in (A) comprises one or more waste gases, preferably one or more waste gases from one or more industri-al processes, wherein more preferably the waste gas stream comprises one or more waste gas streams obtained in processes for producing adipic acid, nitric acid, hydroxyla-mine derivatives, caprolactame, 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, wherein even more preferably the waste gas stream comprises one or more waste gas streams obtained in processes for producing adipic acid and/or nitric acid.
  • gas stream provided in (A) comprises one or more waste gases from an internal combustion engine, preferably from a diesel engine or from a lean burn gasoline engine.
  • Apparatus for the treatment of a gas stream containing NO x comprising a catalyst bed provided in fluid contact with the gas stream to be treated, wherein the cata-lyst bed comprises a zeolitic material according to any one of embodiments 1 to 17 and 84.
  • invention 90 or 91 further comprising one or more devices provided upstream of the catalyst bed for injecting one or more reducing agents into the gas stream, wherein the reducing agent preferably comprises ammonia and/or urea.
  • a zeolitic material according to any one of embodiments 1 to 17 and 84 as a mole-cular sieve, as an adsorbent, for ion-exchange, as a catalyst or a precursor thereof, and/or as a catalyst support or a precursor thereof, preferably as a catalyst or a precursor thereof and/or as a catalyst support or a precursor thereof, more preferably as a catalyst or a pre-cursor thereof, more preferably as a catalyst for the selective catalytic reduction (SCR) of nitrogen oxides NO x ; for the storage and/or adsorption of CO 2 ; for the oxidation of NH 3 , in particular for the oxidation of NH 3 slip in diesel systems; for the decomposition of N 2 O; as an additive in fluid catalytic cracking (FCC) processes; and/or as a catalyst in organic conversion reactions, preferably in the conversion of alcohols to olefins, and more prefer-ably in methanol to olefin (SCR) of
  • Figure 1 displays the results from SCR testing and in particular the NO conversion for the fresh zeolitic materials obtained according to Comparative Example 2 displaying Si:Ga molar ratios of 17 ( “Cu-Ga-CHA (17) ” ) , 33 ( “Cu-Ga-CHA (33) ” ) , and 47 ( “Cu-Ga-CHA (47) ” ) , according to Comparative Example 3 displaying a Si: Ga molar ra-tio of 17 ( “Cu-Ga-CHA (17) *” ) , of a sodium containing sample displaying a Si: Ga molar ratios of 33 ( “Na-Cu-Ga-CHA (33) ” ) , and of Example 4.
  • the temperature in °C is plotted along the abscissa, and the NO conversion rate in %is plotted along the left ordinate.
  • Figure 2 displays the results from SCR testing and in particular the N 2 O make for the fresh zeolitic materials obtained according to Comparative Example 2 displaying Si: Ga molar ratios of 17 ( “Cu-Ga-CHA (17) ” ) , 33 ( “Cu-Ga-CHA (33) ” ) , and 47 ( “Cu-Ga-CHA (47) ” ) , according to Comparative Example 3 displaying a Si: Ga molar ratio of 17 ( “Cu-Ga-CHA (17) *” ) , of a sodium containing sample displaying a Si: Ga molar ratios of 33 ( “Na-Cu-Ga-CHA (33) ” ) , and of Example 4.
  • the tempera-ture in °C is plotted along the abscissa
  • Figure 3 displays the results from SCR testing and in particular the NO conversion for the steamed zeolitic material obtained according to Comparative Example 2 display-ing Si: Ga molar ratios of 17 ( “Cu-Ga-CHA (17) ” ) , 33 ( “Cu-Ga-CHA (33) ” ) , and 47 ( “Cu-Ga-CHA (47) ” ) , according to Comparative Example 3 displaying a Si: Ga mo-lar ratio of 17 ( “Cu-Ga-CHA (17) *” ) , of a sodium containing sample displaying a Si: Ga molar ratios of 33 ( “Na-Cu-Ga-CHA (33) ” ) , and of Example 4.
  • the temperature in °C is plotted along the abscissa, and the NO conversion rate in %is plotted along the ordinate.
  • Figure 4 displays the results from SCR testing and in particular the N 2 O make for the steamed zeolitic material obtained according to Comparative Example 2 display-ing Si: Ga molar ratios of 17 ( “Cu-Ga-CHA (17) ” ) , 33 ( “Cu-Ga-CHA (33) ” ) , and 47 ( “Cu-Ga-CHA (47) ” ) , according to Comparative Example 3 displaying a Si: Ga mo-lar ratio of 17 ( “Cu-Ga-CHA (17) *” ) , of a sodium containing sample displaying a Si:Ga molar ratios of 33 ( “Na-Cu-Ga-CHA (33) ” ) , and of Example 4.
  • the temperature in °C is plotted along the abscissa, and the N 2 O make in %is plotted along the ordinate.
  • Figure 5 displays the X-Ray diffraction pattern for a zeolitic material obtained according to Example 1 ( “Ga, Al-CHA” ; upper line) and Reference Example 2 having a Si: Ga molar ratio of 17 ( “Ga-CHA” ; lower line) .
  • the diffraction angle in 2theta is plotted long the abscissa and the intensity in arbitrary units is plotted along the ordinate.
  • Figure 6 displays the X-Ray diffraction pattern for a zeolitic material obtained according to Example 5 ( “as made [Ga, Al] -AEI (N) ” ) , for the zeolitic material ( “ [Ga, Al] -FAU” ) obtained from Reference Example 4 and for the zeolite Y ( “FAU” ) used as start-ing material in Reference Example 4.
  • the diffraction angle in 2theta is plotted long the abscissa and the intensity in arbitrary units is plotted along the ordinate.
  • Figure 7 displays the X-Ray diffraction pattern for a zeolitic material obtained according to Example 6 (lower line for “as made [Ga, Al] -AEI (P) ” and upper line for “H-form of [Ga, Al] -AEI (P) ” ) .
  • the diffraction angle in 2theta is plotted long the abscissa and the intensity in arbitrary units is plotted along the ordinate.
  • Figure 8 displays the results from SCR testing and in particular the NO conversion for the zeolitic material obtained according to Example 4.
  • the time in min is plotted along the abscissa
  • the conversion rate for NH 3 and NO in % is plotted along the left ordinate
  • the production of NO in ppm is plotted along the right ordinate.
  • the temperature is displayed as regards the respective time pe-riod.
  • Figure 9 displays the results from SCR testing and in particular the NO conversion for the zeolitic material obtained according to Example 8.
  • the time in min is plotted along the abscissa
  • the conversion rate for NH 3 and NO in % is plotted along the left ordinate
  • the production of NO in ppm is plotted along the right ordinate.
  • the temperature is displayed as regards the respective time pe-riod.
  • Figure 10 displays the results from SCR testing and in particular the NO conversion for the zeolitic material obtained according to Example 7.
  • the time in min is plotted along the abscissa
  • the conversion rate for NH 3 and NO in % is plotted along the left ordinate
  • the production of NO in ppm is plotted along the right ordinate.
  • the temperature is displayed as regards the respective time pe-riod.
  • Powder X-ray diffraction (XRD) patterns were routinely collected for Example 1, Comparative Example 2, Comparative Example 3 and Example 4 on a STOE STADI P diffractometer using an image plate detector, Cu K ⁇ radiation and transmission geometry.
  • Si/B ratios of the samples were determined at the ‘Bodemmatie Div van VZW’ (Heverlee, Belgium) .
  • Powder X-ray diffraction (XRD) patterns were collected for Example 5 and Example 6 on a Rigaku Ultima III diffractometer using CuKa radiation (40 kV, 40 mA) .
  • FE-SEM images were obtained on a Hitachi S-5200 microscope operated at 1 kV.
  • Example 1 Comparative Example 2
  • Comparative Example 3 Comparative Example 4
  • Example 5 Bulk elemental analyses for Example 5 and Example 6 were performed on an inductively coupled plasma-atomic emission spectrometer (ICP-AES, Shimad-zu ICPE-9000) .
  • N 2 physisorption and desorption iso-therms were collected using a Micromeritics 3Flex surface analyzer at -196°C after evacuating the samples at 350°C for 12 h under vacuum. From the N 2 isotherms, the specific surface area (S BET ) was determined using the BET method (p/p 0 0.05-0.3) . The specific micropore volume (V micro ) was obtained from t-plot analysis.
  • Catalyst powders were granulated by pressing between two metal bolts followed by crushing and sieving. The fraction with mesh size between 0.250 and 0.500 mm was separated and used for catalytic testing. Catalytic testing of the samples was performed in a quartz fixed bed tube reactor with downstream flow and an internal diameter of 4 mm at atmospheric pressure. 200 mg granulated catalyst (mesh size 0.250 -0.500 mm) was fixed in the middle of the reactor bed using quartz wool. A thermocouple was placed inside the catalyst bed to control the reactor temperature. The catalyst was pretreated by heating at 5 °C/min in a flow of O 2 (30 mL/min) to 450 °C and remaining at 450 °C for 0.5 h.
  • the catalyst was cooled down in a flow of O 2 (30 mL/min) to 150 °C.
  • a gas mixture consisting of 500 ppm NH 3 , 500 ppm NO, 10 %O 2 , 10 %CO 2 and 5 %H 2 O in N 2 was prepared by diluting 0.5 %NH 3 in N 2 (30 mL/min) , 0.5 %NO in N 2 (30 mL/min) , O 2 (30 mL/min) and CO 2 (30 mL/min) in N 2 (150 mL/min) .
  • H 2 O was added to the latter N 2 stream prior to mixing with NH 3 , NO, O 2 and CO 2 .
  • This gas mixture was passed over the catalyst at 150°C using a space velocity of 80,000 h -1 .
  • the catalyst was tested at 150 °C, 200 °C, 250 °C, 350 °C, and 450 °C by remaining 1 h at each temperature step and heating at 5 °C/min in between two temperature steps.
  • the reactor outlet was analyzed using a GASMET FT-IR Gas analyser (Model DX4000) .
  • Example 2 To test the stability of the catalysts, the catalysts according to Comparative Example 2, Com-parative Example 3 and Example 4 were hydrothermally aged by steam treatment in 5 %H 2 O at 750°C for 6 h (5 °C/min) .
  • the catalyst was cooled down to 100°C under O 2 flow (30 mL/min) after pretreatment.
  • a gas mixture of 790 ppm NO and 5.2 %O 2 in N 2 was used.
  • the catalyst was tested at 100 °C, 150 °C, 200 °C, 250 °C, 350 °C, and 450 °C by remaining 1 h at each temperature step and heating at 5°C/min in between two temperature steps.
  • B 3+ -containing CHA was prepared with two different Si/B 3+ ratios based on the literature proce-dures in Regli, L. et al. in J. Phys. Chem. C. 2007, 111, 2992–2999 and Liang, J. et al. in Micro-porous Mesoporous Mater. 2014, 194, 97–105.
  • high B 3+ content CHA was crystal-lized from a gel with a composition of 1 SiO 2 : 0.3 H 3 BO 3 : 0.5 TMAdaOH : 15 H 2 O.
  • TMAdaOH N, N, N-trimethyl-1-adamantylammonium hydroxide, aqueous solution with 30 weight-%of TMAdaOH, 46.44 g) , H 3 BO 3 (2.46 g) , fumed silica (cabosil M5, 7.92 g) and deionized water (3.18 g) were mixed to form a uniform gel.
  • the gel was transferred to Teflon lined autoclaves and heated for 7 days at 150°C under static conditions. The suspension was filtered and the material was thoroughly washed with water followed by drying at 60°C.
  • Low B 3+ content CHA was synthesized in a similar way from a gel with composition 1 SiO 2 : 0.08 H 3 BO 3 : 0.24 TMAdaOH : 22.3 H 2 O, which was heated for 5 days at 160 °C under static conditions. The dried products were calcined in air at 580 °C for 4 h (heating ramp 1°C/min) to obtain the H + -form.
  • the high B 3+ CHA (H-B-CHA (14) ) and the low B 3+ CHA (H-B-CHA (22) ) syntheses resulted in a respective bulk Si/B ratio of 14 and 22.
  • Figure 5 shows the XRD pattern of Reference Example 2 (lower line) .
  • a portion of the sample displaying an Si: Ga molar ratio of 17 was converted to the H-form via ion exchange with ammonium and subsequent calcination and subject to surface area and po-rosity analysis, thus affording a BET surface area of 554 m 2 /g and a micropore volume of 0.27 cm 3 /g.
  • Solution B was added to solution A while stirring, followed by the addition of 0.026 g seeds (2 weight-%with respect to the SiO 2 source) .
  • the suspension was stirred until it was homogeneous, and next crystallized for 5 days at 150 °C. After filtering, washing and drying, the material was calcined in air for 4 h at 580 °C, using a 1°C/min heating ramp.
  • the Si/Ga molar ratio of the obtained ma-terial was 33, the Si/Al molar ratio 22, and the Si/ (Al+Ga) molar ratio 13.2.
  • Figure 5 shows the XRD pattern of Example 1 (upper line) .
  • the product of Reference Example 2 was first brought into the NH 4 + form by exchange for 24 h at 25°C in 1 M NH 4 NO 3 (1 g of zeolite per 150 mL solution) .
  • the dried powders were ex-changed with Cu 2+ using a 0.3 M Cu (CH 3 COO) 2 .3H 2 O solution.
  • 1 g of zeolite was stirred in an appropriate volume of Cu acetate solution for 1 h at 70°C; for instance, 1 g in 3.75 mL of a 0.3 M Cu acetate solution results in 2.5 weight-%Cu loading.
  • samples were abundantly rinsed with distilled water until the washing water was free of Cu 2+ (as determined in a test with NH 4 OH solution) .
  • Reference Example 1 was repeated, wherein Cu was added directly to solution A, in order to avoid the additional step of a Cu exchange in Comparative Example 2.
  • Example 1 The product of Example 1 was first brought into the NH 4 + form by exchange for 24 h at 25°C in 1 M NH 4 NO 3 (1 g of zeolite per 150 mL solution) . Next, the dried powders were exchanged with Cu 2+ using a 0.3 M Cu (CH 3 COO) 2 ⁇ 3H 2 O solution. Depending on the Cu loading desired, 1 g of zeolite was stirred in an appropriate volume of Cu acetate solution for 1 h at 70°C; for instance, 1 g in 3.75 mL of a 0.3 M Cu acetate solution results in 2.5 weight-%Cu loading. After ex-change, samples were abundantly rinsed with distilled water until the washing water was free of Cu 2+ (as determined in a test with NH 4 OH solution) .
  • the [Ga, Al] -FAU had a Si/Ga molar ratio of 212, a Si/Al molar ratio of 120, and a Si/ (Al+Ga) molar ratio of 38.
  • the silicon content was 45.2 weight-%
  • the aluminum content was 0.73 weight-%
  • the gallium content was 1.07 weight-%.
  • Figure 6 shows the XRD patterns of zeolite Y ( “FAU” ) used as starting material in Reference Example 4 and of the gallium and aluminum containing zeolitic material having the framewotk structure type FAU ( [Ga, Al] -FAU) obtained from Reference Example 4.
  • Example 5 Synthesis of a gallium and aluminum containing zeolitic material having the framework structure type AEI ( [Ga, Al] -AEI (N) )
  • the thus prepared gel was crystallized in an autoclave at 150 °C for 3 days under tumbling condition (30 rpm. ) .
  • the solid crystalline product, a zeolitic material having the framework struc-ture type AEI was recovered by filtration, washed with distilled water, and dried overnight at 100 °C under air to obtain the desired product as an asmade material.
  • the thus obtained prod-uct is also referred to herein as “ [Ga, Al] -AEI (N) ” .
  • the obtained as-made [Ga, Al] -AEI (N) was calcined at 600 °C under air for 6 h.
  • zeolitic material 1 g was then treated twice with 100 ml of a 2.5 M NH 4 NO 3 (Wako) aqueous solution at 80 °C for 3 h to obtain the ammo- nium form of the zeolitic material.
  • the obtained zeolitic material in its ammonium form was then calcined at 600 °C for 5 h under air to obtain the H-form of the desired zeolitic material.
  • the as made [Ga, Al] -AEI (N) had a Si/Ga molar ratio of 24, a Si/Al molar ratio of 11, and a Si/(Al+Ga) molar ratio of 7.6.
  • the SiO 2 / (Al 2 O 3 + Ga 2 O 3 ) molar ratio was 21.12.
  • the silicon content was 40.22 weight-%
  • the aluminum content was 3.53 weight-%
  • the gallium content was 4.19 weight-%.
  • Figure 7 shows the XRD patterns of the gallium and aluminum containing zeolitic material hav-ing the framework structure type AEI ( [Ga, Al] -AEI obtained from Reference Example 4.
  • Example 6 Synthesis of a gallium and aluminum containing zeolitic material having the framework structure type AEI ( [Ga, Al] -AEI (P) )
  • 0.45 g NaOH (97%, Wako) were added to 4.0764 g of an aqueous solution of tetraethyl-phosphonium hydroxide (TEPOH; density of the solution of 1.0379 g ml -1 and molar concentra-tion of 2.2915 M, BASF SE) and 1.4517 g distilled water to obtain a first solution.
  • TEPOH tetraethyl-phosphonium hydroxide
  • 0.6 g Ga(NO 3 ) 3 ⁇ 8 H 2 O 99.9%, Wako
  • the molar composition of the resulting gel was 1 SiO 2 : 0.033 Al : 0.033 Ga : 0.2 TEPOH : 0.25 NaOH : 5 H 2 O.
  • the thus prepared gel was crys-tallized in an autoclave at 170 °C for 5 days under tumbling condition (40 rpm) .
  • the solid crys-talline product, a zeolitic material having the framework structure type AEI was recovered by filtration, washed with distilled water, and dried overnight at 100 °C under air to obtain the de-sired product as an as made material.
  • the thus obtained product is also referred to herein as “[Ga, Al] -AEI (P) ” .
  • zeolitic ma-terial was subsequently treated twice with 100 ml of an aqueous solution of 2.5 M NH 4 NO 3 (Wa-ko) at 80 °C for 3 h to obtain the ammonium form of the zeolitic material.
  • the obtained zeolitic material in its ammonium form was then calcined at 600 °C for 5 h under air to obtain the H-form of the desired zeolitic material.
  • the as made [Ga, Al] -AEI (P) had a Si/Ga molar ratio of 22, a Si/Al molar ratio of 19, a Si/ (Al+Ga) molar ratio of 10.2, and a P/ (Al+Ga) molar ratio of 1.1.
  • the SiO 2 / (Al 2 O 3 + Ga 2 O 3 ) molar ratio was 20.39.
  • the silicon content was 37.56 weight-%
  • the aluminum content was 1.91 weight-%
  • the gallium content was 4.27 weight-%
  • the phosphorous content was 4.49 weight-%.
  • the H-form of [Ga, Al] -AEI (P) had a Si/Ga molar ratio of 22, a Si/Al molar ratio of 18.5, a Si/ (Al+Ga) molar ratio of 10, and a P/ (Al+Ga) molar ratio of 0.33.
  • the SiO 2 / (Al 2 O 3 + Ga 2 O 3 ) molar ratio was 20.1.
  • the silicon content was 40.06 weight-%
  • the aluminum content was 2.09 weight-%
  • the gallium content was 4.55 weight-%-%
  • the phosphorous content was 1.46 weight-%.
  • Example 7 Synthesis of Cu- [Ga, Al] -AEI (N) via copper exchange of [Ga, Al] -AEI (N)
  • Example 4 The procedure of Example 4 was repeated using the product of Example 5 instead of the prod-uct of Example 4 to obtain a copper exchanged zeolitic material having a copper content of 2.5 weight-%.
  • Example 8 Synthesis of Cu- [Ga, Al] -AEI (P) via copper exchange of [Ga, Al] -AEI (P)
  • Example 4 The procedure of Example 4 was repeated using the product of Example 6 instead of the prod-uct of Example 4 to obtain a copper exchanged zeolitic material having a copper content of 2.5 weight-%.
  • Example 9 Catalyst testing in SCR –Influence of sodium content
  • the activity for Cu-Ga-CHA (17) obtained according to Comparative Example 2 after a steaming treatment for 6 h at 750°C with 5 volume-%H 2 O de-creased its activity and severely increased the production of N 2 O.
  • the Ga-based Cu-chabazite catalyst according to Comparative Example 3 shows a better steam-stability than for the Ga-based Cu-chabazite which was obtained according to Comparative Example 2, which was obtained by introduction of the Cu directly in the hydrothermal synthesis of the zeo-lite (see results for Cu-Ga-CHA (17) *in Figures 1 to 4) .
  • inventive example Cu-Ga, Al-CHA according to Example 4 displays practically the same activity for the conversion of NOx compared to the comparative examples, all of which display severe deterioration in their activities, in particular at lower temperatures.
  • the N 2 O make remains low for the inventive catalyst, in particular at temperatures above 200°C where it is the second best, wherein at 450°C it displays the lowest N 2 O make of all examples.
  • the inventive copper exchanged gallium and aluminium containing zeolitic material having the framework structure type CHA according to Example 4 shows a high activity and low N 2 O make.
  • the conversion rates of ammonia remained above 90 %for the whole test period and the conversion rates of NO reached a level of 100 %after around 70 minutes of the test and remained above 90 %for the rest of the test period.
  • the N 2 O make it can be seen that in the temperature range of 200 °C and 250 °C the N 2 O reached a level of 6 ppm at maximum whereas the N 2 O make was below 3 ppm for the rest of the test period.
  • the N 2 O make was about 0 to 1 ppm for the temperature of 150 °C and below 1 ppm for a temperature of 450 °C and higher.
  • the inventive copper exchanged gallium and aluminium containing zeolitic material having the framework structure type AEI according to Example 8 shows a comparatively inferior activity as regards the conversion rate of ammonia and NO.
  • the results in view the N 2 O make are exception-ally good.
  • the conversion rate of ammonia was about 100 %for a temperature of 100 °C.
  • the conversion rate of ammonia dropped to a level of about 35 %.
  • the conversion of ammonia reached a level of above 90 %at the end of each phase.
  • the conversion of NO it can be seen that for a temperature below 200 °C but higher than 100 °C the conversion rate reached a level of 35 %at maximum, whereas the conversion rate was above 90 %for a temperature of 200 °C higher.
  • the inventive copper ex-changed gallium and aluminium containing zeolitic material having the framework structure type AEI according to Example 7 shows a similar activity as regards the conversion rate of ammonia and NO as the catalyst according to Example 8.
  • the results in view the N 2 O make are exceptionally good.
  • the N 2 O make remained below 2 pm over the whole test period.
  • the conversion rate of ammonia was about 100 %for a temperature of 100 °C.
  • the conversion rate of ammonia dropped to a level of about 12 %and recovered to about 42 %for the temperature of 150 °C.
  • the conversion of ammonia reached a level of above 90 %at least at the end of each phase.
  • the conversion of NO it can be seen that for a temperature below 200 °C but higher than 100 °C the conversion rate reached a level of 43 %at maximum, whereas the con-version rate was above 90 %for a temperature of 200 °C higher.

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Abstract

L'invention concerne un matériau zéolithique qui comporte du SiO 2, de l'Al 2O 3 et du Ga 2O 3 dans sa structure de charpente, le rapport molaire SiO 2 : Ga 2O 3 de la structure de charpente du matériau zéolithique étant égal ou inférieur à 69, et le rapport molaire SiO 2 : Al 2O 3 de la structure de charpente du matériau zéolithique étant égal ou inférieur à 750. L'invention concerne en outre un procédé de fabrication dudit matériau zéolithique ainsi qu'un procédé de traitement des NO x à l'aide des matériaux zéolithiques selon l'invention, un appareil de traitement d'un courant de gaz contenant des NO x, l'appareil contenant les matériaux zéolithiques selon l'invention, et finalement l'utilisation des matériaux zéolithiques selon la présente invention.
PCT/CN2020/075095 2019-02-14 2020-02-13 Matériau zéolithique contenant de l'aluminium et du gallium et son utilisation en scr WO2020164545A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0432814A1 (fr) * 1989-11-16 1991-06-19 ENIRICERCHE S.p.A. Procédé pour l'alkylation de benzène
WO2011064186A1 (fr) * 2009-11-24 2011-06-03 Basf Se Procédé pour la préparation de zéolites ayant une structure cha
US20120004485A1 (en) * 2010-07-01 2012-01-05 Uop Llc Uzm-5, uzm-5p, and uzm-6 crystalline aluminosilicate zeolites and methods for preparing the same
WO2017100384A1 (fr) * 2015-12-09 2017-06-15 Basf Corporation Matériaux zéolitiques de type cha et procédés pour leur préparation à l'aide de combinaisons de composés cycloalkyl- et éthyltriméthylammonium
CN107635921A (zh) * 2015-04-16 2018-01-26 康斯乔最高科学研究公司 具有aei沸石结构体的含铜的硅铝酸盐材料的直接合成方法，以及其在催化中的应用

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0432814A1 (fr) * 1989-11-16 1991-06-19 ENIRICERCHE S.p.A. Procédé pour l'alkylation de benzène
WO2011064186A1 (fr) * 2009-11-24 2011-06-03 Basf Se Procédé pour la préparation de zéolites ayant une structure cha
US20120004485A1 (en) * 2010-07-01 2012-01-05 Uop Llc Uzm-5, uzm-5p, and uzm-6 crystalline aluminosilicate zeolites and methods for preparing the same
CN107635921A (zh) * 2015-04-16 2018-01-26 康斯乔最高科学研究公司 具有aei沸石结构体的含铜的硅铝酸盐材料的直接合成方法，以及其在催化中的应用
WO2017100384A1 (fr) * 2015-12-09 2017-06-15 Basf Corporation Matériaux zéolitiques de type cha et procédés pour leur préparation à l'aide de combinaisons de composés cycloalkyl- et éthyltriméthylammonium

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