WO2020225419A1 - Synthèse monotope de matériaux zéolitiques à échange de métal - Google Patents

Synthèse monotope de matériaux zéolitiques à échange de métal Download PDF

Info

Publication number
WO2020225419A1
WO2020225419A1 PCT/EP2020/062860 EP2020062860W WO2020225419A1 WO 2020225419 A1 WO2020225419 A1 WO 2020225419A1 EP 2020062860 W EP2020062860 W EP 2020062860W WO 2020225419 A1 WO2020225419 A1 WO 2020225419A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal
group
mixture
mixtures
zeolitic material
Prior art date
Application number
PCT/EP2020/062860
Other languages
English (en)
Inventor
Carlos Lizandara Pueyo
Stefan STREGE
Klemens Massonne
Andrei-Nicolae PARVULESCU
Ulrich Mueller
Kerstin MUELHEIMS
Stephan A Schunk
Sebastian Schaefer
Alvaro GORDILLO
Roger Ruetz
Robert Mueller
Original Assignee
Basf Se
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Se filed Critical Basf Se
Publication of WO2020225419A1 publication Critical patent/WO2020225419A1/fr

Links

Classifications

    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/06—Washing
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/30—Ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
    • C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
    • 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
    • B01J2229/24—After treatment, characterised by the effect to be obtained to stabilize the molecular sieve structure
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/10—Constitutive chemical elements of heterogeneous catalysts of Group I (IA or IB) of the Periodic Table
    • B01J2523/17—Copper
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the present invention relates to a process for the preparation of a metal-exchanged zeolitic ma terial comprising S1O2 and X2O3, wherein X is a trivalent element, in its framework structure. Further, the present invention relates to metal-exchanged zeolitic materials obtained and/or ob tainable according to the inventive process as disclosed herein. Yet further, the present inven tion relates to the use of metal-exchanged zeolitic materials as disclosed herein.
  • zeolitic materials usually involves two steps, a gelation- and crystallization- step.
  • current needs of the chemical industry, in particular as regards high selective catalysts require controlled design of the zeolite properties like surface properties or atomic dispersion of the active sites. This is quite challenging with the current manufacturing concepts.
  • the synthesis of zeolites usually involves the formation of different metastable intermediates which may be fully or in part amorphous and/or crystalline. These metastable intermediates are very difficult to generate on purpose and handle. Therefore, novel and flexible strategies are needed for the preparation of zeolites.
  • R. Limin et al. disclose in Chemical Communications a study on a designed copper-amine com plex as an efficient template for one-pot synthesis of Cu-SSZ-13 zeolite with excellent activity for selective catalytic reduction of NOx by NH 3 .
  • use of a copper complex of tetra ethylenepentamine is disclosed as structure directing agent.
  • X. Lijuan et al. also disclose a one-pot synthesis of a Cu-SSZ-13 and use of the same organo template as R. Limin et al.
  • the study of X. Lijuan et al. relates to the performance of a Cu-SSZ- 13 catalyst prepared by a one-pot synthesis for the selective catalytic reduction of NOx with
  • EP 2297036 B1 discloses a process for the direct synthesis of Cu containing zeolites having CHA structure, the process comprising preparing an aqueous solution containing at least one source for X 2 O 3 and at least one source for YO 2 , at least one structure directing agent, and at least one Cu source.
  • a combination of trimethyl-1 - adamantylammonium and tetramethylammonium or of trimethyl-1 -adamantylammonium and trimethyl benzylammonium can be used as organotemplate.
  • the present invention targets at the development of a novel route for syn thesizing zeolitic materials at mild conditions and controlled kinetics.
  • the present invention targets at the provision of a cost competitive method for producing zeolitic materials.
  • this approach allows for a controlled formation of precursor species, said species usually being amorphous, and their subsequently controlled crystallization. Further, it has been found that, on the one hand, several process steps can be avoided in order to save resources, such as separate ion exchange-, calcination- and/or spray drying-steps and on the other hand, the formation of zeolites can be done with better space time yield values than in prior art pro Waits. Furthermore, it has been surprisingly been found that the proposed emulsion system was demonstrated as feasible for the synthesis of well-defined zeolitic materials in the range of greater than 20 nm to several micrometers.
  • the present invention relates to a process for the preparation of a metal-exchanged zeolitic material comprising S1O2 and X2O3 in its framework structure, wherein X is a trivalent element, said process comprising
  • the present invention relates to a process for the preparation of a metal-exchanged zeolitic material comprising S1O2 and X2O3 in its framework structure, wherein X is a trivalent element, said process comprising (1 ) preparing a first mixture comprising one or more nonpolar organic solvents, one or more polar pro tic solvents, one or more organotemplates as structure directing agents, one or more bases, and one or more emulsifiers;
  • the present invention relates to a metal-exchanged zeolitic material comprising S1O2 and X2O3 in its framework structure, wherein X is a trivalent element, wherein said metal- exchanged zeolitic material is obtained and/or obtainable according to the process of any one of the embodiments disclosed herein.
  • the present invention relates to a use of a metal-exchanged zeolitic material accord ing 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.
  • the preparation of the second mixture in (4) is conducted under an inert atmosphere, more preferably in an inert atmosphere comprising N2, He, Ar, Ne, or mixtures of two or more thereof, more preferably in an inert atmosphere compris ing N2 and/or Ar, wherein more preferably the second mixture in (4) is conducted under an at mosphere consisting of N2 and/or Ar, preferably of Ar.
  • the addition of the one or more sources of a metal M to the second mixture in (5) is conducted under an inert atmosphere, more preferably in an inert atmosphere comprising N2, He, Ar, Ne, or mixtures of two or more thereof, more preferably in an inert at mosphere comprising N2 and/or Ar, wherein more preferably the addition of the one or more sources of a metal M to the second mixture in (5) is conducted under an atmosphere consisting of N2 and/or Ar, preferably of Ar.
  • the preparation of the second mixture in (4) is conducted under the same inert atmosphere as the addition of the one or more sources of a metal M to the sec ond mixture in (5).
  • the one or more nonpolar organic solvents in (1) are selected from the group consisting of (Cs-Cio)alkanes, (C5- Cio)alkenes, (Cs-Cio)aromatic organic compounds, (C 4 -C 8 )alkylethers, (Ci-C3)alkylhalides, or mixtures of two or more thereof, preferably from the group consisting of (C6-Cio)alkanes, ⁇ CQ- Cio)alkenes, (C 6 -Cio)aromatic organic compounds, (C 4 -C 6 )alkylethers, (Ci-C 2 )alkylhalides, or mixtures of two or more thereof, more preferably from the group consisting of (C 6 -Ce)alkanes, (C 6 -Ce)alkenes, (C 6 -C 8 )aromatic organic compounds, or mixtures of two or more thereof, more preferably from the group consisting of (C 6 -
  • the one or more nonpolar organic solvents in (4) are selected from the group consisting of (Cs-Cio)alkanes, (Cs- Cio)alkenes, (Cs-Cio)aromatic organic compounds, (C4-Ce)alkylethers, (Ci-C3)alkylhalides, or mixtures of two or more thereof, preferably from the group consisting of (C 6 -Cio)alkanes, ⁇ C & - Cio)alkenes, (C 6 -Cio)aromatic organic compounds, (C4-C6)alkylethers, (Ci-C2)alkylhalides, or mixtures of two or more thereof, more preferably from the group consisting of (C 6 -Cs)alkanes, (C 6 -Cs)alkenes, (C 6 -C 8 )aromatic organic compounds, or mixtures of two or more thereof
  • the one or more nonpolar organic solvents in (1 ) are the same as the one or more nonpolar organic solvents in (4).
  • the amount of the one or more nonpolar organic solvents in the mixture obtained in (6) and heated in (7) ranges from 10 to 95 weight- % based on 100 weight- % of the total amount of the one or more nonpolar or ganic solvents, the one or more polar protic solvents, and the one or more emulsifiers, prefera bly from 30 to 85 weight-%, more preferably from 50 to 80 weight-%, more preferably from 60 to 75 weight-%, more preferably from 65 to 72 weight-%, and more preferably from 67 to 69 weight-%.
  • the one or more polar protic solvents are selected from the group consisting of n-hexanol, n-pentanol, n-butanol, isopropanol, propanol, ethanol, methanol, water, and mixtures thereof, more preferably from the group consisting of ethanol, methanol, water, and mixtures thereof. It is particularly preferred that the one or more polar protic solvents com prise water, and more preferably that water is used as the one or more polar protic solvents, preferably deionized water.
  • the amount of the one or more polar protic solvents in the mixture obtained in (6) and heated in (7) ranges from 5 to 90 weight- % based on 100 weight- % of the total amount of the one or more nonpolar organic sol vents, the one or more polar protic solvents, and the one or more emulsifiers, more preferably from 10 to 70 weight-%, more preferably from 15 to 50 weight-%, more preferably from 20 to 40 weight-%, more preferably from 26 to 34 weight-%, more preferably from 25 to 35 weight-%, more preferably from 27 to 33 weight-%, and more preferably from 29 to 31 weight-%.
  • the mixture obtained in (6) and heated in (7) comprises water as the one or more polar protic solvents, wherein the H2O : S1O2 molar ratio of the mixture ranges from 1 to 200, preferably from 3 to 100, more preferably from 5 to 50, more preferably from 7 to 30, more preferably from 9 to 25, more preferably from 10 to 20, more preferably from 1 1 to 16, more preferably from 12 to 14, and more preferably from 12.5 to 13.5.
  • the amount of the one or more polar protic sol vents in the mixture obtained in (6) and heated in (7) ranges from 5 to 90 weight-% based on 100 weight-% of the total amount of the one or more nonpolar organic solvents, the one or more polar protic solvents, and the one or more emulsifiers, more preferably from 10 to 70 weight-%, more preferably from 15 to 50 weight-%, more preferably from 20 to 40 weight-%, more prefer ably from 25 to 35 weight-%, more preferably from 27 to 33 weight-%, and more preferably from 29 to 31 weight-%, the mixture obtained in (6) and heated in (7) comprises water as the one or more polar protic solvents, wherein the H2O : S1O2 molar ratio of the mixture ranges from 1 to 200, preferably from 3 to 100, more preferably from 5 to 50, more preferably from 7 to 30, more preferably from 9 to 25, more preferably from 10 to 20, more preferably from 1 1 to 16, more preferably
  • the one or more organotem plates in (1 ) comprise 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, wherein preferably R 1 , R 2 , and R 3 independently from one another stand for al kyl, and wherein R 4 stands for adamantyl.
  • the one or more tetraalkylammonium cation R 1 R 2 R 3 R 4 N + -containing compounds comprise one or more 1 -adamantyltri(Ci-C 3 )alkylammonium compounds, more preferably one or more 1 -adamantyltri(Ci-C 2 )alkylammonium compounds, more preferably one or more compounds selected from the group consisting of 1 -adamantyltriethylammonium com pounds, 1 -adamantyldiethyl-methylalkylammonium compounds, 1 -adamantylethyl-dimethyl- ammonium compounds, 1 -adamantyltrimethylammonium compounds, and mixtures of two or more thereof.
  • the one or more tetraalkylammonium cation R 1 R 2 R 3 R 4 N + -containing compounds comprise one or more 1 -adamantyltrimethylammonium compounds, wherein more preferably the one or more tetraalkylammonium cation R 1 R 2 R 3 R 4 N + - containing compounds consist of one or more 1 -adamantyltrimethylammonium compounds.
  • the one or more organotemplates in (1 ) comprise one or more
  • 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 cycloalkyl, preferably for optionally heterocyclic 5- to 8-membered cycloalkyl, preferably for 5- to 7-membered cycloalkyl, more preferably for 5- or 6-membered cycloalkyl, wherein even more preferably R 4 stands for optionally heterocyclic 6-membered cycloalkyl, and more preferably for cyclohexyl.
  • the one or more organotemplates in (1 ) comprise one or more
  • the one or more tetraalkylammonium cation R 1 R 2 R 3 R 4 N + -containing compounds comprise one or more /V,/V,/V-tri(Ci-C 4 )alkyl-(C 5 -C 7 )cycloalkylammonium compounds, preferably one or more /V,/V,/V-tri(Ci-C3)alkyl-(C5-C6)cycloalkylammonium compounds, more preferably one or more /V,/V,/V-tri(Ci-C2)alkyl-(C5-C6)cycloalkylammonium compounds, more preferably one or more /V,/V,/V-tri(Ci-C2)alkyl-(C5-C6)cycloalkylammonium compounds, more preferably one or more /V,/V,/V-tri(Ci-C2)alkyl-(C5-C6)cycloalkylammonium compounds, more preferably one or more
  • R 1 R 2 R 3 R 4 N + -containing compounds consist of one or more N,N,N- trimethyl-cyclohexylammonium compounds.
  • the one or more organotemplates in (1 ) comprise one or more
  • 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 adamantly, it is preferred that R 1 , R 2 , and R 3 independently from one another stand for optionally branched (Ci-Ce)alkyl, preferably (Ci-Cs)alkyl, more preferably (Ci-C 4 )alkyl, and more preferably for optionally branched (Ci-C3)alkyl, wherein more preferably R 1 , R 2 , and R 3 independently from one another stand for methyl or ethyl, wherein more preferably R 1 , R 2 , and R 3 stand for methyl.
  • optionally branched (Ci-Ce)alkyl preferably (Ci-Cs)alkyl, more preferably (Ci-C 4 )alkyl, and more preferably for optionally branched (Ci-C3)al
  • the one or more organotemplates in (1 ) comprise 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, more preferably for optionally branched (Ci-Ce)alkyl, more preferably (Ci-Cs)alkyl, more preferably (C2-C4)alkyl, and more preferably for optionally branched (C2- C3)alkyl, wherein more preferably R 1 , R 2 , R 3 , and R 4 independently from one another stand for ethyl or propyl, wherein more preferably R 1 , R 2 , R 3 , and R 4 stand for propyl, preferably for n- p ropy I.
  • the one or more organotemplates in (1 ) 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 preferably stands for adamantyl
  • the one or more tetraalkylammonium cation R 1 R 2 R 3 R 4 N + -containing compounds independently of one another are salts, more preferably one or more salts selected from the group consisting of halides, preferably chloride and/or bromide, more preferably chloride, hy droxide, sulfate, nitrate, phosphate, acetate, and mixtures of two or more thereof, more prefera bly from the group consisting of chloride, hydroxide, sulfate, and mixtures of two or more there of, wherein more preferably the one or more organo
  • the one or more organotemplates in (1 ) 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 adamantly
  • the mixture obtained in (6) and heated in (7) displays a molar ratio of the one or more tetraalkylammonium cation R 1 R 2 R 3 R 4 N + -containing compounds to the one or more sources of SiC>2 calculated as SiC>2 in the range of from 0.01 to 2.0, more preferably from 0.05 to 1.0, more preferably from 0.06 to to 0.6, more preferably from 0.07 to 0.55, more preferably from 0.08 to 0.5, more preferably from 0.1 to 0.3, more preferably from 0.12 to 0.25, more preferably from 0.15 to 0.22, more preferably from 0.16 to 0.2, more
  • the S1O2 : X2O3 molar ratio of the mixture obtained in (6) and heated in (7) is in the range of from 1 to 500, more preferably from 2 to 200, more preferably from 5 to 150, more preferably from 10 to 100, more preferably from 15 to 50, more preferably from 19 to 45, more preferably from 20 to 40, more preferably from 24 to 35, more preferably from 25 to 33, and more preferably from 27 to 29.
  • the one or more emulsifiers are selected from the group consisting of ionic and nonionic surfactants, including mixtures thereof, more preferably from the group consisting of nonionic surfactants.
  • the one or more emulsifiers are selected from the group consisting of ionic and nonionic surfactants, including mixtures thereof
  • the ionic surfactants comprise one or more anionic surfactants, more preferably one or more anionic surfactants se lected from the group consisting of salts of (C 6 -Cie)sulfate, (C 6 -Cie)ethersulfate, ⁇ C & - Cie)sulfonate, (C 6 -Ci 8 )sulfosuccinate (C 6 -Cis)phosphate, (C 6 -Ci 8 )carboxylate, and mixtures of two or more thereof, more preferably from the group consisting of salts of (C 8 -Ci 6 )sulfate, (Cs- Ci 6 )ethersulfate, (C 8 -Ci 6 )sulfonate, (C 8 -Ci 6 )sulfosuccinate,
  • the ionic surfac tants comprise one or more cationic surfactants, preferably one or more cationic surfactants selected from the group consisting of primary, secondary, tertiary, and quaternary ammonium compounds, including mixtures of two or more thereof, wherein more preferably the cationic surfactants comprise one or more quaternary ammonium compounds, preferably selected from the group consisting of salts of (C 8 -Ci 8 )trimethylammonium, (C 8 -Ci 8 )pyridinium, benzalkonium, benzethonium, dimethyldioctadecylammonium, cetrimonium, dioctadecyldimethylammonium, and mixtures of two or more thereof, more preferably from the group consisting of salts of cetyltrimethylam
  • the one or more emulsifiers are selected from the group consisting of ionic and nonionic surfactants, including mixtures thereof
  • the ionic surfac tants comprise one or more zwitterionic surfactants, more preferably one or more betaines, wherein more preferably the ionic surfactants comprise cocamidopropylbetaine or alkyldime- thylaminoxide.
  • the nonionic surfac tants are selected from the group consisting of (C 8 -C 22 )alcohols, (C 6 -C 2 o)alcohol ethoxylates with 1 to 8 ethylene oxide units, (C6-C2o)alkyl polyglycosides, polyoxyethylene glycol alkyl ethers, polyoxypropylene glycol alkyl ethers, glucoside alkyl ethers, polyoxyethylene glycol al- kylphenol ethers, glycerol alkyl esters, sorbitan alkyl esters, polyoxyethylene glycol sorbitan alkyl esters, cocamide monoethanolamine, cocamide diethanolamine, dodecyldimethylamine oxide, block copolymers of polyethylene glycol and polypropylene glycol, polyethoxy
  • the one or more nonionic surfactants are selected from the group con sisting of (Ci 6 -Ci 8 )alcohols, (Ci6-Cis)alcohol ethoxylates with 2 to 6 ethylene oxide units, (Ce- Ci4)alkyl polyglycosides, preferably cetyl alcohol, stearyl alcohol, oleyl alcohol, and mixtures of two or more thereof, octaethylene glycol monododecyl ether and/or pentaethylene glycol mono dodecyl ether, polyoxypropylene glycol alkyl ethers, decyl glucoside, lauryl glucoside, myristil glucoside, octyl glucoside, polyoxyethylene glycol octylphenol ethers, nonoxynol-9, glyceryl laurate, polyglycerol polyricinoleate, sorbitan monolaurate, sorbitan monopalm
  • polyg lyceryl-2-d i polyhyd roxystearate diglyceryl- distearate, triglyceryl-distearate, polyoxyethylene (10) oleyl ether, polyoxyethylene (20) oleyl ether, and mixtures of two or more thereof,
  • nonionic surfactant comprises polyoxyethylene (10) oleyl ether and/or polyoxyethylene (20) oleyl ether.
  • the amount of the amount of the one or more emulsifiers in the mixture obtained in (6) and heated in (7) is in the range of from 0.1 to 10 weight- % based on 100 weight- % of the total amount of the one or more nonpolar organic solvents, the one or more polar protic solvents, and the one or more emulsifiers, more prefera- bly from 0.3 to 5 weight-%, more preferably from 0.5 to 3 weight-%, and more preferably from 1 to 2 weight-%.
  • the one or more bases comprise one or more metal hydroxides and/or one or more metal hydroxide precursors, more preferably one or more metal hydroxides, more preferably one or more metal hydroxides selected from the group consisting of potassium hydroxide, sodium hydroxide, magnesium hydroxide, calcium hydroxide, iron hydroxide, alumi num hydroxide, and copper hydroxide, wherein more preferably the one or more bases com prise sodium hydroxide.
  • emulsification in (2) is achieved by agitation, more preferably by stirring and/or sonication, and more preferably by stirring.
  • emulsification in (2) is achieved by use of a homogenizer, more pref erably with a rotor-stator homogenizer, with an ultrasonic homogenizer, with a high pressure homogenizer, by microfluidic systems, or by membrane emulsification, more preferably with a high pressure homogenizer or with a rotor-stator homogenizer, and more preferably with a rotor- stator homogenizer.
  • stirring is performed at a speed in the range of from 500 to 35,000, more prefera bly from 1 ,000 to 32,000, more preferably from 3,000 to 30,000, more preferably from 5,000 to 28,000, more preferably from 7,000 to 26,000, more preferably from 9,000 to 22,000, more preferably from 1 1 ,000 to 20,000, more preferably from 13,000 to 18,000, and more preferably from 15,000 to 16,000.
  • emulsification in (2) is conducted for a period in the range of from 0.1 to 10 min, more preferably from 0.2 to 6 min, more preferably from 0.4 to 4 min, more preferably from 0.6 to 3 min, more preferably from 0.8 to 2.5 min, more preferably from 1 to 2 min, more preferably from 1.2 to 1.8 min, and more preferably from 1.4 to 1.6 min.
  • X is selected from the group consisting of Al, B, In, Ga, and combinations of two or more thereof. It is particularly preferred that X is Al.
  • the one or more sources of X2O3 comprises one or more compounds selected from the group consisting of aluminum salts and aluminum alkoxides, more preferably from the group consisting of aluminates of an alkali metal, aluminum hydroxides, aluminum alkoxides, and mixtures of two or more thereof, wherein more preferably the one or more sources of X2O3 comprises one or more aluminum alkoxides AI(OR)3, wherein R stands for op tionally branched (Ci-Ce)alkyl, preferably (Ci-Cs)alkyl, more preferably (Ci-C 4 )alkyl, and more preferably for optionally branched (Ci-C3)alkyl, wherein more preferably R stands for methyl, ethyl, n-propyl, isopropyl, or mixtures of two or more thereof, more preferably for ethyl, n-propyl, isopropyl, or mixtures of two or more thereof, more preferably for
  • the one or more sources of X2O3 comprises one or more compounds selected from the group consisting of aluminum salts and aluminum alkoxides, preferably from the group consisting of aluminates of an alkali metal
  • the alkali metal is se lected from the group consisting of Li, Na, K, Rb, and Cs, wherein more preferably the alkali metal is Na and/or K, and wherein even more preferably the alkali metal is Na.
  • the metal M is selected from the group consisting of Mg, Ti, Cu, Co, Cr, Ni, Fe, Mo, Mn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, and mixtures of two or more thereof, more preferably from the group consisting of Ti, Cu, Fe, Rh, Pd, Pt, and mixtures of two or more thereof, wherein more preferably the metal M comprises Cu and/or Fe, preferably Cu, wherein more preferably the metal M is Cu and/or Fe, preferably Cu.
  • the one or more sources of a metal M is selected from the group consisting of metal salts, metal alkoxides, metal carbox yl ates, and mixtures of two or more thereof, wherein more preferably the one or more sources of a metal M comprises one or more metal alkoxides and/or metal carboxyl ates, wherein more preferably one or more metal alkoxides are employed as the one or more sources of a metal M.
  • the one or more sources of a metal M is selected from the group consisting of metal salts, metal alkoxides, metal carboxylates, and mixtures of two or more thereof
  • the one or more metal salts are selected from the group consisting of halides, hy droxides, sulfates, nitrates, phosphates, acetates, octadecanoate, 2-(2-methoxy- ethoxy)ethanolate, and mixtures of two or more thereof, more preferably from the group consist ing of chlorides, bromides, sulfates, nitrates, acetates, octadecanoate, 2-(2-methoxy- ethoxy)ethanolate, and mixtures of two or more thereof, more preferably from the group consist ing of bromides, nitrates, octadecanoate, 2-(2-methoxyethoxy)ethanolate, and mixtures of two or more thereof, more preferably from the group
  • the one or more sources of a metal M is selected from the group con sisting of metal salts, metal alkoxides, metal carboxylates, and mixtures of two or more thereof
  • the one or more metal alkoxides comprise a trivalent metal ion and a divalent metal ion, wherein the trivalent metal ion is selected from the group consisting of Al, Ga, In, Fe, Co, Mn, Cr, La, Pr, Ce, Nd, Sm, Gd, Dy, Ho, Er, Yb, Lu, Sc, Y, and combinations of two or more thereof
  • the divalent metal ion is selected from the group consisting of Mg, Ca, Sr, Ba, Zn, Cd, Cu, Ni, Co, Mn, Be, Zr, and combinations of two or more thereof
  • the trivalent metal ion is selected from the group consisting of Al, Ga, In, Fe, Co, Mn, Cr, La, Pr, Ce, Y, and combinations of
  • the divalent metal ion is selected from the group consisting of Cu, Ni, Co, and combinations of two or more thereof,
  • the one or more metal alkoxides comprises Cu and Al as metal ions, wherein more preferably the metal ions in the one or more alkoxides are Cu and Al.
  • the one or more sources of a metal M is selected from the group con sisting of metal salts, metal alkoxides, metal carboxylates, and mixtures of two or more thereof
  • the alkoxides are selected from the group consisting of (Ci-Cio)alkoxides, more preferably of (C3-Cs)alkoxides, more preferably of (Cs-C 7 )alkoxides, where more prefera bly the alkoxides are C6-alkoxides, preferably alkoxides of hexanol, and more preferably alkox ides of n-hexanol.
  • the one or more sources of a metal M is selected from the group con sisting of metal salts, metal alkoxides, metal carboxylates, and mixtures of two or more thereof
  • the carboxylates are selected from the group consisting of (C 10 -C 25 ) carbox ylates, more preferably of (C 16 -C 20 ) carboxylates, more preferably of (C 17 -C 19 ) carboxylates, wherein more preferably the carboxylates are octadecanoate.
  • the one or more sources of a metal M is selected from the group con sisting of metal salts, metal alkoxides, and mixtures of two or more thereof, it is particularly pre ferred that the one or more metal alkoxides comprise CuAh(OR) 6 , wherein R is hexyl, preferably n-hexyl.
  • the one or more sources of S1O 2 comprises one or more compounds selected from the group consisting of silicas, silicates, and mixtures thereof, more preferably from the group consisting of fumed silica, silica hydrosols, reactive amorphous solid silicas, silica gel, silicic acid, water glass, sodium metasilicate hydrate, sesquisilicate, disilicate, colloidal silica, pyrogenic silica, silicic acid esters, tetraalkoxysilanes, and mixtures of two or more thereof,
  • silica more preferably from the group consisting of fumed silica, silica hydrosols, silica gel, silicic acid, water glass, colloidal silica, pyrogenic silica, silicic acid esters, tetraalkoxysilanes, and mixtures of two or more thereof,
  • silica hydrosols preferably from the group consisting of silica hydrosols, silicic acid, water glass, colloidal silica, silicic acid esters, tetraalkoxysilanes, and mixtures of two or more thereof,
  • heating in (7) no particular restriction applies especially as regards the temperature at which the mixture obtained in (6) is heated. It is preferred that heating in (7) is conducted at a temperature in the range of from 80 to 260°C, more preferably from 100 to 240°C, more prefer ably from 120 to 220°C, more preferably from 140 to 200°C, more preferably from 160 to 180°C, and more preferably from 165 to 175°C.
  • heating in (7) is conducted for a period in the range of from 0.5 to 120 h, pref erably from 1 to 1 14 h, more preferably from 3 to 108 h, more preferably from 6 to 102 h, more preferably from 12 to 96 h, more preferably from 18 to 84 h, more preferably from 24 to 72 h, more preferably from 30 to 66 h, more preferably from 36 to 60 h, more preferably from 42 to 54 h, more preferably from 45 to 51 h, and more preferably from 47 to 49 h.
  • heating in (7) is conducted under autogenous pressure.
  • inventive pro cess may comprise further process steps. It is preferred that the process further comprises
  • isolation in (8) is achieved by filtration and/or centrifugation, preferably by filtration.
  • washing in (9) is conducted with a solvent system comprising one or more solvents, wherein preferably the one or more solvents are selected from the group consisting of polar protic sol vents, polar aprotic solvents, and mixtures thereof, more preferably from the group consisting of n-butanol, isopropanol, propanol, ethanol, methanol, water, acetone, and mixtures thereof, more preferably from the group consisting of ethanol, methanol, water, acetone, and mixtures thereof, wherein more preferably the solvent system comprises water or acetone, and wherein more preferably water is used as the solvent system, preferably deionized water.
  • a solvent system comprising one or more solvents, wherein preferably the one or more solvents are selected from the group consisting of polar protic sol vents, polar aprotic solvents, and mixtures thereof, more preferably from the group consisting of n-butanol, isopropanol, propanol,
  • dry ing in (10) is conducted at a temperature in the range of from 20 to 160°C, more preferably from 30 to 140°C, more preferably from 40 to 120°C, more preferably from 50 to 110°C, more prefer ably from 60 to 100°C, more preferably from 70 to 90°C, and more preferably from 75 to 85°C.
  • calcining in (11 ) is conducted at a temperature in the range of from 300 to 750°C, more prefera bly from 325 to 650°C, more preferably from 350 to 600°C, more preferably from 375 to 575 °C, more preferably from 375 to 550°C, more preferably from 400 to 500°C, and more preferably from 425 to 475°C.
  • the mixture obtained in (6) and heated in (7) further comprises seed crystals, wherein the seed crystals preferably comprise one or more zeolitic materials, more preferably one or more zeolitic materials having the framework structure type of the zeolitic ma terial obtained in (7), wherein more preferably the one or more zeolitic materials comprise SSZ- 13 and/or chabazite, preferably SSZ-13.
  • the amount of seed crystals in the mixture is in the range of from 0.1 to 20 weight- % based on 100 weight- % of the one or more sources of SiC>2, calculated as S1O2, and the one or more sources of X2O3, calculated as X2O3, contained in the mixture obtained in (6), more preferably from 0.3 to 15 weight-%, more preferably from 0.5 to 10 weight-%, more pref erably from 1 to 8 weight-%, more preferably from 3 to 7 weight-%, more preferably from 4 to 6 weight-%, and more preferably from 4.5 to 5.5 weight-%.
  • the seed crystals may be added at any point in the process up to and including step (6).
  • the seed crystals may be added in any one of steps (1 ), (3), (4), (5), or (6), or in two or more of said steps, wherein it is preferred according to the present invention that the seed crystals are added as a further component during the prepara tion of the first mixture in (1 ).
  • (7) is conducted in a batch mode and/or in a continuous mode.
  • the process is conducted in a batch mode and/or in a continuous mode.
  • (7) comprises
  • heating in (ii) is conducted at a temperature in the range of from 100 to 300°C, more preferably of from 100 to 280°C, more preferably of from 150 to 270°C, more preferably of from 180 to 260°C, more preferably of from 200 to 250°C, more preferably of from 210 to 240°C, and more preferably of from 220 to 235°C.
  • (7) comprises (i) and (ii)
  • the mixture is fed into the continuous flow reactor at a liquid hourly space velocity in the range of from 0.3 to 20 IT 1 , more preferably of from 0.05 to 10 IT 1 , more preferably from 0.1 to 5 IT 1 , more preferably from 0.2 to 3 IT 1 , more preferably from 0.4 to 2 IT 1 , more preferably from 0.6 to 1.5 IT 1 , more prefera bly from 0.8 to 1.2 IT 1 , and more preferably from 0.9 to 1 IT 1 .
  • the mixture obtained in (6) is continuously fed in (i) and heated in (ii) for at least 1 h, more preferably for a duration in the range of from 3 h to 360 d, more preferably from 6 h to 120 d, more preferably from 12 h to 90 d, more preferably from 18 h to 60 d, more preferably from 1 to 30 d, more preferably from 1 .5 to 25 d, more preferably from 2 to 20 d, more preferably from 2.5 to 15 d, more preferably from 3 to 12 d, more preferably from 3.5 to 8 d, and more preferably from 4 to 6 d.
  • the volume of the contin uous flow reactor is in the range of from 50 cm 3 to 75 m 3 , preferably of from 50 cm 3 to 3 m 3 , preferably from 55 cm 3 to 1 m 3 , more preferably from 60 cm 3 to 0.7 m 3 , more preferably from 65 cm 3 to 0.3 m 3 , more preferably from 70 cm 3 to 0.1 m 3 , more preferably from 75 to 70,000 cm 3 , more preferably from 80 to 50,000 cm 3 , more preferably from 85 to 30,000 cm 3 , more preferably from 90 to 10,000 cm 3 , more preferably from 95 to 7,000 cm 3 , more preferably from 100 to 5,000 cm 3 , more preferably from 105 to 3,000 cm 3 , more preferably from 1 10 to 1 ,000 cm 3 , more preferably from 1 15 to 700 cm 3 , more preferably from 120 to 500 cm 3 , more preferably from 125 to 350 cm 3 , more preferably
  • the continuous flow reac tor is selected among a tubular reactor, a ring reactor, and a continuously oscillating reactor, more preferably among a plain tubular reactor, a tubular membrane reactor, a tubular reactor with Coanda effect, a ring reactor, a continuously oscillating baffled reactor, and combinations thereof, wherein more preferably the continuous flow reactor is a plain tubular reactor and/or a ring reactor, wherein more preferably the continuous flow reactor is a plain tubular reactor.
  • the continuous flow reac tor is a tubular reactor, and wherein at least a portion of the tubular reactor is of a regular cylin drical form having a constant inner diameter perpendicular to the direction of flow, wherein the inner diameter is preferably in the range of from 2 to 1200 mm, more preferably from 3 to 800 mm, more preferably from 3 to 500 mm, more preferably from 4 to 200 mm, more preferably from 4 to 100 mm, more preferably from 4.5 to 50 mm, more preferably from 4.5 to 30 mm, more preferably from 5 to 15 mm, more preferably from 5 to 10 mm, more preferably from 5.5 to 8 mm, and more preferably from 5.5 to 6.5 mm.
  • the continuous flow reac tor has a length in the range of from 0.2 to 5,000 m, more preferably from 0.5 to 3,000 m, more preferably from 1 to 1 ,000 m more preferably from 3 to 500 m more preferably from 3.5 to 200 m, more preferably from 3.5 to 100 m, more preferably from 4 to 50 m, more preferably from 4 to 30 m, more preferably from 4.5 to 20 m, more preferably from 4.5 to 15 m, more preferably from 5 to 10 m, and more preferably from 5 to 7 m.
  • the wall of the continuous flow reactor is made of a metallic material
  • the metallic material comprises one or more metals selected from the group consisting of Ta, Cr, Fe, Ni, Cu, Al, Mo, and combinations and/or alloys of two or more thereof, preferably from the group consisting of Ta, Cr, Fe, Ni, Mo, and combinations and/or alloys of two or more thereof, more preferably from the group consisting of Cr, Fe, Ni, Mo, and combinations and/or alloys of two or more thereof wherein preferably the metallic material comprises a nickel alloy, a nickel-molybdenum alloy, and more preferably a nickel-molybdenum-chromium alloy.
  • the surface of the inner wall of the continuous flow reactor is lined with an organic polymer material
  • the organic polymer material preferably comprises one or more polymers selected from the group consisting of fluorinated polyalkylenes and mixtures of two or more thereof, preferably from the group con sisting of (C2-C3)polyalkylenes and mixtures of two or more thereof, preferably from the group consisting of fluorinated polyethylenes and mixtures of two or more thereof, wherein more pref erably the polymer material comprises poly(tetrafluoroethylene), wherein more preferably the inner wall of the continuous flow reactor is lined with poly(tetrafluoroethylene).
  • the continuous flow reac tor is straight and/or comprises one or more curves with respect to the direction of flow, wherein more preferably the continuous flow reactor is straight and/or has a coiled form with respect to the direction of flow.
  • (7) comprises (i) and (ii)
  • the pressure is in the range of from 0.5 to 15 MPa, more preferably in the range of from 1 to 10 MPa, more preferably from 2 to 8 MPa, more preferably from 3 to 7 MPa, more preferably from 3.5 to 6.5 MPa, more preferably from 4 to 6 MPa, more preferably from 4.5 to 5.5 MPa, and more preferably from 4.8 to 5.2 MPa.
  • the continuous flow reac tor consists of a single stage. Further in the case where (7) comprises (i) and (ii), it is preferred that no matter is added to and/or removed from the mixture during its passage through the continuous flow reactor in (ii), wherein preferably no matter is added, wherein more preferably no matter is added and no mat ter is removed from the mixture during its passage through the continuous flow reactor in (ii).
  • the mixture ob tained in (6) is aged at a temperature in the range of from 40 to 120°C, more preferably from 50 to 1 10°C, more preferably from 60 to 105°C, more preferably from 70 to 100°C, more preferably from 75 to 95°C, and more preferably from 80 to 90°C.
  • the mixture ob tained in (6) is aged for a duration ranging from 1 to 72 h, more preferably from 6 to 60 h, more preferably from 12 to 54 h, more preferably from 14 to 42 h, more preferably from 16 to 36 h, more preferably from 18 to 32 h, and more preferably from 20 to 28 h.
  • (7) further comprises (iii) quenching the reaction product effluent continuously exiting the reactor in (ii) with a liquid comprising one or more solvents and/or via expansion of the reaction product effluent.
  • the liquid comprises one or more solvents selected from the group consisting of polar protic solvents and mixtures thereof, more preferably from the group consisting of n-hexanol, n-pentanol, n-butanol, isopropanol, propanol, ethanol, methanol, water, and mixtures thereof, more preferably from the group con sisting of ethanol, methanol, water, and mixtures thereof, wherein more preferably the liquid comprises water, and wherein more preferably water is used as the liquid, preferably deionized water.
  • solvents selected from the group consisting of polar protic solvents and mixtures thereof, more preferably from the group consisting of n-hexanol, n-pentanol, n-butanol, isopropanol, propanol, ethanol, methanol, water, and mixtures thereof, more preferably from the group con sisting of ethanol, methanol, water, and mixtures thereof, wherein more preferably
  • the mean particle size D50 by volume as determined according to ISO 13320:2009 of the zeolitic material obtained in (7) is of at least 0.5 pm, and is more prefer ably in the range of from 0.5 to 1.5 pm, more preferably in the range of from 0.6 to 1 .0 pm, and more preferably in the range of from 0.6 to 0.8 pm.
  • the present invention relates to a metal-exchanged zeolitic material comprising S1O2 and X2O3 in its framework structure, wherein X is a trivalent element, wherein said metal- exchanged zeolitic material is obtained and/or obtainable according to the process of any one of the embodiments disclosed herein.
  • the metal-exchanged zeolitic material has a framework struc ture type selected from the group consisting of MFI, BE A, CHA, AEI, MWW, LEV, GME, FAU, FER, MEL, MOR, and intergrowth structures thereof, more preferably from the group consisting of MFI, BE A, CHA, AEI, MWW, and intergrowth structures thereof, more preferably from the group consisting of BE A, CHA, AEI, M FI, and intergrowth structures thereof, wherein more pref- erably the zeolitic material has a CHA and/or AEI and/or MFI type framework structure, prefera bly a CHA or MFI type framework structure.
  • a framework struc ture type selected from the group consisting of MFI, BE A, CHA, AEI, MWW, LEV, GME, FAU, FER, MEL, MOR, and intergrowth structures thereof, more preferably from the group consisting of MFI, BE A
  • the metal-exchanged zeolitic material is metal- exchanged SSZ-13 and/or chabazite, more preferably metal-exchanged SSZ-13.
  • the metal-exchanged zeolitic material is metal-exchanged Silicalite, ZSM-5, [Fe-Si-0]-M FI, [Ga-Si-0]-M FI, [As-Si-0]-M FI, 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 , FeS-1 , or a mixture of two or more thereof, more preferably Silicalite, ZSM-5, AMS-1 B, AZ-1 , Encilite, FZ-1 , LZ-105, Mutinaite, N U-4, N U-5, TS-1 , TSZ, TSZ-III,
  • the present invention relates to a use of a metal-exchanged 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, preferably as a catalyst or a precursor thereof and/or as a catalyst support or a precur sor thereof, more preferably as a catalyst or a precursor thereof, more preferably as a catalyst for the selective catalytic reduction (SCR) of nitrogen oxides NO x ; for the storage and/or adsorp tion 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 preferably in m
  • a process for the preparation of a metal-exchanged zeolitic material comprising S1O 2 and X 2 O 3 in its framework structure, wherein X is a trivalent element, said process comprising (1 ) preparing a first mixture comprising one or more nonpolar organic solvents, one or more polar protic solvents, one or more organotemplates as structure directing agents, one or more bases, and optionally one or more emulsifiers;
  • the one or more nonpolar organic solvents in (1 ) and (4) are selected from the group consisting of (C5-Cio)alkanes, (Cs-Cio)alkenes, (Cs-Cio)aromatic organic compounds, (C4- Ce)alkylethers, (Ci-C3)alkylhalides, or mixtures of two or more thereof, preferably from the group consisting of (C 6 -Cio)alkanes, (C 6 -Cio)alkenes, (C 6 -Cio)aromatic organic com pounds, (C4-C6)alkylethers, (Ci-C2)alkylhalides, or mixtures of two or more thereof, prefer ably from the group consisting of (C 6 -Ce)alkanes, (C 6 -Ce)alkenes, (C 6 -C 8 )aromatic organic compounds, or mixtures of two or more thereof
  • any one of embodiments 1 to 4 wherein the one or more polar protic sol vents are selected from the group consisting of n-hexanol, n-pentanol, n-butanol, isopro panol, propanol, ethanol, methanol, water, and mixtures thereof,
  • polar protic solvents preferably from the group consisting of ethanol, methanol, water, and mixtures thereof, wherein more preferably the one or more polar protic solvents comprise water, and where in more preferably water is used as the one or more polar protic solvents, preferably de ionized water.
  • the one or more organotemplates in (1 ) comprise 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, wherein preferably R 1 , R 2 , and R 3 independently from one another stand for alkyl, and wherein R 4 stands for adamantyl.
  • any one of embodiments 1 to 8, wherein the one or more tetraalkylammo nium cation R 1 R 2 R 3 R 4 N + -containing compounds comprise one or more 1 -adamantyltri(Ci- C 3 )alkylammonium compounds, preferably one or more 1 -adamantyltri(Ci-C2)alkyl- ammonium compounds, more preferably one or more compounds selected from the group consisting of 1 -adamantyl triethylammonium compounds, 1 -adamantyldiethyl-methylalkyl- ammonium compounds, 1 -adamantylethyl-dimethylammonium compounds, 1 - adamantyltrimethylammonium compounds, and mixtures of two or more thereof, wherein more preferably the one or more tetraalkylammonium cation R 1 R 2 R 3 R 4 N + - containing compounds comprise one or more 1 -adamantyltri
  • R 1 R 2 R 3 R 4 N + - containing compounds consist of one or more 1 -adamantyltrimethylammonium com pounds.
  • the one or more organotemplates in (1 ) comprise one or more tetraalkylammonium cation R 1 R 2 R 3 R 4 N + -containing com pounds, wherein R 1 , R 2 , and R 3 independently from one another stand for alkyl, and wherein R 4 stands for cycloalkyl, preferably for optionally heterocyclic 5- to 8-membered cycloalkyl, preferably for 5- to 7-membered cycloalkyl, more preferably for 5- or 6- membered cycloalkyl, wherein even more preferably R 4 stands for optionally heterocyclic 6-membered cycloalkyl, and more preferably for cyclohexyl.
  • 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(Ci-C 4 )alkyl-(C 5 - C 7 )cycloalkylammonium compounds, preferably one or more TV, TV, V-tri (C i -C3)al kyl-(Cs- C6)cycloalkylammonium compounds, more preferably one or more TV, TV, TV-tri(Ci-C2)alkyl- (C 5 -C 6 )cycloalkylammonium compounds, more preferably one or more TV, TV, TV-tri (C i - C 2 )alkyl-cyclopentylammonium and/or one or more TV, TV, TV-tri(Ci-C2)alkyl- cyclohexylammonium compounds, more preferably one or more compounds selected from /V,/V,/V
  • the one or more organotemplates in (1 ) comprise 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, prefer ably for optionally branched (Ci-Ce)alkyl, preferably (Ci-Cs)alkyl, more preferably (C2- C4)alkyl, and more preferably for optionally branched (C2-C3)alkyl, wherein more prefera bly R 1 , R 2 , R 3 , and R 4 independently from one another stand for ethyl or propyl, wherein more preferably R 1 , R 2 , R 3 , and R 4 stand for propyl, preferably for n-propyl.
  • R 1 R 2 R 3 R 4 N + -containing compounds are salts, preferably one or more salts selected from the group consisting of halides, preferably chloride and/or bromide, more preferably chloride, hydroxide, sulfate, nitrate, phosphate, acetate, and mixtures of two or more thereof, more preferably from the group consisting of chloride, hydroxide, sulfate, and mixtures of two or more thereof, wherein more preferably the one or more organotem plate compounds are hydroxides and/or chlorides, and even more preferably hydroxides.
  • emulsifiers are selected from the group consisting of ionic and nonionic surfactants, including mixtures thereof, preferably from the group consisting of nonionic surfactants.
  • the ionic surfactants comprise one or more ani onic surfactants, preferably one or more anionic surfactants selected from the group con sisting of salts of (C 6 -Cis)sulfate, (C 6 -Cie)ethersulfate, (C 6 -Ci 8 )sulfonate, ⁇ C & - Ci 8 )sulfosuccinate (C 6 -Cis)phosphate, (C 6 -Ci 8 )carboxylate, and mixtures of two or more thereof, more preferably from the group consisting of salts of (C 8 -Ci 6 )sulfate, (Ce- Ci 6 )ethersulfate, (C 8 -Ci 6 )sulfonate, (C 8 -Ci 6 )sulfosuccinate, (C 8 -Ci 6 )phosphate, (Ce- Ci 6 )carboxylate, and mixtures of two or more thereof, more
  • the ionic surfactants comprise one or more cationic surfactants, preferably one or more cationic surfactants selected from the group consisting of primary, secondary, tertiary, and quaternary ammonium compounds, includ ing mixtures of two or more thereof, wherein more preferably the cationic surfactants comprise one or more quaternary ammonium compounds, preferably selected from the group consisting of salts of (C 8 -Ci 8 )trimethylammonium, (C 8 -Ci 8 )pyridinium, benzalkoni- um, benzethonium, dimethyldioctadecylammonium, cetrimonium, dioctadecyldime- thylammonium, and mixtures of two or more thereof, more preferably from the group con sisting of salts of cetyltrimethylammonium, dodecyltrimethylammonium, cetylpyridinium, benzalkon
  • the ionic surfactants comprise one or more zwitterionic surfactants, preferably one or more betaines, wherein more pref erably the ionic surfactants comprise cocamidopropyl betaine or alkyldimethylaminoxide.
  • nonionic surfactants are selected from the group consisting of (C8-C22)alcohols, (C6-C2o)alcohol ethoxylates with 1 to 8 ethylene oxide units, (C6-C2o)alkyl polyglycosides, polyoxyethylene glycol alkyl ethers, polyoxypropylene glycol alkyl ethers, glucoside alkyl ethers, polyoxyethylene glycol al- kylphenol ethers, glycerol alkyl esters, sorbitan alkyl esters, polyoxyethylene glycol sorbi- tan alkyl esters, cocamide monoethanolamine, cocamide diethanolamine, dodecyldime- thylamine oxide, block copolymers of polyethylene glycol and polypropylene glycol, poly- ethoxylated tallow amine, and mixtures of two or more thereof,
  • the one or more nonionic surfactants are selected from the group consisting of (Ci4-C2o)alcohols, (C 8 -Ci 8 )alcohol ethoxylates with 2 to 6 ethylene oxide units, (Ce-Ci 8 )alkyl polyglycosides, octaethylene glycol monododecyl ether and/or pen- taethylene glycol monododecyl ether, polyoxypropylene glycol alkyl ethers, decyl gluco side, lauryl glucoside, myristil glucoside, octyl glucoside, polyoxyethylene glycol octylphe- nol ethers, preferably triton X-100, nonoxynol-9, glyceryl laurate, polyglycerol polyricinole- ate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan mono
  • the one or more nonionic surfactants are selected from the group consisting of (Ci 6 -Ci 8 )alcohols, (Ci 6 -Cis)alcohol ethoxylates with 2 to 6 ethylene oxide units, (Cs-Ci4)alkyl polyglycosides, preferably cetyl alcohol, stearyl alcohol, oleyl alcohol, and mixtures of two or more thereof, octaethylene glycol monododecyl ether and/or pen- taethylene glycol monododecyl ether, polyoxypropylene glycol alkyl ethers, decyl gluco- side, lauryl glucoside, myristil glucoside, octyl glucoside, polyoxyethylene glycol octylphe- nol ethers, nonoxynol-9, glyceryl laurate, polyglycerol polyricinoleate, sorbitan
  • polyglyceryl-2-dipolyhydroxystearate diglyc- eryl-distearate, triglyceryl-distearate, C13/15 - PEG 3 , C13 - PEG 2 , glyceryl monooleate, sorbitan monooleate, polyglycerol-3-polyricinoleate, C16/18 - PEG 2 , oleyl - PEG 2 , PEG 20 - sorbitan monooleate, functionalized polyisobutene, C16/18 - PEGg, polyoxyethylene (10) oleyl ether, polyoxyethylene (20) oleyl ether, and mixtures of two or more thereof, more preferably from the group consisting of polyg lyceryl-2-d i polyhyd roxystearate, diglyc- eryl-distearate, triglyceryl-distearate, polyoxyethylene (10) oleyl ether
  • nonionic surfactant comprises polyoxyethylene (10) oleyl ether and/or polyoxyethylene (20) oleyl ether.
  • the one or more bases comprise one or more metal hydroxides and/or one or more metal hydroxide precursors, preferably one or more metal hydroxides, more preferably one or more metal hydroxides selected from the group consisting of potassium hydroxide, sodium hydroxide, magnesium hydrox ide, calcium hydroxide, iron hydroxide, aluminum hydroxide, and copper hydroxide, wherein more preferably the one or more bases comprise sodium hydroxide.
  • emulsification in (2) is achieved by agitation, preferably by stirring and/or sonication, and more preferably by stirring.
  • emulsification in (2) is achieved by use of a homogenizer, preferably with a rotor-stator homogenizer, with an ultrasonic homogenizer, with a high pressure homogenizer, by microfluidic systems, or by mem brane emulsification, more preferably with a high pressure homogenizer or with a rotor- stator homogenizer, and more preferably with a rotor-stator homogenizer.
  • a homogenizer preferably with a rotor-stator homogenizer, with an ultrasonic homogenizer, with a high pressure homogenizer, by microfluidic systems, or by mem brane emulsification, more preferably with a high pressure homogenizer or with a rotor- stator homogenizer, and more preferably with a rotor-stator homogenizer.
  • X is selected from the group consisting of Al, B, In, Ga, and combinations of two or more thereof, X preferably being Al.
  • the one or more sources of X2O3 comprises one or more compounds selected from the group consisting of aluminum salts and aluminum alkoxides, preferably from the group consisting of aluminates of an alkali metal, aluminum hydroxides, aluminum alkoxides, and mixtures of two or more thereof, wherein more preferably the one or more sources of X2O3 comprises one or more alumi num alkoxides AI(OR)3, wherein R stands for optionally branched (Ci-Ce)alkyl, preferably (Ci-Cs)alkyl, more preferably (Ci-C 4 )alkyl, and more preferably for optionally branched (Ci-C3)alkyl, wherein more preferably R stands for methyl, ethyl, n-propyl, isopropyl, or mixtures of two or more thereof, more preferably for ethyl, n-propyl, isopropyl, or
  • the alkali metal is selected from the group con sisting of Li, Na, K, Rb, and Cs, wherein preferably the alkali metal is Na and/or K, and wherein even more preferably the alkali metal is Na.
  • the metal M is selected from the group consisting of Mg, Ti, Cu, Co, Cr, Ni, Fe, Mo, Mn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, and mixtures of two or more thereof, preferably from the group consisting of Ti, Cu, Fe, Rh,
  • any one of embodiments 1 to 31 wherein the one or more sources of a metal M is selected from the group consisting of metal salts, metal alkoxides, metal car- boxy I ates, and mixtures of two or more thereof, wherein preferably the one or more sources of a metal M comprises one or more metal alkoxides and/or metal carboxylates, wherein more preferably one or more metal alkoxides are employed as the one or more sources of a metal M.
  • the one or more metal salts are selected from the group consisting of halides, hydroxides, sulfates, nitrates, phosphates, acetates, octade- canoate, 2-(2-methoxyethoxy)ethanolate, and mixtures of two or more thereof, preferably from the group consisting of chlorides, bromides, sulfates, nitrates, acetates, octadecano- ate, 2-(2-methoxyethoxy)ethanolate, and mixtures of two or more thereof, more preferably from the group consisting of bromides, nitrates, octadecanoate, 2-(2-methoxyethoxy)- ethanolate, and mixtures of two or more thereof, wherein more preferably the one or metal salts comprise nitrates, octadecanoate, and/or 2-(2-methoxyethoxy)ethanolate, preferably 2-(2-methoxyethoxy)ethanol
  • the one or more metal alkoxides comprise a trivalent metal ion and a divalent metal ion, wherein the tri valent metal ion is selected from the group consisting of Al, Ga, In, Fe, Co, Mn, Cr, La, Pr, Ce, Nd, Sm, Gd, Dy, Ho,
  • the divalent metal ion is selected from the group consisting of Mg, Ca, Sr, Ba, Zn, Cd, Cu, Ni, Co, Mn, Be, Zr, and combinations of two or more thereof, wherein preferably the trivalent metal ion is selected from the group consisting of Al, Ga, In, Fe, Co, Mn, Cr, La, Pr, Ce, Y, and combinations of two or more thereof, and the divalent metal ion is selected from the group consisting of Zn, Cu, Ni, Co, Mn, and combinations of two or more thereof,
  • the trivalent metal ion is selected from the group consisting of Al, Ga, Y, and combinations of two or more thereof
  • the divalent metal ion is selected from the group consisting of Cu, Ni, Co, and combinations of two or more thereof
  • more preferably the one or more metal alkoxides comprises Cu and Al as metal ions, wherein more preferably the metal ions in the one or more alkoxides are Cu and Al.
  • alkoxides are selected from the group consisting of (Ci-Cio)alkoxides, preferably of (C3-C8)alkoxides, more preferably of (C5-C7)alkoxides, where more preferably the alkoxides are C 6 -alkoxides, preferably alkoxides of hexanol, and more preferably alkoxides of n-hexanol.
  • silica preferably from the group consisting of fumed silica, silica hydrosols, reactive amorphous solid silicas, silica gel, silicic acid, water glass, sodium metasilicate hydrate, sesquisilicate, disilicate, colloidal silica, pyrogenic silica, silicic acid esters, tetraalkoxysilanes, and mix tures of two or more thereof,
  • silica more preferably from the group consisting of fumed silica, silica hydrosols, silica gel, silicic acid, water glass, colloidal silica, pyrogenic silica, silicic acid esters, tetraalkoxysilanes, and mixtures of two or more thereof,
  • silica hydrosols more preferably from the group consisting of silica hydrosols, silicic acid, water glass, col loidal silica, silicic acid esters, tetraalkoxysilanes, and mixtures of two or more thereof, more preferably from the group consisting of water glass, colloidal silica, silicic acid es ters, tetraalkoxysilanes, and mixtures of two or more thereof
  • the one or more sources of S1O2 is selected from the group con sisting of water glass, colloidal silica, and mixtures thereof, wherein more preferably col loidal silica is employed as the one or more sources of S1O2.
  • (I ), (3), (4), (5), (6), and (7) are performed under agitation of the mixture, preferably under stirring and/or sonication of the mixture, and more preferably under stirring of the mixture.
  • heating in (7) is conducted at a temperature in the range of from 80 to 260°C, preferably from 100 to 240°C, more prefer ably from 120 to 220°C, more preferably from 140 to 200°C, more preferably from 160 to 180°C, and more preferably from 165 to 175°C.
  • heating in (7) is conducted for a period in the range of from 0.5 to 120 h, preferably from 1 to 114 h, more preferably from 3 to 108 h, more preferably from 6 to 102 h, more preferably from 12 to 96 h, more prefer ably from 18 to 84 h, more preferably from 24 to 72 h, more preferably from 30 to 66 h, more preferably from 36 to 60 h, more preferably from 42 to 54 h, more preferably from 45 to 51 h, and more preferably from 47 to 49 h.
  • the process of any one of embodiments 1 to 41 wherein heating in (7) is conducted un der autogenous pressure.
  • the process of any one of embodiments 1 to 42, wherein the process further comprises
  • n-butanol isopropanol, propanol, ethanol, methanol, water, acetone, and mixtures thereof,
  • the solvent system comprises water or acetone, and wherein more preferably water is used as the solvent system, preferably deionized water.
  • drying in (10) is conducted at a temperature in the range of from 20 to 160°C, preferably from 30 to 140°C, more prefera bly from 40 to 120°C, more preferably from 50 to 110°C, more preferably from 60 to 100°C, more preferably from 70 to 90°C, and more preferably from 75 to 85°C.
  • the mixture obtained in (6) and heated in (7) further comprises seed crystals, wherein the seed crystals preferably com prise one or more zeolitic materials, more preferably one or more zeolitic materials having the framework structure type of the zeolitic material obtained in (7), wherein more prefera bly the one or more zeolitic materials comprise SSZ-13 and/or chabazite, preferably SSZ- 13.
  • heating in (ii) is conducted at a temperature in the range of from 100 to 300 °C, preferably of from 100 to 280 °C, more preferably of from 150 to 270 °C, more preferably of from 180 to 260 °C, more preferably of from 200 to 250 °C, more preferably of from 210 to 240 °C, and more preferably of from 220 to 235 °C.
  • any one of embodiments 51 to 54, wherein the volume of the continuous flow reactor is in the range of from 50 cm 3 to 75 m 3 , preferably of from 50 cm 3 to 3 m 3 , more preferably from 55 cm 3 to 1 m 3 , more preferably from 60 cm 3 to 0.7 m 3 , more prefer ably from 65 cm 3 to 0.3 m 3 , more preferably from 70 cm 3 to 0.1 m 3 , more preferably from 75 to 70,000 cm 3 , more preferably from 80 to 50,000 cm 3 , more preferably from 85 to 30,000 cm 3 , more preferably from 90 to 10,000 cm 3 , more preferably from 95 to 7,000 cm 3 , more preferably from 100 to 5,000 cm 3 , more preferably from 105 to 3,000 cm 3 , more preferably from 110 to 1 ,000 cm 3 , more preferably from 115 to 700 cm 3 , more preferably from 120 to 500 cm 3 , more preferably from 125 to 350 cm 3 , more preferably from 130 to 250 cm 3
  • the continuous flow reactor is selected among a tubular reactor, a ring reactor, and a continuously oscillating reactor, preferably among a plain tubular reactor, a tubular membrane reactor, a tubular reactor with Coanda effect, a ring reactor, a continuously oscillating baffled reactor, and combina tions thereof, wherein more preferably the continuous flow reactor is a plain tubular reac tor and/or a ring reactor, wherein more preferably the continuous flow reactor is a plain tubular reactor.
  • the continuous flow reactor is a tubular reactor, and wherein at least a portion of the tubular reactor is of a regular cylindri cal form having a constant inner diameter perpendicular to the direction of flow, wherein the inner diameter is preferably in the range of from 2 to 1200 mm, more preferably from 3 to 800 mm, more preferably from 3 to 500 mm, more preferably from 4 to 200 mm, more preferably from 4 to 100 mm, more preferably from 4.5 to 50 mm, more preferably from 4.5 to 30 mm, more preferably from 5 to 15 mm, more preferably from 5 to 10 mm, more preferably from 5.5 to 8 mm, and more preferably from 5.5 to 6.5 mm.
  • any one of embodiments 51 to 57, wherein the continuous flow reactor has a length in the range of from 0.2 to 5,000 m, preferably from 0.5 to 3,000 m, more prefer ably from 1 to 1 ,000 m more preferably from 3 to 500 m more preferably from 3.5 to 200 m, more preferably from 3.5 to 100 m, more preferably from 4 to 50 m, more preferably from 4 to 30 m, more preferably from 4.5 to 20 m, more preferably from 4.5 to 15 m, more preferably from 5 to 10 m, and more preferably from 5 to 7 m.
  • the wall of the continuous flow reactor is made of a metallic material, wherein the metallic material comprises one or more metals selected from the group consisting of Ta, Cr, Fe, Ni, Cu, Al, Mo, and combi nations and/or alloys of two or more thereof, preferably from the group consisting of Ta,
  • the metallic material comprises a nickel alloy, a nickel- molybdenum alloy, and more preferably a nickel-molybdenum-chromium alloy.
  • the organic polymer material preferably comprises one or more polymers selected from the group consisting of fluorinated polyalkylenes and mixtures of two or more thereof, more prefera bly from the group consisting of (C2-C3)polyalkylenes and mixtures of two or more there of, preferably from the group consisting of fluorinated polyethylenes and mixtures of two or more thereof, wherein more preferably the polymer material comprises
  • any one of embodiments 51 to 65 wherein prior to (i) the mixture obtained in (6) is aged at a temperature in the range of from 40 to 120 °C, preferably from 50 to 110 °C, more preferably from 60 to 105 °C, more preferably from 70 to 100 °C, more prefera bly from 75 to 95 °C, and more preferably from 80 to 90 °C.
  • ethanol more preferably from the group consisting of ethanol, methanol, water, and mixtures thereof,
  • the liquid comprises water, and wherein more preferably water is used as the liquid, preferably deionized water.
  • a metal-exchanged zeolitic material comprising S1O 2 and X 2 O 3 in its framework structure, wherein X is a trivalent element, wherein said metal-exchanged zeolitic material is ob tained and/or obtainable according to the process of any one of embodiments 1 to 70.
  • metal-exchanged zeolitic material of embodiment 71 wherein the metal-exchanged zeolitic material has a framework structure type selected from the group consisting of MFI, BEA, CHA, AEI, MWW, LEV, GME, FAU, FER, MEL, MOR, and intergrowth structures thereof, preferably from the group consisting of MFI, BEA, CHA, AEI, MWW, and inter growth structures thereof, more preferably from the group consisting of BEA, CHA, AEI, MFI, and intergrowth structures thereof, wherein more preferably the zeolitic material has a CHA and/or AEI and/or MFI type framework structure, preferably a CHA or MFI type framework structure.
  • a framework structure type selected from the group consisting of MFI, BEA, CHA, AEI, MWW, LEV, GME, FAU, FER, MEL, MOR, and intergrowth structures thereof, preferably from the group consisting of MFI, BEA,
  • a metal-exchanged zeolitic material according to any one of embodiments 71 to 74 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, 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 precursor thereof, more preferably as a catalyst for the selective catalytic re duction (SCR) of nitrogen oxides NO x ; for the storage and/or adsorption of CO 2 ; for the ox idation of NH 3 , in particular for the oxidation of NH 3 slip in diesel systems; for the decom position 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 preferably in methanol to
  • Figures 1-3, and 5 respectively show the SEM images of a portion of a sample of the product obtained from Reference Example 2 and Examples 2, 3, and 5, respectively, at different magnifications, wherein the scale in the images are indicated by the leg end at the bottom right of the respective image.
  • Figure 4 displays a conceptual diagram of the location of the copper sources in the emul sion synthesis depending on its chemical nature.
  • HRTEM data were collected with an FEI Tecnai G2 Spirit Twin TEM operating at 120 kV using a Gatan US1000 2k x 2k CCD camera.
  • Powder X-ray diffraction (PXRD) data was collected using a diffractometer (D8 Advance Series II, Bruker AXS GmbH) equipped with a LYNXEYE detector operated with a copper anode X-ray tube running at 40kV and 40mA.
  • the geometry was Bragg-Brentano, and air scattering was reduced using an air scatter shield.
  • Crystallinity of the samples was determined using the software DIF- F RAC. EVA provided by Bruker AXS GmbH, Düsseldorf. The method is described on page 121 of the user manual. The default parameters for the calculation were used.
  • phase composition The phase composition was computed against the raw data using the modelling software DIFFRAC.TOPAS provided by Bruker AXS GmbH, Düsseldorf. The crystal structures of the identified phases, instrumental parameters as well the crystallite size of the individual phases were used to simulate the diffraction pattern. This was fit against the data in addition to a function modelling the background intensities.
  • Data collection The samples were homogenized in a mortar and then pressed into a standard flat sample holder provided by Bruker AXS GmbH for Bragg-Brentano geometry data collection. The flat surface was achieved using a glass plate to compress and flatten the sample powder. The data was collected from the angular range 2 to 70 ° 2Theta with a step size of 0.02°
  • Reference Example 3 Synthesis of a zeolitic material having a CHA type framework structure
  • the suspension was filtrated and the separated solids washed with water until the washing water had a pH of 7.
  • the solids were dried over night at 120 °C and subsequently calcined in air at 550 °C for 2 h, wherein the heating rate was set to 2 °C per min.
  • the obtained solids had a crystallinity of 94 % and comprised a CHA phase, a ZSM-39 phase, and a Kenyaite phase, as determined according to Reference Example 2.
  • Copper aluminum hexanolate (CuAh(OHex) 8 ) which was used for the examples was prepared as disclosed in WO 2016/096990 A1.
  • Comparative Example 1 One-pot synthesis of a Cu-CHA with lower amount of Cu source
  • the second mixture was added to the first mixture.
  • the resulting mixture having a water to o-xylene ratio of about 30 to 70 volume-% was stirred for 10 min in the Teflon insert.
  • the mix ture was then subjected to hydrothermal treatment for 48 h at 170 °C under vigorous stirring.
  • the solids were filtered of using a Buchner funnel equipped with a filter paper (white ribbon) and washed with 100-150 ml de-ionized water and approximately 50 ml acetone.
  • the obtained solids were dried at 80 °C and subsequently calcined in air at 550 °C for 2 h (the heating rate was set to 2 °C per min).
  • the relative content of silicon, aluminum and copper has been determined using TEM micros copy for Example 3, as determined according to Reference Example 1. The results are listed in table 1.
  • the zeolitic material of Example 3 comprised only CHA as unique crystalline phase.
  • the observed crystallinity in the XRD was 78 %.
  • the zeolitic material of Example 3 comprised a comparatively high content of aluminum and copper, indicating that the introduction of a metal source via the organic phase of the emulsion is very effective.
  • Example 4 Preparation of a Cu-containing CHA zeolite using a different Cu source
  • Example 4 Example 3 was repeated whereby a different copper source has been used in a different amount.
  • the source and amount thereof is listed in table 2.
  • the ratio of water to o-xylene was approximately 30 to 70 volume-%.
  • the zeolitic material of Example 4 comprised only CHA as unique crystalline phase.
  • the observed crystallinity in the XRD was 71 %.
  • Figure 5 shows the SEM image of the zeolitic materials according to Example 4. It was found that the particles had sizes between 100 nm and up to greater than 5 pm. Surprisingly, particles with bigger sizes were obtained for Example 4 where the Cu source was placed“near” (see image for Cu(OMEE)2 as source) or in the water phase (see e. g. image for“Cu as chloride”) of the water/oil emulsion system.
  • a conceptual drawing is given in figure 4 showing a general overview where the different species are located in the water/oil emulsion system.
  • Example 4 the zeolitic material of Example 4 comprised a comparatively high content of aluminum and copper. Further, it was found that the amount of Cu and Al introduced in the zeo litic framework structure was lower in comparison to Example 3 synthesized using CuAl2(OHex)6 as precursor.
  • Example 3 was repeated whereby each time a different copper source has been used in a different amount. Further, the copper source was added to the first mixture and not to the second mixture. The source and amount thereof are listed in table 4 be low for each example. The ratio of water to o-xylene was the same for all examples 5-8 being approximately 30 to 70 volume-%.
  • Figure 5 shows the SEM images of the zeolitic materials according to Examples 5-8 wherein the Cu source was varied. It was found that the particles had sizes between 100 nm and up to greater than 5 pm, depending on the used Cu source. Surprisingly, particles with bigger sizes were obtained for those examples where the Cu source was placed“near” (see image for CU(OM EE)2 as source) or in the water phase (see e. g. image for“Cu as chloride”) of the wa ter/oil emulsion system.
  • a conceptual drawing is given in figure 4 showing a general overview where the different species are located in the water/oil emulsion system.
  • the zeolitic material with comparatively high contents of aluminum and copper was the material synthesized using CuAh(OHex) 6 , indicating that the introduction of metal sources via the organic phase of the emulsion is the most effective as regards the inventive synthetic approach.
  • the addition of copper salts in form of acetate or sulfate led to the introduc tion of less copper in the final particles, suggesting that the Cu incorporation using metal salts via the aqueous phase of the emulsion is comparatively less effective.
  • the resulting reaction mixture was then subjected to hydro- thermal conditions at a temperature of 175 °C under stirring for 5 days. After that, the reaction mixture was cooled to room temperature, filtrated with a Buchner funnel (blue ribbon paper fil ter) and the thus obtained solids washed with 250 ml de-ionized water and subsequently with 50 ml acetone. The resulting washed solids were dried at 80 °C for 16 h.
  • Example 10 Preparation of a Cu-containing CHA zeolite
  • the reaction mixture was then subjected to hydrothermal conditions at a temperature of 170 °C under stirring for 96 h. After that, the reaction mixture was cooled to room temperature, filtrated with a Buchner funnel (blue ribbon paper filter) and the thus obtained solids washed with about 125 ml de-ionized water and subsequently with about 50 ml acetone. The resulting washed sol ids were dried at 80 °C for 16 h and then calcined in air at a temperature of 550 °C for 2 h, whereby a heating rate of 2 °C/min was applied.
  • the zeolit- ic material of Example 10 comprised only CHA as unique crystalline phase.
  • the observed crys tallinity in the XRD was at least 80 %.
  • No copper oxide reflexes were observed in the powder X- ray diffraction pattern.
  • the resulting product had a copper content of 4 weight-%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

La présente invention concerne un procédé de préparation d'un matériau zéolitique à échange de métal comprenant du SiO2 et du X2O3 dans sa structure d'ossature, X étant un élément trivalent, comprenant (1) la préparation d'un premier mélange contenant un ou plusieurs solvants organiques non polaires, un ou plusieurs solvants protiques polaires, une ou plusieurs matrices organiques en tant qu'agents d'orientation de structure, une ou plusieurs bases et éventuellement un ou plusieurs émulsifiants ; (2) l'émulsion dudit mélange ; (3) l'ajout d'une ou de plusieurs sources de SiO2 au mélange émulsionné ; (4) la préparation d'un second mélange comprenant un ou plusieurs solvants organiques non polaires ; (5) l'ajout d'une ou de plusieurs sources d'un métal M au second mélange ; (6) l'ajout du second mélange au premier mélange ; (7) le chauffage du mélange obtenu à l'étape (6) à des fins de cristallisation, le premier mélange préparé à l'étape (1) et/ou le second mélange préparé à l'étape (4) comprenant en outre une ou plusieurs sources de X2O3. En outre, la présente invention concerne un matériau zéolitique à échange de métal et son utilisation.
PCT/EP2020/062860 2019-05-09 2020-05-08 Synthèse monotope de matériaux zéolitiques à échange de métal WO2020225419A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP19173471 2019-05-09
EP19173471.4 2019-05-09

Publications (1)

Publication Number Publication Date
WO2020225419A1 true WO2020225419A1 (fr) 2020-11-12

Family

ID=66476469

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2020/062860 WO2020225419A1 (fr) 2019-05-09 2020-05-08 Synthèse monotope de matériaux zéolitiques à échange de métal

Country Status (1)

Country Link
WO (1) WO2020225419A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011095589A1 (fr) 2010-02-05 2011-08-11 Grillo Zinkoxid Gmbh Nanoparticules de zno de forme prismatique et leur effet sur des propriétés optiques
EP2297036B1 (fr) 2008-05-21 2014-04-16 Basf Se Procédé de synthèse directe de zéolithes contenant du cu et dotées d'une structure cha
WO2016096990A1 (fr) 2014-12-19 2016-06-23 Basf Se Procédé de préparation de matériaux de type oxyde, de matériaux de type hydroxyde double lamellaire, de matériaux de type hydroxyde et de matériaux à base de carbonate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2297036B1 (fr) 2008-05-21 2014-04-16 Basf Se Procédé de synthèse directe de zéolithes contenant du cu et dotées d'une structure cha
WO2011095589A1 (fr) 2010-02-05 2011-08-11 Grillo Zinkoxid Gmbh Nanoparticules de zno de forme prismatique et leur effet sur des propriétés optiques
WO2016096990A1 (fr) 2014-12-19 2016-06-23 Basf Se Procédé de préparation de matériaux de type oxyde, de matériaux de type hydroxyde double lamellaire, de matériaux de type hydroxyde et de matériaux à base de carbonate

Non-Patent Citations (18)

* Cited by examiner, † Cited by third party
Title
J. ZHU ET AL., REACTION CHEMISTRY AND ENGINEERING, vol. 3, 2018, pages 844 - 848
K. IWAKAI ET AL., MICROPOROUS AND MESOPOROUS MATERIALS, vol. 141, 2001, pages 167 - 174
LIJUAN XIE ET AL: "Excellent Performance of One-Pot Synthesized Cu-SSZ-13 Catalyst for the Selective Catalytic Reduction of NO x with NH 3", ENVIRONMENTAL SCIENCE & TECHNOLOGY, vol. 48, no. 1, 7 January 2014 (2014-01-07), US, pages 566 - 572, XP055285466, ISSN: 0013-936X, DOI: 10.1021/es4032002 *
LIMIN REN ET AL: "Designed copper-amine complex as an efficient template for one-pot synthesis of Cu-SSZ-13 zeolite with excellent activity for selective catalytic reduction of NOx by NH3", CHEMICAL COMMUNICATIONS, vol. 47, no. 35, 1 January 2011 (2011-01-01), pages 9789, XP055054153, ISSN: 1359-7345, DOI: 10.1039/c1cc12469b *
LIMIN REN ET AL: "Electronic Supplementary Information Designed Copper-amine Complex as an Efficient Template for One-pot Synthesis of Cu-SSZ-13 Zeolite with Excellent Activity for Selective Catalytic Reduction of NOx by NH 3", 31 May 2011 (2011-05-31), XP055285774, Retrieved from the Internet <URL:http://www.rsc.org/suppdata/cc/c1/c1cc12469b/c1cc12469b.pdf> [retrieved on 20160705] *
LING ZHANG ET AL: "Recent advances in the preparation of zeolites for the selective catalytic reduction of NOx in diesel engines", REACTION CHEMISTRY & ENGINEERING, vol. 4, no. 6, 1 January 2019 (2019-01-01), pages 975 - 985, XP055620552, DOI: 10.1039/C8RE00214B *
NILAM L CHAUHAN ET AL: "Synthesis of zeolite ferrierite-Role of emulsifiers", INDIAN JOURNAL OF CHEMICAL TECHNOLOGY,, vol. 18, 1 September 2011 (2011-09-01), pages 335 - 342, XP002719103 *
P. SHARMA ET AL., JOURNAL OF COLLOID AND INTERFACE SCIENCE, vol. 422, 2014, pages 45 - 53
R. LIMIN ET AL., CHEMICAL COMMUNICATIONS A STUDY
R. LIMIN ET AL., THE STUDY OF X
R. LIMIN ET AL.: "Designed copper-amine complex as an efficient template for one-pot synthesis of Cu-SSZ-13 zeolite with excellent activity for selective catalytic reduction of NOx by NH3", CHEMICAL COMMUNICATIONS, vol. 47, no. 35, 2011, pages 9789 - 9790, XP055054153, DOI: 10.1039/c1cc12469b
R. MARTINEZ-FRANCO ET AL.: "Efficient One-Pot Preparation of Cu-SSZ-13 Materials using Cooperative OSDAs for their Catalytic Application in the SCR of NOx", CHEMCATCHEM, vol. 5, no. 11, 2013, pages 3316 - 3323, XP055285597, DOI: 10.1002/cctc.201300141
RAQUEL MARTINEZ-FRANCO ET AL: "Efficient One-Pot Preparation of Cu-SSZ-13 Materials using Cooperative OSDAs for their Catalytic Application in the SCR of NOx", CHEMCATCHEM, vol. 5, no. 11, 21 May 2013 (2013-05-21), DE, pages 3316 - 3323, XP055285597, ISSN: 1867-3880, DOI: 10.1002/cctc.201300141 *
X. LIJUAN ET AL.: "Excellent Performance of One-Pot Synthesized Cu-SSZ-13 Catalyst for the Selective Catalytic Reduction of NOx with NH3", ENVIRONMENTAL SCIENCE & TECHNOLOGY, vol. 48, no. I, 2014, pages 566 - 572, XP055285466, DOI: 10.1021/es4032002
Y. SHEN ET AL., BULLETIN MATERIAL SCIENCE, vol. 34, 2011, pages 755 - 758
YING ZHANG ET AL: "Nonionic emulsion-mediated synthesis and characterization of Zeolite Y", JOURNAL OF SOL-GEL SCIENCE AND TECHNOLOGY, KLUWER ACADEMIC PUBLISHERS, BO, vol. 54, no. 2, 19 March 2010 (2010-03-19), pages 212 - 219, XP019792535, ISSN: 1573-4846 *
YUGUO SHEN ET AL: "Nonionic emulsion-mediated synthesis of zeolite beta", BULLETIN OF MATERIALS SCIENCE, SPRINGER INDIA, NEW DELHI, vol. 34, no. 4, 19 October 2011 (2011-10-19), pages 755 - 758, XP019966973, ISSN: 0973-7669, DOI: 10.1007/S12034-011-0191-4 *
Z. LING ET AL.: "Recent advances in the preparation of zeolites for the selective catalytic reduction of NOx in diesel engines", REACTION CHEMISTRY & ENGINEERING, vol. 4, no. 6, 2018, pages 975 - 985, XP055620552, DOI: 10.1039/C8RE00214B

Similar Documents

Publication Publication Date Title
JP6392860B2 (ja) モレキュラーシーブ、その製造及びその使用
JP4919948B2 (ja) ヘテロ構造非ｚｓｍ−４８シーディングによるｚｓｍ−４８結晶の合成
US10029244B2 (en) Process for preparing a titanium-containing zeolitic material having an MWW framework structure
CA2581309C (fr) Procede de synthese de zeolithe beta avec de la diethylenetriamine
JP2015110219A (ja) ケイ酸チタニウム分子篩およびその合成
CN112110457B (zh) 一种定向堆砌生长的zsm-5纳米薄片团聚体的制备方法
JP6526689B2 (ja) Ｍｗｗ型の骨格構造を有するスズ含有のゼオライト材料
KR20180021859A (ko) 알루미노실리케이트 제올라이트 ssz-98의 합성
WO2018164989A1 (fr) Catalyseur zéolithique de type titanosilicate contenant des nanoparticules d&#39;or encapsulées, procédé de synthèse et d&#39;utilisation
Cheong et al. Rapid synthesis of nanocrystalline zeolite W with hierarchical mesoporosity as an efficient solid basic catalyst for nitroaldol Henry reaction of vanillin with nitroethane
CN112469666A (zh) 使用负载有机模板的晶种连续合成沸石材料的方法
WO2020225419A1 (fr) Synthèse monotope de matériaux zéolitiques à échange de métal
CN114751426A (zh) B-Al-ZSM-5分子筛的制备方法与应用
US10807874B2 (en) Mordenite zeolite and production method therefor
CN111655370A (zh) 用于制造空心zsm-5和ts-1沸石的方法
US10843930B1 (en) Systems and methods for synthesis of ZSM-22 zeolite
CN111099610B (zh) Stf沸石分子筛的制备方法
JP2012031009A (ja) Ｚｓｍ−５型ゼオライトの合成方法
CN110407231B (zh) 合成含铜cha结构分子筛的方法及含铜cha结构分子筛
CN112573537A (zh) 一种mre分子筛的制备方法
WO2016140869A1 (fr) Procédé de conversion de composé oxygéné en oléfine à l&#39;aide de zéolite 2-d de type pentasil
EP3898513A1 (fr) Matériaux zéolithiques de type cha et leurs procédés de préparation
US10710888B2 (en) Beta zeolite and method for producing same
WO2020063784A1 (fr) Matériau zéolithique contenant du gallium et son utilisation en scr
JP6391986B2 (ja) ベータ型ゼオライト及びその製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20723872

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20723872

Country of ref document: EP

Kind code of ref document: A1