WO2020225409A1 - Process for a continuous synthesis of a cha zeolitic material from an emulsion - Google Patents

Process for a continuous synthesis of a cha zeolitic material from an emulsion Download PDF

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Publication number
WO2020225409A1
WO2020225409A1 PCT/EP2020/062827 EP2020062827W WO2020225409A1 WO 2020225409 A1 WO2020225409 A1 WO 2020225409A1 EP 2020062827 W EP2020062827 W EP 2020062827W WO 2020225409 A1 WO2020225409 A1 WO 2020225409A1
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Prior art keywords
range
group
zeolitic material
compounds
alkyl
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PCT/EP2020/062827
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French (fr)
Inventor
Hannah SCHREYER
Andrei-Nicolae PARVULESCU
Ulrich Mueller
Tatsuya Okubo
Toru Wakihara
Kenta Iyoki
Zhendong Liu
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Basf Se
The University Of Tokyo
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Publication of WO2020225409A1 publication Critical patent/WO2020225409A1/en

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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7015—CHA-type, e.g. Chabazite, LZ-218
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/02—Crystalline silica-polymorphs, e.g. silicalites dealuminated aluminosilicate zeolites

Definitions

  • the present invention relates to a continuous process for the preparation of a zeolitic material as well as to a zeolitic material obtainable or obtained by said process. Furthermore, the pre sent invention relates to the use of the inventive zeolitic material, in particular as a catalyst.
  • zeolitic materials preferably using simple starting compounds involves a com plex process of self organization which often necessitates special conditions such as elevated temperatures and/or pressure, wherein such reactions typically require the heating of starting materials under autogenous pressure for obtaining the zeolitic material after lengthy reaction times ranging from days to several weeks. Accordingly, due to the often harsh reaction condi tions and the long reaction times, batch synthesis has long been the method of choice for syn thesizing zeolitic materials. Batch reactions however present numerous limitations, in particular relative to the levels of space-time-yield which may be attained.
  • WO 2015/185625 A relates to a process for the preparation of a zeolitic material of the CHA-type framework structure using cycloalkylammonium compounds in combination with a tetraalkylammonium compound for achieving improvements in cast-effectiveness.
  • the synthesis of the zeolites having the CHA-type framework structure was conducted batch-wise in an autoclave.
  • WO 201 1/064186 A1 and EP 2 325 143 A2 respectively relate to a process for the preparation of zeolites having the CHA framework structure which employ tetrame- thylammonium hydroxide in addition to at least one organic structure directing agent.
  • structure directing agents which may be used to this effect, said documents mention N,N,N- trimethylcyclohexylammonium compounds among several compounds as possible structure directing agents for obtaining a zeolitic material having the CHA framework structure, wherein however N,N,N-trimethyl-1 -adamantyltrimethylammonium compounds are preferably and effec tively taught in said documents for obtaining the aforementioned material.
  • Zones et al. "A Study of Guest/Host Energetics for the Synthesis of Cage Structures NON and CHA" in Studies in Surface Science and Catalysis, Vol. 84, pp. 29-36, Elsevier Science B.V.
  • WO 2013/182974 A relates to the use of trimethylcyclohexylammoniumhydroxide as organo- template for the synthesis of CHA-type zeolitic materials involving crystallization times of 48 hours or more.
  • the operation time can be significantly prolonged com pared to known processes whereby the advantages of comparatively short synthesis time as regards the preparation of a zeolitic material can be maintained compared to known batch pro cess when applying a continuous process for the preparation of zeolitic materials according to the present invention.
  • the preparation of a chabazite which is particularly used for automotive emission catalysts which normally takes more than 20 h syn thesis time may be prepared in less than 2 h.
  • the present invention relates to a continuous process for preparing a zeolitic material comprising YO 2 and optionally X 2 O 3 in its framework structure, wherein Y is a tetravalent ele ment and X is a trivalent element, said process comprising
  • the reactant stream comprises a reactant mixture comprising a non-polar liquid solvent system, one or more emulsifiers, and a mixture of one or more sources of YO 2 , optionally one or more sources of X 2 O 3 , seed crystals, a polar pro tic liquid solvent system, and one or more
  • the zeolitic material has a framework structure type selected from the group consisting of AEI, AFX, ANA, BEA, BEC, CAN, CHA, CDO, EMT, ERI, EUO, FAU, FER, GME, HEU, ITH, ITW, KFI, LEV, MEI, MEL, MFI, MOR, MTN, MWW, OFF, RRO, RTH, SAV, SFW, SZR, TON, and a mixture of two or more thereof, more preferably from the group consisting of CAN, AEI, EMT, SAV, SZR, KFI, ERI, OFF, RTH, GME, AFX, SFW, BEA, CHA, FAU, FER,
  • a framework structure type selected from the group consisting of AEI, AFX, ANA, BEA, BEC, CAN, CHA, CDO, EMT, ERI, EUO, FAU, FER, GME, HEU, ITH, IT
  • Y is selected from the group consisting of Si, Ge, Sn, Ti, Zr, and combina tions of two or more thereof, preferably from the group consisting of Si, Ge, Ti, and combina tions of two or more thereof, more preferably from the group consisting of Si, Ti, and a combina tion thereof, wherein more preferably Y is Si.
  • X is selected from the group consisting of B, Al, Ga, In, and combina tions of two or more thereof, preferably from the group consisting of B, Al, Ga, and combinations of two or more thereof, more preferably from the group consisting of Al, Ga, and a combination thereof, wherein more preferably X is Al.
  • the zeolitic material has the CHA framework structure type comprising YO 2 and X 2 O 3 , wherein Y is Si and X is Al.
  • the zeolitic material has the AEI framework structure type comprising YO 2 and X 2 O 3 , wherein Y is Si and X is Al.
  • the flow reactor according to (i) is selected among a tubular reactor, and a ring reactor, more preferably among a plain tubular reactor, a tubular membrane reactor, a tubular reactor with Coanda effect, a ring reactor, and combinations thereof, wherein more preferably the flow reactor is a plain tubular reactor and/or a ring reactor, wherein more preferably the flow reactor is a plain tubular reactor.
  • the flow reactor according to (i) comprises a reaction zone having a volume in the range of from 5 to 5000 cm 3 , more preferably in the range of from 5 to 2500 cm 3 , more pref erably in the range of from 10 to 1000 cm 3 , more preferably in the range of from 10 to 100 cm 3 , more preferably in the range of from 20 to 50 cm 3 , more preferably in the range of from 20 to 30 cm 3 , more preferably in the range of from 25 to 30 cm 3 .
  • the flow reactor according to (i) comprises a reaction zone having a length in the range of from 0.2 to 100 m, more preferably in the range of from 0.5 to 50 m, more prefera bly in the range of from 1 .0 to 10 m, more preferably in the range of from 1 .5 to 5.0 m, more preferably in the range of from 1 .75 to 3.50 m, more preferably in the range of from 2.00 to 2.50 m.
  • the flow reactor according to (i) comprises a tubular reactor
  • the inner diameter is preferably in the range of from 0.1 to 100 mm, more preferably in the range of from 0.1 to 50 mm, more prefera bly in the range of from 0.2 to 25 mm, more preferably in the range of from 0.5 to 10 mm, more preferably in the range of from 0.5 to 5.0 mm, more preferably in the range of from 1 .0 to 3.5 mm, more preferably in the range of from 1 .5 to 2.5 mm, more preferably in the range of from 1 .75 to 2.25 mm, more preferably in the range of from 1 .95 to 2.05 mm.
  • the wall of the flow reactor according to (i) 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 combinations and/or alloys of two or more thereof, more 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,
  • the surface of the inner wall of the flow reactor is lined with an organ ic polymer material, wherein 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 consisting 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 preferably the polymer material comprises
  • the flow reactor consists of a single stage.
  • the one or more sources of YO 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, disil icate, 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,
  • the one or more sources of S1O 2 is selected from the group consisting of water glass, colloidal silica, and mixtures thereof, wherein more preferably colloidal silica is employed as the one or more sources of Si0 2 .
  • the one or more sources of X 2 O 3 comprises one or more aluminum salts, more preferably an aluminate of an alkali metal and/or aluminum hydroxide, preferably aluminum hydroxide, wherein more preferably the one or more sources of X 2 O 3 is an aluminate of an alkali metal and/or aluminum hydroxide, preferably aluminum hydroxide, wherein the alkali metal is preferably selected 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 seed crystals comprise a zeolitic material, wherein the zeolitic material comprises YO 2 and optionally X 2 O 3 , wherein Y is a tetravalent element and X is a trivalent ele ment, wherein preferably Y is selected from the group consisting of Si, Ge, Sn, Ti, Zr, and com binations of two or more thereof, preferably from the group consisting of Si, Ge, Ti, and combi nations of two or more thereof, more preferably from the group consisting of Si, Ti, and a com bination thereof, wherein more preferably Y is Si, and wherein preferably X is selected from the group consisting of B, Al, Ga, In, and combinations of two or more thereof, preferably from the group consisting of B, Al, Ga, and combinations of two or more thereof, more preferably from the group consisting of Al, Ga, and a combination thereof, wherein more preferably X is Al.
  • the framework structure type of the zeolitic material comprised in the seed crystals no particular restriction applies. It is preferred that the zeolitic material comprised in the seed crystals has a framework structure selected from the group consisting of AEI, AFX, ANA, BE A, BEC, CAN, CHA, CDO, EMT, ERI, EUO, FAU, FER, GME, HEU, ITH, ITW, KFI, LEV, MEI,
  • MEL MFI
  • MOR MTN, MWW, OFF, RRO, RTH, SAV, SFW, SZR, TON, and a mixture of two or more thereof, preferably from the group consisting of CAN, AEI, EMT, SAV, SZR, KFI, ERI,
  • the zeolitic material comprised in the seed crystals has a CHA-type framework structure. It is particularly preferred that the zeolitic material comprised in the seed crystals and having a CHA-type framework structure is selected from the group consisting of Willhendersonite, ZYT-6, SAPO-47, Na-Chabazite, Chabazite, LZ-218,
  • the zeolitic material comprised in the seed crystals and having a CHA- type framework structure comprises chabazite and/or SSZ-13, preferably chabazite, and where in more preferably the zeolitic material comprised in the seed crystals and having a CHA-type framework structure is chabazite and/or SSZ-13, preferably SSZ-13.
  • the zeolitic material comprised in the seed crystals has a AEI -type framework structure. It is particularly preferred that the zeolitic material comprised in the seed crystals and having a AEI -type framework structure is selected from the group consisting of SSZ-39, SAPO-18, SIZ-8, including mixtures of two or more thereof, where in more preferably the zeolitic material comprised in the seed crystals and having a AEI -type framework structure comprises SSZ-39, and wherein more preferably the zeolitic material com prised in the seed crystals and having a AEI-type framework structure is SSZ-39.
  • the amount of seed crystals in the mixture according to (ii) is in the range of from 0.1 to 20 wt.-% based on 100 wt-% of S1O2 contained in the mixture, more pref erably from 1 to 18 wt.-%, more preferably from 5 to 15 weight-%, more preferably from 7 to 13 weight-%, more preferably from 8 to 12 weight-%, more preferably from 9 to 1 1 weight-%, and more preferably from 9.5 to 10.5 weight-%.
  • the seed crystals are ground prior to (ii), wherein more preferably grinding is carried out in a mill selected from the group consisting of a stirred media mill, a planetary ball mill, a ball mill, a roller mill, a kneader, a high shear mixer, and a mix muller,
  • a mill selected from the group consisting of a stirred media mill, a planetary ball mill, a ball mill, a roller mill, a kneader, a high shear mixer, and a mix muller
  • a stirred media mill a ball mill, a roller mill, a planetary mill, and a high shear mixer
  • the seed crystals are ground prior to (ii). It is particularly preferred that in the case where the seed crystals are ground prior to (ii) grinding is carried out in a ball mill and/or in a planetary ball mill, preferably in a ball mill.
  • balls are used made of a material selected from the group consisting of stainless steel, ceramic, and rub ber, more preferably from the group consisting of chrome steel, flint, zirconia, silicon nitride, and lead antimony alloy, wherein more preferably the balls of the ball mill are made of zirconia and/or silicon nitride, preferably of zirconia.
  • the grinding media comprises grinding balls, preferably having a diame ter in the range of from 50 to 1000 pm, more preferably of from 100 to 750 pm, more preferably of from 150 to 500 pm, more preferably of from 200 to 400 pm, and more preferably of from 250 to 350 pm.
  • the grinding media further comprises a liquid solvent system, preferably water.
  • the filling degree of the grinding balls in the ball mill is in the range of from 60 to 90%, more preferably of from 70 to 80 %, and more preferably of from 73 to 77 %.
  • the ball mill is operated at a speed in the range of from 500 to 6,000 rpm, more preferably of from 1 ,000 to 5,000 rpm, more preferably of from 2,000 to 4,500 rpm, more preferably of from 2,500 to 4,000 rpm, more preferably of from 2,600 to 3,800 rpm, more preferably of from 2,700 to 3,500 rpm, more preferably of from 2,800 to 3,200 rpm, and more preferably of from 2,900 to 3,100 rpm.
  • the one or more tetraalkylammonium cation containing compounds 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 is alkyl, and wherein R 4 is cycloalkyl, wherein preferably R 1 , R 2 , and R 3 in the one or more tetraalkylammonium cation R 1 R 2 R 3 R 4 N + -containing compounds inde pendently from one another stand for optionally branched (Ci-Ce)alkyl, preferably (Ci-Cs)alkyl, more preferably (Ci-C4)alkyl, and more preferably for optionally branched (Ci-C3)alkyl, wherein more preferably R 1 , R 2 , and R 3
  • the one or more tetraalkylammonium cation containing compounds 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 independently from one another is alkyl, and wherein R 4 is cycloalkyl
  • R 4 stands for optionally branched and/or optionally cyclic (C 1 -C 9 ) alkyl, preferably for optionally branched and/or optionally cyclic (Ci-Ce) alkyl, preferably for optionally branched and/or option ally cyclic (C 1 -C 7 ) alkyl, more preferably for optionally branched and/or optionally cyclic (Ci-Ce) alkyl
  • R 4 more stands for optionally heterocyclic 5- to 8-membered cycloalkyl, preferably for 5- to 7-membered cycloalkyl
  • the one or more tetraalkylammonium cation containing compounds 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 independently from one another is alkyl, and wherein R 4 is cycloalkyl
  • R 1 , R 2 , and R 3 in the one or more tetraalkylammonium cation R 1 R 2 R 3 R 4 N + -containing compounds independently from one another stand for alkyl, and wherein R 4 stands for cyclo hexyl.
  • the one or more tetraalkylammonium cation containing compounds 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 independently from one another is alkyl, and wherein R 4 is cycloalkyl
  • the one or more tetraalkylammonium cation R 1 R 2 R 3 R 4 N + -containing compounds comprise one or more A/,A/,A/-tri(Ci-C4)alkyl-(C5-C7)cycloalkylammonium compounds, prefera bly one or more /V, V,A/-tri(Ci-C3)alkyl-(C5-C6)cycloalkylammonium compounds, more preferably one or more /V,/V,/V-tri(Ci-C 2 )alkyl-(C 5 -C 6 )cycloal
  • the one or more tetraalkylammonium cation containing compounds are selected from the group consisting of A,A/-di(Ci-C 4 )alkyl-3,5-di(Ci-C 4 )alkylpyrrolidinium compounds, /V,/V-di(Ci-C 4 )alkyl-3,5-di(Ci-C 4 )alkylpiperidinium compounds, /V,/V-di(Ci-C 4 )alkyl-
  • the one or more tetraalkylammonium cation containing compounds are se lected from the group consisting of A/,/ ⁇ /-di(Ci-C 4 )aikyl-3,5-di(Ci-C 4 )alkylpyrrolidinium com pounds, A/,A/-di(Ci-C 4 )alkyl-3,5-di(Ci-C 4 )alkylpiperidinium compounds, A, A/-d i (C 1 -C 4 )a I ky I-3 , 5- di(Ci-C 4 )alkylhexahydroazepinium compounds, /V,/V-di(Ci-C 4 )alkyl-2,6-di(Ci- C 4 )alkylpyrrolidinium compounds, A/,A-di(Ci-C 4 )alkyl-2,6-di(Ci-C 4 )alkylpiperidin
  • L/, /V-d ia I ky I-3 , 5-d i a I ky I py rrol i d i n i u m compounds, A,/V-dialkyl-3,5- dialkylpiperidinium compounds, and/or A,/V-dialkyl-3,5-dialkylhexahydroazepinium compounds display the c/s configuration
  • the one or more ammonium cation R 1 R 2 R 3 R 4 N + -containing compounds are selected from the group consisting of /V,A/-di(Ci-C 2 )alkyl-c/s-3,5-di(Ci-C 2 )alkylpiperidinium compounds, and mixtures of two or more thereof, wherein more preferably the one or more ammonium cation containing compounds comprise one or more A/,A-dimethyl-c?/s-3,5- dimethylpiperidinium compounds.
  • the one or more tetraalkylammonium cation containing compounds are salts, more preferably 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 tetraalkylammonium cation containing compounds are tetraalkylammonium hydroxides and/or bromides, and more preferably tetraalkylammonium hy droxides.
  • the reactant mixture may comprise further components. It is preferred that the reactant mixture according to (ii) further contains one or more tetraalkylammonium cation R 5 R 6 R 7 R 8 N + -containing compounds, wherein R 5 , R 6 , R 7 , and R 8 , independently from one another stand for optionally substituted and/or optionally branched (Ci-Ce)alkyl, preferably (Ci-Cs)alkyl, more preferably (Ci-C 4 )alkyl, more preferably (Ci-C3)alkyl, and even more preferably for optionally substituted methyl or ethyl, wherein even more preferably R 5 , R 6 , R 7 , and R 8 stand for optionally substituted methyl, preferably unsubstituted methyl.
  • R 5 , R 6 , R 7 , and R 8 stand for optionally substituted methyl, preferably unsubstituted methyl.
  • the one or more tetraalkylammonium cation R 5 R 6 R 7 R 8 N + -containing compounds comprise one or more compounds selected from the group consisting of tetra(Ci- C 6 )alkylammonium compounds, more preferably tetra(Ci-C5)alkylammonium compounds, more preferably tetra(Ci-C 4 )alkylammonium compounds, and more preferably tetra(Ci- C 3 )alkylammonium compounds, wherein independently from one another the alkyl substituents are optionally branched, and wherein more preferably the one or more tetraalkylammonium cat ion R
  • R 5 R 6 R 7 R 8 [ j + -containing compounds consists of one or more tetramethylammonium compounds.
  • the reactant mixture according to (ii) further contains one or more tetraalkylammonium cation R 5 R 6 R 7 R 8 N + -containing compounds, wherein R 5 , R 6 , R 7 , and R 8 , independently from one another stand for optionally substituted and/or optionally branched (Ci- C 6 )alkyl
  • the one or more tetraalkylammonium cation R 5 R 6 R 7 R 8 N + -containing compounds are salts, more 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 con sisting of chloride, hydroxide, sulfate, and mixtures of two or more thereof, wherein more pref erably the one or more tetraalkyl
  • the reactant mixture according to (ii) further contains one or more tetraalkylammonium cation R 5 R 6 R 7 R 8 N + -containing compounds, wherein R 5 , R 6 , R 7 , and R 8 , independently from one another stand for optionally substituted and/or optionally branched (Ci- Ce)alkyl
  • the one or more tetraalkylammonium cation containing compounds 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 independently from one another is alkyl, and wherein R 4 is cycloalkyl, wherein the molar ratio R 5 R 6 R 7 R 8 N + : R 1 R 2 R 3 R 4 N + of the one or more tetraalkylammonium cations R S R 6 R 7 R 8 N + to the one or more tetraalkyl
  • the one or more tetraalkylammonium cation containing compounds 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 independently from one another is alkyl, and wherein R 4 is cycloalkyl, wherein the molar ratio SiC>2 : R 1 R 2 R 3 R 4 N + of the one or more sources of SiC>2 to the one or more tetraalkylammo nium cation R 1 R 2 R 3 R 4 N + -containing compounds in the mixture provided according to step (i) is in the range of from 0.1 to 20, more preferably from 0.5 to 15.0, more preferably from 2.0 to 1 1 .0, more preferably from 4.0 to 9.0, more preferably from 5.1 to 7.6, more preferably from 7.1 to 5.6, more preferably from 6.1 to 6.6, and even more preferably from 6.3 to 6.4.
  • the mixture provided according to step (i) comprises one or more sources of X2O3
  • the molar ratio S1O2 : X2O3 of the one or more sources of YO2 to the one or more sources of X2O3 is in the range of from 5 to 40, more preferably from 15 to 31 , more preferably from 20.0 to 26.0, more preferably from 24.0 to 32.0, more preferably from 26.0 to 30.0, more preferably from 26.7 to 28.8, more preferably from 27.2 to 28.3, and even more preferably from 27.7 to 27.8.
  • the polar protic liquid solvent system comprises one or more of n-butanol, isopropanol, propanol, ethanol, methanol, and water, more preferably one or more of ethanol, methanol, and water, wherein more preferably the polar protic liquid solvent system comprises, more preferably consists of, water, more preferably deionized water.
  • the polar protic liquid solvent system comprises water, wherein the molar ratio SiC>2 : H2O of the one or more sources of YO2 to water is in the range of from 0.1 to 50, more preferably from 0.5 to 30, more preferably from 1 to 25, more preferably from 2 to 21 , more preferably from 5 to 18, more preferably from 8 to 15, more preferably from 10.0 to 13.0, and even more preferably from 11.0 to 12.0.
  • the non-polar liquid solvent system comprises one or more of (C 5 - Cio)alkanes, (Cs-Cio)alkenes, (C5-Cio)aromatic organic compounds, (C4-Ce)alkylethers, (Ci- C3)alkylhalides, or mixtures of two or more thereof, more preferably from the group consisting of (C 6 -Cio)alkanes, (C 6 -Cio)alkenes, (C 6 -Cio)aromatic organic compounds, (C4-C6)alkylethers, (Ci-C2)alkylhalides, or mixtures of two or more thereof, preferably from the group consisting of (C 6 -Ce)alkanes, (Ce-Cejalkenes, (Ce-Csjaromatic organic compounds, or mixtures of two or more thereof, wherein more preferably the non-polar liquid solvent system comprises one or more of hexane, hept
  • the reactant mixture according to (II) comprises the non-polar liquid solvent system in an amount in the range of from 20 to 75 weight-%, more preferably in the range of from 30 to 65 weight-%, more preferably in the range of from 35 to 60 weight-%, more preferably in the range of from 40 to 55 weight-%, more preferably in the range of from 43 to 52 weight-%, more preferably in the range of from 45 to 50 weight-%, more preferably in the range of from 46.0 to 49.0 weight-%, more preferably in the range of from 47.0 to 48.0 weight-%.
  • 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 comprise ionic surfactants
  • the ionic surfactants comprise one or more anionic surfactants, more preferably one or more anion ic surfactants selected from the group consisting of salts of (C 6 -Cie)sulfate, (Ce- Cie)ethersulfate, (C 6 -Ci 8 )sulfonate, (C 6 -Ci 8 )sulfosuccinate (Ce-Ciejphosphate, (Ce- Cie)carboxylate, and mixtures of two or more thereof, more preferably from the group consisting of salts of (C 8 -Ci 6 )sulfate, (C 8 -Ci 6 )ethersulfate, (C8-Ci6)sulfonate, (C 8 -Ci 6 )sulfosuccinate, (Ce- Ci 6 )phosphate, (C 8 -Ci 6 )carbox
  • the one or more emulsifiers comprise ionic surfactants
  • the ionic surfactants comprise one or more cationic surfactants, more 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, (Cs- Ci 8 )pyridinium, benzalkonium, benzethonium, dimethyldioctadecylammonium, cetrimonium, dioctadecyldimethylammonium, and mixtures of two or more thereof, more preferably from the group consisting of salts of cetyltrimethylammonium, dodecyltrimethylammonium, cetylpyri
  • the one or more emulsifiers comprise ionic surfactants
  • the ionic surfactants comprise one or more zwitterionic surfactants, more preferably one or more betaines, wherein more preferably the ionic surfactants comprise cocamidopropyl betaine or alkyldimethylaminoxide.
  • the nonionic surfactants are selected from the group consisting of (C 8 -C 22 )alcohols, (Ce- C2o)alcohol ethoxylates with 1 to 8 ethylene oxide units, (C 6 -C 2 o)alkyl polyglycosides, polyoxy ethylene glycol alkyl ethers, polyoxypropylene glycol alkyl ethers, glucoside alkyl ethers, poly oxyethylene glycol alkylphenol ethers, glycerol alkyl esters, sorbitan alkyl esters, polyoxyeth ylene glycol sorbitan alkyl esters, cocamide monoethanolamine, cocamide diethanolamine, do- decyldimethylamine oxide, block copolymers of polyethylene glycol and polypropylene glycol, polyethoxylated tallow amine, and mixtures of two or
  • the one or more nonionic surfactants are selected from the group con sisting of (Ci4-C2o)alcohols, (Ce-Ciejalcohol ethoxylates with 2 to 6 ethylene oxide units, (Ce- Cie)alkyl polyglycosides, octaethylene glycol monododecyl ether and/or pentaethylene glycol monododecyl ether, polyoxypropylene glycol alkyl ethers, decyl glucoside, lauryl glucoside, myristil glucoside, octyl glucoside, polyoxyethylene glycol octylphenol ethers, preferably triton X- 100, nonoxynol-9, glyceryl laurate, polyglycerol polyricinoleate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monoole
  • the one or more nonionic surfactants are selected from the group con sisting of (Ci 6 -Ci 8 )alcohols, (Ci 6 -Ci 8 )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, sorbit
  • polyglyceryl-2-dipolyhydroxystearate diglyceryl- distearate, triglyceryl-distearate, C13/15 - PEG 3 , C13 - PEG 2 , glyceryl monooleate, sorbitan monooleate, polyglycerol-3-polyricinoleate, 016/18 - PEG 2 , oleyl - PEG 2 , PEG 20 - sorbitan monooleate, functionalized polyisobutene, 016/18 - PEGg, polyoxyethylene (10) oleyl ether, polyoxyethylene (20) oleyl ether, and mixtures of two or more thereof,
  • polyglyceryl-2-dipolyhydroxystearate preferably from the group consisting of polyglyceryl-2-dipolyhydroxystearate, 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 reactant mixture according to (ii) compris es the one or more emulsifiers in an amount in the range from 20 to 75 weight-%, preferably in the range of from 30 to 65 weight-%, more preferably in the range of from 35 to 60 weight-%, more preferably in the range of from 40 to 55 weight-%, more preferably in the range of from 43 to 52 weight-%, more preferably in the range of from 45 to 50 weight-%, more preferably in the range of from 46.0 to 49.0 weight-%, more preferably in the range of from 47.0 to 48.0 weight- %.
  • the reactant mixture according to (ii) comprises the mixture in an amount in the range of from 2.0 to 7.5 weight-%, more preferably in the range of from 3.0 to 6.5 weight-%, more preferably in the range of from 3.5 to 6.0 weight-%, more preferably in the range of from 4.0 to 5.5 weight-%, more preferably in the range of from 4.3 to 5.2 weight-%, more preferably in the range of from 4.5 to 5.0 weight-%, more preferably in the range of from 4.60 to 4.90 weight-%, more preferably in the range of from 4.70 to 4.80 weight-%.
  • the reactant mixture according to (ii) is a gel.
  • the process of the present invention may comprise further process steps. It is preferred that the process further comprises after (i) and prior to (ii)
  • the pretreatment conditions in (b) comprise a temperature in the range of from 80 to 175 °C, more preferably in the range of from 90 to 170 °C, more preferably in the range of from 100 to 165 °C, more preferably in the range of from 110 to 160 °C, more preferably in the range of from 120 to 155 °C, and more preferably in the range of from 130 to 150 °C.
  • the process further comprises (a) and (b) after (i) and prior to (ii), it is preferred that the pretreatment conditions in (b) comprise hydrothermal conditions.
  • the pretreatment conditions in (b) are applied for a duration in the range of from 1 to 72 h, more preferably in the range of from 6 to 60 h, more preferably in the range of from 12 to 54 h, more preferably in the range of from 14 to 42 h, more preferably in the range of from 16 to 36 h, more preferably in the range of from 18 to 32 h, and more preferably in the range of from 20 to 28 h.
  • the process of the present invention may comprise further process steps. It is preferred that the process further comprises after (i) and prior to (ii) subjecting the reactant mixture to emulsifying conditions. In the case where the process further comprises after (i) and prior to (ii) subjecting the reactant mixture to emulsifying conditions, it is preferred that the emulsifying conditions comprise agita tion of the reactant mixture, more preferably by stirring and/or sonication, and more preferably by stirring.
  • the process further comprises after (i) and prior to (ii) subjecting the reactant mixture to emulsifying conditions
  • the emulsifying conditions com prise use of a homogenizes more preferably with a rotor-stator homogenizes with an ultrasonic homogenizes with a high pressure homogenizes by microfluidic systems, or by membrane emulsification, more preferably with an ultrasonic homogenizes
  • the process further comprises after (i) and prior to (ii) subjecting the reactant mixture to emulsifying conditions
  • the emulsifying conditions are applied for a period ranging from 0.1 to 15 min, preferably from 1 to 13 min, more preferably from 2 to 12 min, more preferably from 3 to 11 min, more preferably from 4 to 10 min, more preferably from 5 to 9 min, more preferably from 6.0 to 8.0 min, and more preferably from 6.5 to 7.5 min.
  • a reactant stream is continuously passed through the reaction zone according to (i), wherein the reactant stream comprises a reactant mixture, the reactant stream being subject to crystallization conditions in the reaction zone par ticularly effecting a conversion of at least a portion of the components comprised in the reactant stream to obtain a product stream.
  • the reactant stream comprises a reactant mixture
  • the reactant stream being subject to crystallization conditions in the reaction zone par ticularly effecting a conversion of at least a portion of the components comprised in the reactant stream to obtain a product stream.
  • no matter is added to and/or removed from the reactant stream during its passage through the reaction zone comprised in the flow reactor according to (i), wherein more preferably no matter is added, wherein more preferably no matter is added and no matter is removed from the reactant stream during its passage through the reaction zone comprised in the flow reactor according to (i).
  • the crystallization conditions according to (iii) comprise heating the reactant stream at a temperature in the range of from 160 to 320°C, preferably of from 170 to 300 °C, more preferably of from 175 to 295 °C, more preferably of from 190 to 290°C, more preferably of from 210 to 270°C, more preferably of from 220 to 260°C, more preferably of from 230 to 250°C, more preferably of from 235 to 245°C, and more preferably of from 237 to 243 °C.
  • the crystallization conditions according to (iii) comprise autogenous pressure, more preferably a pressure in the range of from 17 to 25 MPa, preferably in the range of from 12 to 20 MPa, more preferably in the range of from 14 to 18 MPa, more preferably in the range of from 15.0 to 17.0 MPa, more preferably in the range of from 15.5 to 16.5 MPa.
  • the reactant stream is passed in the reactant zone with a flow rate in the range of from 0.01 to 20 ml/min, more preferably in the range of from 0.1 to 15 ml/min, more preferably in the range of from 0.15 to 11 ml/min, more preferably in the range of from 0.20 to 1.00 ml/min, more preferably in the range of from 0.35 to 0.80 ml/min, more preferably in the range of from 0.40 to 0.70 ml/min, more preferably in the range of from 0.50 to 0.65 ml/min, more preferably in the range of from 0.55 to 0.59 ml/min.
  • the reactant stream is passed in the reactant zone with a liquid hour ly space velocity in the range of from 0.05 to 10 h 1 , more preferably in the range of from 0.1 to 5 IT 1 , more preferably in the range of from 0.5 to 2.0 ir 1 , more preferably in the range of from 0.8 to 1.5 IT 1 , more preferably in the range of from 1.0 to 1.3 ir 1 , more preferably in the range of from 1.1 to 1.2 IT 1 .
  • the process of the present invention may comprise further process steps. It is preferred that after (i) and prior to (ii) the reactant stream is heated at a temperature in the range of from 45 to 135 °C, more preferably in the range of from 65 to 1 15 °C, more preferably in the range of from 75 to 105 °C, more preferably in the range of from 80 to 100 °C, more pref erably in the range of from 85 to 95 °C.
  • the reactant stream is continuously fed into the flow reactor for a dura tion ranging from 0.1 h to 140 d, more preferably from 0.15 h to 100 d, more preferably from 0.2 h to 70 d, more preferably from 0.5 h to 50 d, more preferably from 1 h to 40 d, more preferably from 2 h to 35 d, more preferably from 5 h to 30 d, more preferably from 10 h to 25 d, more preferably from 15 h to 20 d, more preferably from 20 h to 15 d, and more preferably from 1 d to 10 d.
  • the process of the present invention may comprise further process steps. It is preferred that the process further comprises
  • the process further comprises (iv).
  • isolating in (iv) is achieved by filtration and/or centrifugation, more preferably by centrifugation.
  • the process further comprises (v).
  • washing in (v) is conducted with a solvent system comprising one or more solvents, wherein preferably the one or more solvents are selected from the group con sisting of polar protic solvents and mixtures thereof,
  • the process further comprises (vi).
  • drying in (vi) is conducted at a temperature in the range of from 20 to 160 °C, more preferably in the range of from 30 to 140 °C, more preferably in the range of from 40 to 120 °C, more preferably in the range of from 50 to 1 10 °C, more preferably in the range of from 60 to 100 °C, more preferably in the range of from 70 to 90 °C, and more preferably in the range of from 75 to 85 °C.
  • the process further comprises (vii).
  • the calcining in (vii) is effected at a temperature in the range from 300 to 750 °C, more preferably from 325 to 650 °C, more preferably from 350 to 600 °C, more preferably from 375 to 550 °C, more preferably from 400 to 500 °C, and more preferably from 425 to 475 °C.
  • the process of the present invention may comprise further process steps. It is preferred that the process further comprises
  • the step of sub jecting the zeolitic material to an ion-exchange procedure includes the steps of
  • the one or more metal ions are selected from the group consisting of ions of alkaline earth metal elements and/or tran sition metal elements, more preferably from the group consisting of ions of metals selected from group 4 and groups 6-1 1 of the Periodic Table of the Elements, more preferably from group 4 and groups 8-1 1 , wherein more preferably the one or more metal ions are selected from the group consisting of ions 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 ions of Ti, Cu, Fe, Rh, Pd, Pt, and mixtures of two or more thereof, wherein more preferably the at least one ionic non-framework element or compound contained in the zeolitic material is ion-exchanged against Cu and/or Fe, preferably against Cu.
  • the process further comprises (viii)
  • the zeo litic material is ion-exchanged such as to obtain a loading of the one or more metal ions in the zeolitic material ranging from 0.1 to 15 weight- % calculated as the element and based on 100 weight- % of SiC>2 contained in the zeolitic material, more preferably from 0.5 to 10 weight-%, more preferably from 1 to 8 weight-%, more preferably from 1.5 to 7 weight-%, more preferably from 2 to 6 weight-%, more preferably from 2.5 to 5.5 weight-%, more preferably from 3 to 5 weight-%, more preferably from 3.5 to 4.5 weight-%.
  • the zeolitic material obtained from crystallization in (ill) may have unique properties.
  • the zeolitic material obtained from crystallization in (iii) may have a mean particle size D50 by volume as determined according to ISO 13320:2009 of at least 0.5 pm, preferably 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 zeolitic material obtainable and/or obtained according to the process of any one of the embodiments disclosed herein.
  • the present invention relates to a use of a zeolitic material obtainable and/or obtained according to the process of 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 cata lyst support or a precursor 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 adsorption of CO2; for the oxidation of NH3, 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 crack ing (FCC) processes; and/or as a catalyst in organic conversion reactions, preferably in the conversion of alcohols to olefins, and more
  • a continuous process for preparing a zeolitic material comprising YO2 and optionally X2O3 in its framework structure, wherein Y is a tetravalent element and X is a trivalent element, said process comprising
  • the reactant stream comprises a reactant mixture comprising a non-polar liquid solvent system, one or more emulsifiers, and a mixture of one or more sources of YO2, optionally one or more sources of X2O3, seed crystals, a polar protic liquid solvent sys tem, and one or more tetraalkylammonium cation containing compounds as structure di recting agent;
  • the zeolitic material has a framework structure type selected from the group consisting of AEI, AFX, ANA, BE A, BEC, CAN, CHA, CDO, EMT, ERI, EUO, FAU, FER, GME, HEU, ITH, ITW, KFI, LEV, MEI, MEL, MFI, MOR, MTN, MWW, OFF, RRO, RTH, SAV, SFW, SZR, TON, and a mixture of two or more thereof, preferably from the group consisting of CAN , AEI, EMT, SAV, SZR, KFI, ERI, OFF, RTH, GME, AFX, SFW, BE A, CHA, FAU, FER, HEU, LEV, MEI, MEL, MFI, MOR, MWW, and a mixture of two or more thereof, more preferably from the group consisting of AEI, BE A, CHA, ERI, FAU, FER, HEU, LEV
  • Y is selected from the group consisting of Si, Ge, Sn, Ti, Zr, and combinations of two or more thereof, preferably from the group con sisting of Si, Ge, Ti, and combinations of two or more thereof, more preferably from the group consisting of Si, Ti, and a combination thereof, wherein more preferably Y is Si.
  • X is selected from the group con sisting of B, Al, Ga, In, and combinations of two or more thereof, preferably from the group consisting of B, Al, Ga, and combinations of two or more thereof, more preferably from the group consisting of Al, Ga, and a combination thereof, wherein more preferably X is Al.
  • the zeolitic material has the CHA framework structure type comprising YO2 and X2O3, wherein Y is Si and X is Al.
  • the flow reactor according to (i) is selected among a tubular reactor, and a ring reactor, preferably among a plain tubular re actor, a tubular membrane reactor, a tubular reactor with Coanda effect, a ring reactor, and combinations thereof, wherein more preferably the flow reactor is a plain tubular reac tor and/or a ring reactor, wherein more preferably the flow reactor is a plain tubular reac tor.
  • the flow reactor according to (i) comprises a reaction zone having a volume in the range of from 5 to 5000 cm 3 , preferably in the range of from 5 to 2500 cm 3 , more preferably in the range of from 10 to 1000 cm 3 , more preferably in the range of from 10 to 100 cm 3 , more preferably in the range of from 20 to 50 cm 3 , more preferably in the range of from 20 to 30 cm 3 , more preferably in the range of from 25 to 30 cm 3 .
  • the flow reactor according to (i) comprises a reaction zone having a length in the range of from 0.2 to 100 m, preferably in the range of from 0.5 to 50 m, more preferably in the range of from 1.0 to 10 m, more preferably in the range of from 1.5 to 5.0 m, more preferably in the range of from 1.75 to 3.50 m, more preferably in the range of from 2.00 to 2.50 m.
  • the flow reactor according to (i) comprises a tubular reactor, and wherein at least a portion of the flow reactor is of a regu lar cylindrical form having a constant inner diameter perpendicular to the direction of flow, wherein the inner diameter is preferably in the range of from 0.1 to 100 mm, more prefer ably in the range of from 0.1 to 50 mm, more preferably in the range of from 0.2 to 25 mm, more preferably in the range of from 0.5 to 10 mm, more preferably in the range of from 0.5 to 5.0 mm, more preferably in the range of from 1.0 to 3.5 mm, more preferably in the range of from 1.5 to 2.5 mm, more preferably in the range of from 1.75 to 2.25 mm, more preferably in the range of from 1.95 to 2.05 mm.
  • the wall of the flow reactor ac cording to (i) reactor is made of a metallic material, wherein the metallic material compris es 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 consist- ing of Ta, Cr, Fe, Ni, Mo, and combinations and/or alloys of two or more thereof, prefera bly from the group consisting of Cr, Fe, Ni, Mo, and combinations and/or alloys of two or more thereof.
  • any one of embodiments 1 to 1 1 wherein the surface of the inner wall of the flow reactor is lined with an organic polymer material, wherein 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 consisting 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 preferably the polymer material comprises poly(tetrafluoroethylene), where in more preferably the inner wall of the continuous flow reactor is lined with
  • the flow reactor is straight and/or comprises one or more curves with respect to the direction of flow, wherein prefer ably the continuous flow reactor is straight.
  • the flow reactor consists of a single stage.
  • the one or more sources of YO2 comprises one or more compounds selected from the group consisting of silicas, silicates, and mixtures thereof,
  • 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 SiC>2 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.
  • the one or more sources of X 2 O 3 comprises one or more aluminum salts, preferably an aluminate of an alkali metal and/or aluminum hydroxide, preferably aluminum hydroxide, wherein more preferably the one or more sources of X 2 O 3 is an aluminate of an alkali metal and/or aluminum hydrox ide, preferably aluminum hydroxide,
  • the alkali metal is preferably selected 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 seed crystals comprise a zeoltic material
  • the zeolitic material comprises YO2 and optionally X2O3, wherein Y is a tetra valent element and X is a trivalent element
  • preferably Y is selected from the group consisting of Si, Ge, Sn, Ti, Zr, and combinations of two or more thereof, preferably from the group consisting of Si, Ge, Ti, and combinations of two or more there of, more preferably from the group consisting of Si, Ti, and a combination thereof, wherein more preferably Y is Si
  • preferably X is selected from the group consisting of B, Al, Ga, In, and combinations of two or more thereof, preferably from the group consist ing of B, Al, Ga, and combinations of two or more thereof, more preferably from the group consisting of Al, Ga, and a combination thereof, wherein more preferably X is Al.
  • the zeolitic material comprised in the seed crystals has a framework structure selected from the group consisting of AEI, AFX, ANA, BEA, BEC, CAN, CHA, CDO, EMT, ERI, EUO, FAU, FER, GME, HEU, ITH, ITW, KFI, LEV, MEI, MEL, MFI, MOR, MTN, MWW, OFF, RRO, RTH, SAV, SFW, SZR, TON, and a mixture of two or more thereof, preferably from the group consisting of CAN, AEI, EMT, SAV, SZR, KFI, ERI, OFF, RTH, GME, AFX, SFW, BEA, CHA, FAU, FER, HEU, LEV, MEI, MEL, MFI, MOR, MWW, and a mixture of two or more thereof, more preferably from the group consisting of AEI, BEA, CHA, FAU, FER, HEU,
  • the zeolitic material comprised in the seed crystals has a CHA-type framework structure
  • the zeolitic material comprised in the seed crystals and having a CHA-type framework structure is se lected 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 comprised in the seed crystals and having a CHA-type framework structure comprises chabazite and/or SSZ-13, preferably chabazite, and wherein more preferably the zeolitic material comprised in the seed crystals and hav ing a CHA-type framework structure is chabazite and/or SSZ-13, preferably SSZ-13.
  • the zeolitic material comprised in the seed crystals has a AEI-type framework structure
  • the zeolitic material comprised in the seed crystals and having a AEI-type framework structure is se lected from the group consisting of SSZ-39, SAPO-18, SIZ-8, including mixtures of two or more thereof, wherein more preferably the zeolitic material comprised in the seed crystals and having a AEI-type framework structure comprises SSZ-39, and wherein more prefer ably the zeolitic material comprised in the seed crystals and having a AEI-type framework structure is SSZ-39.
  • any one of embodiments 1 to 20, wherein the amount of seed crystals in the mixture according to (ii) is in the range of from 0.1 to 20 wt.-% based on 100 wt.-% of S1O2 contained in the mixture, preferably from 1 to 18 wt.-%, more preferably from 5 to 15 weight-%, more preferably from 7 to 13 weight-%, more preferably from 8 to 12 weight-%, more preferably from 9 to 11 weight-%, and more preferably from 9.5 to 10.5 weight-%.
  • any one of embodiments 1 to 21 wherein the seed crystals are ground prior to (ii), wherein preferably grinding is carried out in a mill selected from the group consisting of a stirred media mill, a planetary ball mill, a ball mill, a roller mill, a kneader, a high shear mixer, and a mix muller,
  • a mill selected from the group consisting of a stirred media mill, a planetary ball mill, a ball mill, a roller mill, a kneader, a high shear mixer, and a mix muller
  • a stirred media mill preferably from the group consisting of a stirred media mill, a ball mill, a roller mill, a plan etary mill, and a high shear mixer,
  • tetraalkylammonium cation containing compounds comprise 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 is alkyl, and wherein R 4 is cycloalkyl, wherein preferably R 1 , R 2 , and R 3 in the one or more tetraalkylammonium cation R 1 R 2 R 3 R 4 N + -containing compounds inde pendently from one another stand for optionally branched (Ci-Ce)alkyl, preferably (Ci- Cejalkyl, 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
  • R 4 stands for optionally branched and/or option ally cyclic (C 1 -C 9 ) alkyl, preferably for optionally branched and/or optionally cyclic (Ci-Ce) alkyl, preferably for optionally branched and/or optionally cyclic (C 1 -C 7 ) alkyl, more prefer ably for optionally branched and/or optionally cyclic (Ci-Ce) alkyl, wherein R 4 more prefer ably stands 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.
  • R 1 R 2 R 3 R 4 N + -containing compounds comprise one or more A/,A/,/ ⁇ /-tri(Ci-C4)alkyl-(C5-C7)cycloalkylammonium compounds, preferably one or more A/,A/,/V-th(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,A/,/V-tri(Ci-C2)alkyl-cyc!opentylammonium and/or one or more N,N,N- tri(Ci- C2)alkyl-cyclohexylammonium compounds, more preferably one or more compounds se lected from L/,/n,/V-triethyl-cyclohex
  • tetraalkylammonium cation containing compounds are selected from the group consisting of /V,/V-di(Ci-C 4 )alkyl-3,5-di(Ci-C 4 )alkylpyrrolidinium compounds, A,/V-di(Ci-C 4 )alkyl-3,5- di(Ci-C4)alkylpiperidinium compounds, A ,/V-di(Ci-C 4 )alkyl-3,5-di(Ci- C4)alkylhexahydroazepinium compounds, V,A/-di(Ci-C 4 )alkyl-2,6-di(Ci- C4)alkylpyrrolidinium compounds, A,/V-di(Ci-C 4 )alkyl-2,6-di(Ci-C 4 )alkylpiperidinium com pounds, /V,/V-di(Ci-C 4 )alkyl
  • A/,/V-di(Ci-C 2 )alkyl-3,5-di(Ci- C2)alkylpyrrolidinium compounds A,/V-di(Ci-C 2 )alkyl-3,5-di(Ci-C 2 )alkylpiperidinium com pounds, /V,/V-di(Ci-C 2 )alkyl-3,5-di(Ci-C 2 )alkylhexahydroazepinium compounds, N,N- di(Ci-C 2 )alkyl-2,6-di(Ci-C 2 )alkylpyrrolidinium compounds, /V,/V-di(Ci-C 2 )alkyl-2,6-di(Ci- C2)alkylpiperidinium compounds, L, LZ-d i (C i -C 2 )al kyl-2 , 6-d i (C 1 )alkyl-2 , 6-d
  • pounds, A/,/V-dialkyl-3,5-dialkylpiperidinium compounds, and/or A/,A/-dialkyl-3,5- dialkylhexahydroazepinium compounds display the os configuration, the trans configura tion, or contain a mixture of the c/s and trans isomers,
  • the one or more ammonium cation R 1 R 2 R 3 R 4 N + -containing com pounds are selected from the group consisting of L/, A-d i (C i -C 2 )a I ky I- c/s-3 , 5-d i (C 1 - C2)alkylpiperidinium compounds, and mixtures of two or more thereof, wherein more pref erably the one or more ammonium cation containing compounds comprise one or more V,A-dimethyl-c/5-3,5-dimethylpiperidinium compounds.
  • tetraalkylammonium cation containing compounds are salts, preferably 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 bromide, chloride, hydroxide, sulfate, and mixtures of two or more thereof, wherein more preferably the one or more tetraalkylammonium cation containing compounds are tetraalkylammoni um hydroxides and/or bromides, and more preferably tetraalkylammonium hydroxides.
  • R S R 6 R 7 R 8 N + -containing compounds comprise one or more compounds selected from the group consisting of tetra(Ci-C 6 )alkylammonium compounds, preferably tetra(Ci- C5)alkylammonium compounds, more preferably tetra(Ci-C4)alkylammonium compounds, and more preferably tetra(Ci-C3)alkylammonium compounds, wherein independently from one another the alkyl substituents are optionally branched, and wherein more preferably the one or more tetraalkylammonium cation
  • R 5 R 6 R 7 R 8 N + -containing compounds are se lected from the group consisting of optionally branched tetrapropylammonium compounds, ethyltripropylammonium compounds, diethyldipropylammonium compounds, triethylprop- ylammonium compounds, methyltripropylammonium compounds, dimethyldi
  • tetraalkylammonium cation R 5 R 6 R 7 R 8 N + -containing compounds consists of one or more tetramethylammonium compounds.
  • the process of embodiment 35 or 36, wherein the one or more tetraalkylammonium cation R 5 R 6 R 7 R 8 N + -containing compounds are salts, preferably one or more salts selected from the group consisting of halides, preferably chloride and/or bromide, more preferably chlo ride, 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 tetraalkylammonium cation R 5 R 6 R 7 R 8 N + -containing compounds are tetraalkylammonium hydroxides and/or chlorides, and even more preferably t
  • tetraalkylammonium cation containing compounds comprise 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 is alkyl, and wherein R 4 is cycloalkyl, wherein the molar ratio
  • R 5 R 6 R 7 R 8 N + ; R 1 R 2 R 3 R 4 N + of the one or more tetraalkylammonium cations R 5 R 6 R 7 R 8 N + to the one or more tetraalkylammonium cations R 1 R 2 R 3 R 4 N + in the mixture provided accord ing to step (i) is in the range of from 0.01 to 5, preferably from 0.05 to 2, more preferably from 0.1 to 1.5, more preferably from 0.2 to 1.2, more preferably from 0.3 to 1.1 , more preferably from 0.4 to 1.0, more preferably from 0.5 to 0.9, and even more preferably from 0.6 to 0.8.
  • tetraalkylammonium cation containing compounds comprise 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 is alkyl, and wherein R 4 is cycloalkyl, wherein the molar ratio S1O2 : R I R 2 R 3 R 4 N + of the one or more sources of S1O2 to the one or more tetraalkylammonium cation R 1 R 2 R 3 R 4 N + -containing compounds in the mixture provided according to step (i) is in the range of from 0.1 to 20, preferably from 0.5 to 15.0, more preferably from 2.0 to
  • step (i) comprises one or more sources of X2O3 , wherein the molar ratio S1O2 : X2O3 of the one or more sources of YO2 to the one or more sources of X2O3 is in the range of from 5 to 40, preferably from 15 to 31 , more preferably from 20.0 to 26.0, more preferably from 24.0 to 32.0, more preferably from 26.0 to 30.0, more preferably from 26.7 to 28.8, more preferably from 27.2 to 28.3, and even more preferably from 27.7 to 27.8.
  • the polar protic liquid solvent system comprises one or more of n-butanol, isopropanol, propanol, ethanol, methanol, and water, more preferably one or more of ethanol, methanol, and water, wherein more preferably the polar protic liquid solvent system comprises, more preferably consists of, water, more preferably deionized water.
  • the polar protic liquid solvent system comprises water, wherein the molar ratio S1O2 : H2O of the one or more sources of YO2 to water is in the range of from 0.1 to 50, preferably from 0.5 to 30, more prefera bly from 1 to 25, more preferably from 2 to 21 , more preferably from 5 to 18, more prefer ably from 8 to 15, more preferably from 10.0 to 13.0, and even more preferably from 11.0 to 12.0.
  • non-polar liquid solvent sys tem comprises one or more of (C5-Cio)alkanes, (Cs-Cio)aikenes, (Cs-Cio)aromatic organ ic compounds, (C4-C8)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 & - Cio)aromatic organic compounds, (C 4 -C 6 )alkylethers, (Ci-C2)alkylhalides, or mixtures of two or more thereof, preferably from the group consisting of (Ce-Cejalkanes, (Ce- Ce)alkenes, (Ce-Cejaromatic organic compounds, or mixtures of two or more thereof, wherein more preferably the non-polar liquid solvent
  • the reactant mixture according to (ii) comprises the non-polar liquid solvent system in an amount in the range of from 20 to 75 weight-%, preferably in the range of from 30 to 65 weight-%, more preferably in the range of from 35 to 60 weight-%, more preferably in the range of from 40 to 55 weight-%, more preferably in the range of from 43 to 52 weight-%, more preferably in the range of from 45 to 50 weight-%, more preferably in the range of from 46.0 to 49.0 weight-%, more preferably in the range of from 47.0 to 48.0 weight-%.
  • 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 -Cie)sulfate, (C 6 -Ci 8 )ethersulfate, (C 6 -Ci 8 )sulfonate, (Ce- Ci 8 )sulfosuccinate (Ce-Ci 8 )phosphate, (C 6 -Ci 8 )carboxylate, and mixtures of two or more thereof, more preferably from the group consisting of salts of (Cs-Ci 6 )sulfate, (Ce- Ci 6 )ethersulfate, (C 8 -Ci 6 )carboxylate, and mixture
  • 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 (Ce-Cisjtrimethylammonium, (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, benzalkonium,
  • the ionic surfactants comprise one or more zwitterionic surfactants, preferably one or more betaines, wherein more pref erably the ionic surfactants comprise cocamidopropylbetaine 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 gly col alkylphenol ethers, glycerol alkyl esters, sorbitan alkyl esters, polyoxyethylene glycol sorbitan alkyl esters, cocamide monoethanolamine, cocamide diethanolamine, dodecyl- dimethylamine oxide, block copolymers of polyethylene glycol and polypropylene glycol, polyethoxylated 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, (Ce-Ci 8 )alcohol ethoxylates with 2 to 6 ethylene oxide units, (C 8 -Cis)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 monostea
  • the one or more nonionic surfactants are selected from the group consisting of (Ci 6 -Ci 8 )alcohols, (Ci 6 -Ci 8 )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 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
  • nonionic surfactant comprises polyoxyethylene (10) oleyl ether and/or polyoxyethylene (20) oleyl ether.
  • the reactant mixture according to (ii) comprises the one or more emulsifiers in an amount in the range from 20 to 75 weight-%, preferably in the range of from 30 to 65 weight-%, more preferably in the range of from 35 to 60 weight-%, more preferably in the range of from 40 to 55 weight-%, more preferably in the range of from 43 to 52 weight-%, more preferably in the range of from 45 to 50 weight-%, more preferably in the range of from 46.0 to 49.0 weight-%, more prefera bly in the range of from 47.0 to 48.0 weight-%.
  • the reactant mixture according to (ii) comprises the mixture in an amount in the range of from 2.0 to 7.5 weight-%, prefer ably in the range of from 3.0 to 6.5 weight-%, more preferably in the range of from 3.5 to 6.0 weight-%, more preferably in the range of from 4.0 to 5.5 weight-%, more preferably in the range of from 4.3 to 5.2 weight-%, more preferably in the range of from 4.5 to 5.0 weight-%, more preferably in the range of from 4.60 to 4.90 weight-%, more preferably in the range of from 4.70 to 4.80 weight-%.
  • emulsifying conditions comprise use of a homogenizer, preferably with a rotor-stator homogenizes with an ultrasonic homogeniz es with a high pressure homogenizer, by microfluidic systems, or by membrane emulsifi cation, more preferably with an ultrasonic homogenizer.
  • any one of embodiments 1 to 62, wherein the crystallization conditions according to (ill) comprise heating the reactant stream at a temperature in the range of from 160 to 320°C, preferably of from 170 to 300 °C, more preferably of from 175 to 295 °C, more preferably of from 190 to 290°C, more preferably of from 210 to 270°C, more preferably of from 220 to 260°C, more preferably of from 230 to 250°C, more preferably of from 235 to 245°C, and more preferably of from 237 to 243 °C.
  • any one of embodiments 1 to 63, wherein the crystallization conditions according to (ill) comprise autogenous pressure, preferably a pressure in the range of from 17 to 25 MPa, preferably in the range of from 12 to 20 MPa, more preferably in the range of from 14 to 18 MPa, more preferably in the range of from 15.0 to 17.0 MPa, more preferably in the range of from 15.5 to 16.5 MPa.
  • autogenous pressure preferably a pressure in the range of from 17 to 25 MPa, preferably in the range of from 12 to 20 MPa, more preferably in the range of from 14 to 18 MPa, more preferably in the range of from 15.0 to 17.0 MPa, more preferably in the range of from 15.5 to 16.5 MPa.
  • ethanol more preferably from the group consisting of ethanol, methanol, water, and mixtures thereof,
  • drying in (vi) is conducted at a temperature in the range of from 20 to 160 °C, preferably in the range of from 30 to 140 °C, more preferably in the range of from 40 to 120 °C, more preferably in the range of from 50 to 110 °C, more preferably in the range of from 60 to 100 °C, more preferably in the range of from 70 to 90 °C, and more preferably in the range of from 75 to 85 °C.
  • any one of embodiments 69 to 73 wherein the process further comprises (viii) subjecting the zeolitic material obtained in (iv), (v), (vi), or (vii) to an ion-exchange procedure, wherein at least one ionic non-framework element or compound contained in the zeolitic material is ion-exchanged against one or more metal ions.
  • the step of subjecting the zeolitic material to an ion-exchange procedure includes the steps of
  • the one or more metal ions are selected from the group consisting of ions of alkaline earth metal elements and/or transition metal elements, preferably from the group consisting of ions of metals selected from group 4 and groups 6-1 1 of the Periodic Table of the Elements, more preferably from group 4 and groups 8-1 1 , wherein more preferably the one or more metal ions are selected from the group consisting of ions 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 ions of Ti, Cu, Fe, Rh, Pd, Pt, and mixtures of two or more thereof, wherein more preferably the at least one ionic non-framework element or compound contained in the zeolitic mate rial is ion-exchanged against Cu and/or Fe, preferably against Cu.
  • a zeolitic material obtainable and/or obtained according to the process of any one of em bodiments 1 to 78.
  • a zeolitic material according to embodiment 79 as a molecular sieve, as an adsor bent, 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 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 oxi dation 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 methanol to ole fin (MTO) catalysis; more preferably for the selective cata
  • Figure 1 shows the X-ray diffraction pattern (measured using Cu K alpha- 1 radiation) of the zeolitic materials obtained according to Example 1 before (see Flow_1_220°C- 240°C _before) and after (see Flow_J __220°C-240°C after) applying the inventive process on a reaction mixture according to Reference example 1.
  • the angle 2 theta in ° is shown along the abscissa and the intensity is plotted along the ordinate in arbitrary units.
  • the resulting mixture had a molar ratio Si0 2 : AI2O3 : CHTMAOH : TMAOH : H2O of silica to alumina to cyclohexyltrimetylammonium hydroxide to tetramethylammonium hydroxide to water of 1 : 0.036 : 0.158 : 0.1 13 : 11.5. Said mixture was further stirred for 10 min before the addition of 0.120 g of CHA seed crystals.
  • the seed crystals were milled prior to use in a bead-milling apparatus (LMZ015, Ashizawa Finetech Ltd.) whereby 10 g of the source of the seed crystals were dispersed in 300 ml of water and milled with the bead-milling apparatus for 120 min at 3000 rpm using zirconia beads with a diameter of 300 pm. In the vessel, 75% of the volume were filled with zirconia beads. After the milling treatment, the slurry was centrifuged, and the residual solid was recovered. The seed crystals thus obtained had a crystallinity of 43 % as de- termined according to reference example 3.
  • LMZ015, Ashizawa Finetech Ltd. Ashizawa Finetech Ltd.
  • the mixture was then charged to a 23ml Teflon- lined autoclave for aging at 140 °C for 24 h with 20 rpm tumbling. 6.57 g of the aged gel were mixed with 6.57 g of cyclohexane and 0.657 g of polyoxyethylene(10)oleyiether. The mixture was homogenized using a ultrasonic homogenizer (Hielscher UP400S) for 7 min for obtaining a gel.
  • a ultrasonic homogenizer Hielscher UP400S
  • Reference example 2 Determination of X-ray diffraction pattern and the crystallinity
  • the powder X-ray diffraction (XRD) patterns were collected using a diffractometer (Rigaku Ulti ma IV) equipped with a D/Tex Ultra detector operated with Cu Ka monochromatized radiation at 40 kV and 40 mA. A scan step was 0.02° at a scan speed of 207min. Crystallinity was calculat ed using integrated peak areas of the peaks in 2theta range of 20° to 35°.
  • Reference example 3 Determination of X-ray diffraction pattern and the crystallinity
  • 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.
  • Example 1 Process for the continuous preparation of a zeolitic material having the CHA framework structure type
  • the flow reactor for testing the continuous preparation of a zeolitic material having the CHA framework structure type comprised a stainless synthesis tube lined with Teflon having an inner diameter of 2.0 mm, a pump for providing the reactant stream comprising the reactant mixture, a reactant mixture tank, eight sequentially arranged heaters for heating a reaction zone, and a product tank.
  • the temperature of the tube was regulated by hot/cold water.
  • the gel obtained from Reference Example 1 was charged into the flow reactor and crystallized at a temperature 240 °C for 920 s, whereby the gel was first heated by a first heater to a tem perature T1 of 220 °C and then by the following seven heaters to a temperature T2 of 240 °C.
  • the conditions as listed in tables 1 and 2 were applied during said time.
  • a zeolitic material was obtained having the CHA framework structure type with a crystallinity of 51.5 % after a reaction time of 920 s compared to a crystallinity of 4.1 % before applying the inventive process, whereby the crystallinity was determined according to Reference Example 2.

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Abstract

The present invention relates to a continuous process for preparing a zeolitic material comprising YO2 and optionally X2O3 in this its framework structure, wherein Y is a tetravalent element and X is a trivalent element, said process comprising. (i) providing a flow reactor comprising a reaction zone; (ii) continuously passing a reactant stream through the reaction zone according to (i), wherein the reactant stream comprises a reactant mixture comprising a non-polar liquid solvent system, one or more emulsifiers, and a mixture of one or more sources of YO2, optionally one or more sources of X2O3, seed crystals, a polar protic liquid solvent system, and one or more tetraalkylammonium cation containing compounds as structure directing agent; (iii) subjecting the reactant stream to crystallization conditions in the reaction zone and removing a product stream from the reaction zone, wherein the product stream comprises the zeolitic material. Furthermore, the invention further to a zeolitic material obtainable and/or obtained according to the inventive process, as well as to the use of said zeolitic material.

Description

PROCESS FOR A CONTINUOUS SYNTHESIS OF A CHA ZEOLITIC MATERIAL FROM AN EMULSION
TECHNICAL FIELD
The present invention relates to a continuous process for the preparation of a zeolitic material as well as to a zeolitic material obtainable or obtained by said process. Furthermore, the pre sent invention relates to the use of the inventive zeolitic material, in particular as a catalyst.
INTRODUCTION
The synthesis of zeolitic materials preferably using simple starting compounds involves a com plex process of self organization which often necessitates special conditions such as elevated temperatures and/or pressure, wherein such reactions typically require the heating of starting materials under autogenous pressure for obtaining the zeolitic material after lengthy reaction times ranging from days to several weeks. Accordingly, due to the often harsh reaction condi tions and the long reaction times, batch synthesis has long been the method of choice for syn thesizing zeolitic materials. Batch reactions however present numerous limitations, in particular relative to the levels of space-time-yield which may be attained.
In this respect, WO 2015/185625 A relates to a process for the preparation of a zeolitic material of the CHA-type framework structure using cycloalkylammonium compounds in combination with a tetraalkylammonium compound for achieving improvements in cast-effectiveness. Ac cording to the examples, the synthesis of the zeolites having the CHA-type framework structure was conducted batch-wise in an autoclave.
According to Wakihara et al. in Reaction Chemistry and Engineering 2018 the continuous prep aration of zeolitic materials would be extremely challenging due to the sharp viscosity increase taking place during the synthesis. As a general approach, a process for preparing zeolitic mate rials having the ERI, BEA or CHA framework structure type is discussed based on an emulsion system together with a Teflon-lined pipe reactor offering the opportunity to address said issue.
WO 201 1/064186 A1 and EP 2 325 143 A2, on the other hand, respectively relate to a process for the preparation of zeolites having the CHA framework structure which employ tetrame- thylammonium hydroxide in addition to at least one organic structure directing agent. Among the structure directing agents which may be used to this effect, said documents mention N,N,N- trimethylcyclohexylammonium compounds among several compounds as possible structure directing agents for obtaining a zeolitic material having the CHA framework structure, wherein however N,N,N-trimethyl-1 -adamantyltrimethylammonium compounds are preferably and effec tively taught in said documents for obtaining the aforementioned material. Zones et al. "A Study of Guest/Host Energetics for the Synthesis of Cage Structures NON and CHA" in Studies in Surface Science and Catalysis, Vol. 84, pp. 29-36, Elsevier Science B.V.
(1994) describes the synthesis of SSZ-13 using a variety of organotemplates including the tri- methylcyclohexylammonium cation, wherein the latter would display very low rates of crystalliza tion in particular when compared to the use of the adamantyltrimethylammonium cation.
WO 2013/182974 A relates to the use of trimethylcyclohexylammoniumhydroxide as organo- template for the synthesis of CHA-type zeolitic materials involving crystallization times of 48 hours or more.
Consequently, there remains a need for a cost-effective process for the production of zeolitic materials in particular having the CHA- or AEI-type framework structure. Furthermore, and in addition thereto, there remains the need to improve continuous processes of zeolitic materials such that crystallization takes place within a flow reactor without being limited to short operation periods in view of clogging issues.
Furthermore, there is an ongoing need for improved zeolitic materials in particular having the CHA- or AEI-type framework structure, in particular with respect to the catalytic properties for use in a variety of application and in particular for use in the treatment of NOx in automotive exhaust gas as catalyst and/or catalyst support. This applies in particular in view of national legislation and environmental policy which require increasing effectiveness of environmental catalysts such as Cu-Chabazite and related zeolitic materials. Furthermore, there is a need for improving the process the preparation of such materials, in particular relative to the costs and efficiency thereof.
DETAILED DESCRIPTION
It was therefore an object of the present invention to provide an improved continuous process for preparing a zeolitic material which allows for extended periods of uninterrupted operation, in particular on an industrial scale.
Thus, it has surprisingly been found that the operation time can be significantly prolonged com pared to known processes whereby the advantages of comparatively short synthesis time as regards the preparation of a zeolitic material can be maintained compared to known batch pro cess when applying a continuous process for the preparation of zeolitic materials according to the present invention. In particular, it has been found that the preparation of a chabazite which is particularly used for automotive emission catalysts which normally takes more than 20 h syn thesis time may be prepared in less than 2 h.
Furthermore and in addition thereto, it has surprisingly been found that by applying the process of the present invention the disadvantages, in particular clogging, of known continuous pro cesses can be considerably diminished. Therefore, the present invention relates to a continuous process for preparing a zeolitic material comprising YO2 and optionally X2O3 in its framework structure, wherein Y is a tetravalent ele ment and X is a trivalent element, said process comprising
(i) providing a flow reactor comprising a reaction zone;
(ii) continuously passing a reactant stream through the reaction zone according to (i), wherein the reactant stream comprises a reactant mixture comprising a non-polar liquid solvent system, one or more emulsifiers, and a mixture of one or more sources of YO2, optionally one or more sources of X2O3, seed crystals, a polar pro tic liquid solvent system, and one or more
tetraalkylammonium cation containing compounds as structure directing agent;
(iii) subjecting the reactant stream to crystallization conditions in the reaction zone and remov ing a product stream from the reaction zone, wherein the product stream comprises the zeolitic material.
It is preferred that the zeolitic material has a framework structure type selected from the group consisting of AEI, AFX, ANA, BEA, BEC, CAN, CHA, CDO, EMT, ERI, EUO, FAU, FER, GME, HEU, ITH, ITW, KFI, LEV, MEI, MEL, MFI, MOR, MTN, MWW, OFF, RRO, RTH, SAV, SFW, SZR, TON, and a mixture of two or more thereof, more preferably from the group consisting of CAN, AEI, EMT, SAV, SZR, KFI, ERI, OFF, RTH, GME, AFX, SFW, BEA, CHA, FAU, FER,
HEU, LEV, MEI, MEL, MFI, MOR, MWW, and a mixture of two or more thereof, more preferably from the group consisting of AEI, BEA, CHA, ERI, FAU, FER, GME, LEV, MFI, MOR, MWW, and a mixture of two or more thereof, more preferably from the group consisting of AEI, BEA, CHA, ERI and a mixture thereof, wherein more preferably the zeolitic material has the CHA or the AEI framework structure type.
It is preferred that Y is selected from the group consisting of Si, Ge, Sn, Ti, Zr, and combina tions of two or more thereof, preferably from the group consisting of Si, Ge, Ti, and combina tions of two or more thereof, more preferably from the group consisting of Si, Ti, and a combina tion thereof, wherein more preferably Y is Si.
Further, it is preferred that X is selected from the group consisting of B, Al, Ga, In, and combina tions of two or more thereof, preferably from the group consisting of B, Al, Ga, and combinations of two or more thereof, more preferably from the group consisting of Al, Ga, and a combination thereof, wherein more preferably X is Al.
According to a first alternative, it is preferred that the zeolitic material has the CHA framework structure type comprising YO2 and X2O3, wherein Y is Si and X is Al.
According to a second alternative, it is preferred the zeolitic material has the AEI framework structure type comprising YO2 and X2O3, wherein Y is Si and X is Al.
As regards the geometry of the flow reactor according to (i), no particular restriction applies. It is preferred that the flow reactor according to (i) is selected among a tubular reactor, and a ring reactor, more preferably among a plain tubular reactor, a tubular membrane reactor, a tubular reactor with Coanda effect, a ring reactor, and combinations thereof, wherein more preferably the flow reactor is a plain tubular reactor and/or a ring reactor, wherein more preferably the flow reactor is a plain tubular reactor.
It is preferred that the flow reactor according to (i) comprises a reaction zone having a volume in the range of from 5 to 5000 cm3, more preferably in the range of from 5 to 2500 cm3, more pref erably in the range of from 10 to 1000 cm3, more preferably in the range of from 10 to 100 cm3, more preferably in the range of from 20 to 50 cm3, more preferably in the range of from 20 to 30 cm3, more preferably in the range of from 25 to 30 cm3.
It is preferred that the flow reactor according to (i) comprises a reaction zone having a length in the range of from 0.2 to 100 m, more preferably in the range of from 0.5 to 50 m, more prefera bly in the range of from 1 .0 to 10 m, more preferably in the range of from 1 .5 to 5.0 m, more preferably in the range of from 1 .75 to 3.50 m, more preferably in the range of from 2.00 to 2.50 m.
In the case where the flow reactor according to (i) comprises a tubular reactor, it is preferred that at least a portion of the flow reactor is of a regular cylindrical form having a constant inner diameter perpendicular to the direction of flow, wherein the inner diameter is preferably in the range of from 0.1 to 100 mm, more preferably in the range of from 0.1 to 50 mm, more prefera bly in the range of from 0.2 to 25 mm, more preferably in the range of from 0.5 to 10 mm, more preferably in the range of from 0.5 to 5.0 mm, more preferably in the range of from 1 .0 to 3.5 mm, more preferably in the range of from 1 .5 to 2.5 mm, more preferably in the range of from 1 .75 to 2.25 mm, more preferably in the range of from 1 .95 to 2.05 mm.
As regards the chemical or physical nature of the wall of the flow reactor, no particular re striction applies. It is preferred that the wall of the flow reactor according to (i) 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 combinations and/or alloys of two or more thereof, more 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.
Further, it is preferred that the surface of the inner wall of the flow reactor is lined with an organ ic polymer material, wherein 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 consisting 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 preferably the polymer material comprises
poly(tetrafluoroethylene), wherein more preferably the inner wall of the continuous flow reactor is lined with poly(tetrafluoroethylene). It is preferred that the flow reactor 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.
It is preferred that the flow reactor consists of a single stage.
As regards the chemical or physical nature of the one or more sources of YO2, no particular restriction applies. It is preferred that the one or more sources of YO2 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, disil icate, colloidal silica, pyrogenic silica, silicic acid esters, tetraalkoxysilanes, and mixtures of two or more thereof,
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,
more 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,
more preferably from the group consisting of water glass, colloidal silica, silicic acid esters, tetraalkoxysilanes, and mixtures of two or more thereof
more preferably from the group consisting of water glass, colloidal silica, and mixtures thereof, wherein more preferably the one or more sources of S1O2 is selected from the group consisting of water glass, colloidal silica, and mixtures thereof, wherein more preferably colloidal silica is employed as the one or more sources of Si02.
As regards the chemical or physical nature of the one or more sources of X2O3, no particular restriction applies. It is preferred that the one or more sources of X2O3 comprises one or more aluminum salts, more preferably an aluminate of an alkali metal and/or aluminum hydroxide, preferably aluminum hydroxide, wherein more preferably the one or more sources of X2O3 is an aluminate of an alkali metal and/or aluminum hydroxide, preferably aluminum hydroxide, wherein the alkali metal is preferably selected 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.
It is preferred that the seed crystals comprise a zeolitic material, wherein the zeolitic material comprises YO2 and optionally X2O3, wherein Y is a tetravalent element and X is a trivalent ele ment, wherein preferably Y is selected from the group consisting of Si, Ge, Sn, Ti, Zr, and com binations of two or more thereof, preferably from the group consisting of Si, Ge, Ti, and combi nations of two or more thereof, more preferably from the group consisting of Si, Ti, and a com bination thereof, wherein more preferably Y is Si, and wherein preferably X is selected from the group consisting of B, Al, Ga, In, and combinations of two or more thereof, preferably from the group consisting of B, Al, Ga, and combinations of two or more thereof, more preferably from the group consisting of Al, Ga, and a combination thereof, wherein more preferably X is Al. As regards the framework structure type of the zeolitic material comprised in the seed crystals, no particular restriction applies. It is preferred that the zeolitic material comprised in the seed crystals has a framework structure selected from the group consisting of AEI, AFX, ANA, BE A, BEC, CAN, CHA, CDO, EMT, ERI, EUO, FAU, FER, GME, HEU, ITH, ITW, KFI, LEV, MEI,
MEL, MFI, MOR, MTN, MWW, OFF, RRO, RTH, SAV, SFW, SZR, TON, and a mixture of two or more thereof, preferably from the group consisting of CAN, AEI, EMT, SAV, SZR, KFI, ERI,
OFF, RTH, GME, AFX, SFW, BE A, CHA, FAU, FER, HEU, LEV, MEI, MEL, MFI, MOR, MWW, and a mixture of two or more thereof, more preferably from the group consisting of AEI, BEA, CHA, ERI, FAU, FER, GME, LEV, MFI, MOR, MWW, and a mixture of two or more thereof, more preferably from the group consisting of AEI, BEA, CHA, ERI and a mixture thereof, where in more preferably the zeolitic material comprised in the seed crystals has the CHA or the AEI framework structure type.
According to a first alternative, it is preferred that the zeolitic material comprised in the seed crystals has a CHA-type framework structure. It is particularly preferred that the zeolitic material comprised in the seed crystals and 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 , |Li-Na| [Al- Si-0]-CHA, (Ni(deta)2)-UT-6, SSZ-13, and SSZ-62, including mixtures of two or more thereof, more preferably from the group consisting of ZYT-6, SAPO-47, Na-Chabazite, Chabazite, LZ- 218, Linde D, Linde R, SAPO-34, ZK-14, K-Chabazite, Phi, DAF-5, UiO-21 , SSZ-13, and SSZ- 62, including mixtures of two or more thereof,
more preferably from the group consisting of Chabazite, Linde D, Linde R, SAPO-34, SSZ-13, and SSZ-62, including mixtures of two or more thereof,
more preferably from the group consisting of Chabazite, SSZ-13, and SSZ-62, including mix tures of two or three thereof,
wherein more preferably the zeolitic material comprised in the seed crystals and having a CHA- type framework structure comprises chabazite and/or SSZ-13, preferably chabazite, and where in more preferably the zeolitic material comprised in the seed crystals and having a CHA-type framework structure is chabazite and/or SSZ-13, preferably SSZ-13.
According to a second alternative, it is preferred that the zeolitic material comprised in the seed crystals has a AEI -type framework structure. It is particularly preferred that the zeolitic material comprised in the seed crystals and having a AEI -type framework structure is selected from the group consisting of SSZ-39, SAPO-18, SIZ-8, including mixtures of two or more thereof, where in more preferably the zeolitic material comprised in the seed crystals and having a AEI -type framework structure comprises SSZ-39, and wherein more preferably the zeolitic material com prised in the seed crystals and having a AEI-type framework structure is SSZ-39.
Further, it is preferred that the amount of seed crystals in the mixture according to (ii) is in the range of from 0.1 to 20 wt.-% based on 100 wt-% of S1O2 contained in the mixture, more pref erably from 1 to 18 wt.-%, more preferably from 5 to 15 weight-%, more preferably from 7 to 13 weight-%, more preferably from 8 to 12 weight-%, more preferably from 9 to 1 1 weight-%, and more preferably from 9.5 to 10.5 weight-%.
It is preferred that the seed crystals are ground prior to (ii), wherein more preferably grinding is carried out in a mill selected from the group consisting of a stirred media mill, a planetary ball mill, a ball mill, a roller mill, a kneader, a high shear mixer, and a mix muller,
more preferably from the group consisting of a stirred media mill, a ball mill, a roller mill, a planetary mill, and a high shear mixer,
and more preferably from the group consisting of a ball mill, a planetary ball mill, a high shear mixer, and a mix muller,
wherein more preferably grinding is carried out in a ball mill and/or a planetary ball mill, prefera bly in a ball mill.
It is preferred that the seed crystals are ground prior to (ii). It is particularly preferred that in the case where the seed crystals are ground prior to (ii) grinding is carried out in a ball mill and/or in a planetary ball mill, preferably in a ball mill. In this regard, it is further preferred that balls are used made of a material selected from the group consisting of stainless steel, ceramic, and rub ber, more preferably from the group consisting of chrome steel, flint, zirconia, silicon nitride, and lead antimony alloy, wherein more preferably the balls of the ball mill are made of zirconia and/or silicon nitride, preferably of zirconia.
In the case where grinding is carried out in a ball mill, it is preferred that a grinding media is used. It is preferred that the grinding media comprises grinding balls, preferably having a diame ter in the range of from 50 to 1000 pm, more preferably of from 100 to 750 pm, more preferably of from 150 to 500 pm, more preferably of from 200 to 400 pm, and more preferably of from 250 to 350 pm.
In the case where grinding is carried out in a ball mill using a grinding media, it is further pre ferred that the grinding media further comprises a liquid solvent system, preferably water.
In the case where the seed crystals are ground prior to (ii) in a ball mill and/or in a planetary ball mill, preferably in a ball mill, it is further preferred that the filling degree of the grinding balls in the ball mill is in the range of from 60 to 90%, more preferably of from 70 to 80 %, and more preferably of from 73 to 77 %.
In the case where the seed crystals are ground prior to (ii) in a ball mill, it is further preferred the ball mill is operated at a speed in the range of from 500 to 6,000 rpm, more preferably of from 1 ,000 to 5,000 rpm, more preferably of from 2,000 to 4,500 rpm, more preferably of from 2,500 to 4,000 rpm, more preferably of from 2,600 to 3,800 rpm, more preferably of from 2,700 to 3,500 rpm, more preferably of from 2,800 to 3,200 rpm, and more preferably of from 2,900 to 3,100 rpm. As regards the one or more tetraalkylammonium cation containing compounds, it is preferred that the one or more tetraalkylammonium cation containing compounds comprise one or more tetraalkylammonium cation R1R2R3R4N+-containing compounds, wherein R1, R2, and R3 inde pendently from one another is alkyl, and wherein R4 is cycloalkyl, wherein preferably R1, R2, and R3 in the one or more tetraalkylammonium cation R1 R2R3R4N+-containing compounds inde pendently from one another stand for optionally branched (Ci-Ce)alkyl, preferably (Ci-Cs)alkyl, more preferably (Ci-C4)alkyl, and more preferably for optionally branched (Ci-C3)alkyl, wherein more preferably R1, R2, and R3 independently from one another stand for methyl or ethyl, wherein more preferably R1, R2, and R3 stand for methyl.
In the case where the one or more tetraalkylammonium cation containing compounds comprise one or more tetraalkylammonium cation R1 R2R3R4N+-containing compounds, wherein R1, R2, and R3 independently from one another is alkyl, and wherein R4 is cycloalkyl, it is preferred that R4 stands for optionally branched and/or optionally cyclic (C1-C9) alkyl, preferably for optionally branched and/or optionally cyclic (Ci-Ce) alkyl, preferably for optionally branched and/or option ally cyclic (C1-C7) alkyl, more preferably for optionally branched and/or optionally cyclic (Ci-Ce) alkyl, wherein R4 more preferably stands 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 R4 stands for optionally heterocyclic 6-membered cycloalkyl, and more preferably for cyclohexyl.
Further in the case where the one or more tetraalkylammonium cation containing compounds comprise one or more tetraalkylammonium cation R1 R2R3R4N+-containing compounds, wherein R1, R2, and R3 independently from one another is alkyl, and wherein R4 is cycloalkyl, it is pre ferred that R1, R2, and R3 in the one or more tetraalkylammonium cation R1 R2R3R4N+-containing compounds independently from one another stand for alkyl, and wherein R4 stands for cyclo hexyl.
Further in the case where the one or more tetraalkylammonium cation containing compounds comprise one or more tetraalkylammonium cation R1 R2R3R4N+-containing compounds, wherein R1, R2, and R3 independently from one another is alkyl, and wherein R4 is cycloalkyl, it is pre ferred that the one or more tetraalkylammonium cation R1 R2R3R4N+-containing compounds comprise one or more A/,A/,A/-tri(Ci-C4)alkyl-(C5-C7)cycloalkylammonium compounds, prefera bly one or more /V, V,A/-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-cyclopentylammonium and/or one or more /V,/V,/V-tri(Ci- C2)alkyl-cyclohexylammonium compounds, more preferably one or more compounds selected from A , V,A/-triethyl-cyclohexylammonium, /V,/V-diethyl-/V-methyl-cyclohexylammonium, N,N- dimethyl-ZV-ethyl-cyclohexylammonium, /V,/V,/V-trimethyl-cyclohexylammonium compounds, and mixtures of two or more thereof, wherein more preferably the one or more tetraalkylammonium cation R1 R2R3R4N+-containing compounds comprise one or more A/,/V-dimethyl-A/-ethyl- cyclohexylammonium and/or / ,/V,A-trimethyl-cyclohexylammonium compounds, more prefera bly one or more /V,/V,A/-trimethyl-cyc!ohexylammonium compounds. Further, it is preferred that the one or more tetraalkylammonium cation containing compounds are selected from the group consisting of A,A/-di(Ci-C4)alkyl-3,5-di(Ci-C4)alkylpyrrolidinium compounds, /V,/V-di(Ci-C4)alkyl-3,5-di(Ci-C4)alkylpiperidinium compounds, /V,/V-di(Ci-C4)alkyl-
3.5-di(Ci-C4)alkylhexahydroazepinium compounds, L , LZ-d i (C i -C 4 )al kyl-2 , 6-d i (C 1 - C4)alkylpyrrolidinium compounds, A/,A/-di(Ci-C4)alkyl-2,6-di(Ci-C4)alkylpiperidinium com pounds, /V,/V-di(Ci-C4)alkyl-2,6-di(Ci-C4)alkylhexahydroazepinium compounds, and mixtures of two or more thereof,
more preferably from the group consisting of /V,/V-di(Ci-C3)alkyl-3,5-di(Ci-C3)alkylpyrrolidinium compounds, A ,A/-di(Ci-C3)alkyl-3,5-di(Ci-C3)alkylpiperidinium compounds, /V,/V-di(Ci-C3)alkyl-
3.5-di(Ci-C3)alkylhexahydroazepinium compounds, L/, /V-d i (C 1 -C 3 )al kyl-2 , 6-d i (C 1 - C3)alkylpyrrolidinium compounds, A/,A/-di(Ci-C3)alkyl-2,6-di(Ci-C3)alkylpiperidinium com pounds, A/,A/-di(Ci-C3)alkyl-2,6-di(Ci-C3)alkylhexahydroazepinium compounds, and mixtures of two or more thereof,
more preferably from the group consisting of //,/V-di(Ci-C2)alkyl-3,5-di(Ci-C2)alkylpyrrolidinium compounds, /V,A/-di(Ci-C2)alkyl-3,5-di(Ci-C2)alkylpiperidinium compounds, A/,A/-di(Ci-C2)alkyl-
3.5-di(Ci-C2)alkylhexahydroazepinium compounds, A A-d i (C 1 -C 2 )al kyl-2 , 6-d i (C 1 - C2)alkylpyrrolidinium compounds, A/, V-di(Ci-C2)alkyl-2,6-di(Ci-C2)alkylpiperidinium com pounds, A,A/-di(Ci-C2)alkyl-2,6-di(Ci-C2)alkyihexahydroazepinium compounds, and mixtures of two or more thereof,
more preferably from the group consisting of /V,A/-di(Ci-C2)alkyl-3,5-di(Ci-C2)alkylpiperidinium compounds, A/,A-di(Ci-C2)alkyl-2,6-di(Ci-C2)alkylpiperidinium compounds, and mixtures of two or more thereof, wherein more preferably the one or more tetraalkylammonium cation contain ing compounds comprise one or more A/,/V-dimethyl-3,5-dimethylpiperidinium and/or N,N- diethyl-2,6-dimethylpiperidinium compounds, preferably one or more A/,A/-dimethyl-3,5- dimethylpiperidinium compounds.
In the case where the one or more tetraalkylammonium cation containing compounds are se lected from the group consisting of A/,/\/-di(Ci-C4)aikyl-3,5-di(Ci-C4)alkylpyrrolidinium com pounds, A/,A/-di(Ci-C4)alkyl-3,5-di(Ci-C4)alkylpiperidinium compounds, A, A/-d i (C 1 -C 4 )a I ky I-3 , 5- di(Ci-C4)alkylhexahydroazepinium compounds, /V,/V-di(Ci-C4)alkyl-2,6-di(Ci- C4)alkylpyrrolidinium compounds, A/,A-di(Ci-C4)alkyl-2,6-di(Ci-C4)alkylpiperidinium com pounds, /V,A/-di(Ci-C4)alkyl-2,6-di(Ci-C4)alkylhexahydroazepinium compounds, and mixtures of two or more thereof, it is preferred that the A,/V-diaikyl-3,5-dialkyipyrrolidinium compounds, N,N- dialkyl-3,5-dialkylpiperidinium compounds, and/or /V,/V-dialkyl-3,5-dialkylhexahydroazepinium compounds display the c/s configuration, the trans configuration, or contain a mixture of the c/s and trans isomers,
wherein preferably the L/, /V-d ia I ky I-3 , 5-d i a I ky I py rrol i d i n i u m compounds, A,/V-dialkyl-3,5- dialkylpiperidinium compounds, and/or A,/V-dialkyl-3,5-dialkylhexahydroazepinium compounds display the c/s configuration,
wherein more preferably the one or more ammonium cation R1R2R3R4N+-containing compounds are selected from the group consisting of /V,A/-di(Ci-C2)alkyl-c/s-3,5-di(Ci-C2)alkylpiperidinium compounds, and mixtures of two or more thereof, wherein more preferably the one or more ammonium cation containing compounds comprise one or more A/,A-dimethyl-c?/s-3,5- dimethylpiperidinium compounds.
It is preferred that the one or more tetraalkylammonium cation containing compounds are salts, more preferably 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 tetraalkylammonium cation containing compounds are tetraalkylammonium hydroxides and/or bromides, and more preferably tetraalkylammonium hy droxides.
The reactant mixture may comprise further components. It is preferred that the reactant mixture according to (ii) further contains one or more tetraalkylammonium cation R5R6R7R8N+-containing compounds, wherein R5, R6, R7, and R8, independently from one another stand for optionally substituted and/or optionally branched (Ci-Ce)alkyl, preferably (Ci-Cs)alkyl, more preferably (Ci-C4)alkyl, more preferably (Ci-C3)alkyl, and even more preferably for optionally substituted methyl or ethyl, wherein even more preferably R5, R6, R7, and R8 stand for optionally substituted methyl, preferably unsubstituted methyl.
In the case where the reactant mixture according to (ii) further contains one or more
tetraalkylammonium cation R5R6R7R8N+-containing compounds, wherein R5, R6, R7, and R8, independently from one another stand for optionally substituted and/or optionally branched (Ci- Ce)alkyl, it is preferred that the one or more tetraalkylammonium cation R5R6R7R8N+-containing compounds comprise one or more compounds selected from the group consisting of tetra(Ci- C6)alkylammonium compounds, more preferably tetra(Ci-C5)alkylammonium compounds, more preferably tetra(Ci-C4)alkylammonium compounds, and more preferably tetra(Ci- C3)alkylammonium compounds, wherein independently from one another the alkyl substituents are optionally branched, and wherein more preferably the one or more tetraalkylammonium cat ion R5R6R7R8N+-containing compounds are selected from the group consisting of optionally branched tetrapropylammonium compounds, ethyltripropylammonium compounds, diethyldi- propylammonium compounds, triethylpropylammonium compounds, methyltripropylammonium compounds, dimethyldipropylammonium compounds, trimethylpropylammonium compounds, tetraethylammonium compounds, triethylmethylammonium compounds, diethyldimethylammo- nium compounds, ethyltrimethylammonium compounds, tetramethylammonium compounds, and mixtures of two or more thereof, preferably from the group consisting of optionally branched tetraethylammonium compounds, triethylmethylammonium compounds, diethyldimethylammo- nium compounds, ethyltrimethylammonium compounds, tetramethylammonium compounds, and mixtures of two or more thereof, preferably from the group consisting of tetramethylammo nium compounds, wherein more preferably the one or more tetraalkylammonium cation
R5R6R7R8[ j+-containing compounds consists of one or more tetramethylammonium compounds.
Further in the case where the reactant mixture according to (ii) further contains one or more tetraalkylammonium cation R5R6R7R8N+-containing compounds, wherein R5, R6, R7, and R8, independently from one another stand for optionally substituted and/or optionally branched (Ci- C6)alkyl, it is preferred that the one or more tetraalkylammonium cation R5R6R7R8N+-containing compounds are salts, more 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 con sisting of chloride, hydroxide, sulfate, and mixtures of two or more thereof, wherein more pref erably the one or more tetraalkylammonium cation R5R6R7R8N+-containing compounds are tetraalkylammonium hydroxides and/or chlorides, and even more preferably tetraalkylammoni um hydroxides.
Further in the case where the reactant mixture according to (ii) further contains one or more tetraalkylammonium cation R5R6R7R8N+-containing compounds, wherein R5, R6, R7, and R8, independently from one another stand for optionally substituted and/or optionally branched (Ci- Ce)alkyl, it is preferred that the one or more tetraalkylammonium cation containing compounds comprise one or more tetraalkylammonium cation R1 R2R3R4N+-containing compounds, wherein R1, R2, and R3 independently from one another is alkyl, and wherein R4 is cycloalkyl, wherein the molar ratio R5R6R7R8N+ : R1R2R3R4N+ of the one or more tetraalkylammonium cations RSR6R7R8N+ to the one or more tetraalkylammonium cations R1R2R3R4N+ in the mixture provid ed according to step (i) is in the range of from 0.01 to 5, preferably from 0.05 to 2, more prefer ably from 0.1 to 1 .5, more preferably from 0.2 to 1.2, more preferably from 0.3 to 1 .1 , more preferably from 0.4 to 1 .0, more preferably from 0.5 to 0.9, and even more preferably from 0.6 to 0.8.
It is preferred that the one or more tetraalkylammonium cation containing compounds comprise one or more tetraalkylammonium cation R1 R2R3R4N+-containing compounds, wherein R1, R2, and R3 independently from one another is alkyl, and wherein R4 is cycloalkyl, wherein the molar ratio SiC>2 : R1R2R3R4N+ of the one or more sources of SiC>2 to the one or more tetraalkylammo nium cation R1 R2R3R4N+-containing compounds in the mixture provided according to step (i) is in the range of from 0.1 to 20, more preferably from 0.5 to 15.0, more preferably from 2.0 to 1 1 .0, more preferably from 4.0 to 9.0, more preferably from 5.1 to 7.6, more preferably from 7.1 to 5.6, more preferably from 6.1 to 6.6, and even more preferably from 6.3 to 6.4.
In the case where the mixture provided according to step (i) comprises one or more sources of X2O3 , it is preferred that the molar ratio S1O2 : X2O3 of the one or more sources of YO2 to the one or more sources of X2O3 is in the range of from 5 to 40, more preferably from 15 to 31 , more preferably from 20.0 to 26.0, more preferably from 24.0 to 32.0, more preferably from 26.0 to 30.0, more preferably from 26.7 to 28.8, more preferably from 27.2 to 28.3, and even more preferably from 27.7 to 27.8.
It is preferred that the polar protic liquid solvent system comprises one or more of n-butanol, isopropanol, propanol, ethanol, methanol, and water, more preferably one or more of ethanol, methanol, and water, wherein more preferably the polar protic liquid solvent system comprises, more preferably consists of, water, more preferably deionized water. Further, it is preferred that the polar protic liquid solvent system comprises water, wherein the molar ratio SiC>2 : H2O of the one or more sources of YO2 to water is in the range of from 0.1 to 50, more preferably from 0.5 to 30, more preferably from 1 to 25, more preferably from 2 to 21 , more preferably from 5 to 18, more preferably from 8 to 15, more preferably from 10.0 to 13.0, and even more preferably from 11.0 to 12.0.
It is preferred that the non-polar liquid solvent system comprises one or more of (C5- Cio)alkanes, (Cs-Cio)alkenes, (C5-Cio)aromatic organic compounds, (C4-Ce)alkylethers, (Ci- C3)alkylhalides, or mixtures of two or more thereof, more preferably from the group consisting of (C6-Cio)alkanes, (C6-Cio)alkenes, (C6-Cio)aromatic organic compounds, (C4-C6)alkylethers, (Ci-C2)alkylhalides, or mixtures of two or more thereof, preferably from the group consisting of (C6-Ce)alkanes, (Ce-Cejalkenes, (Ce-Csjaromatic organic compounds, or mixtures of two or more thereof, wherein more preferably the non-polar liquid solvent system comprises one or more of hexane, heptane, octane, cyclohexane, cycloheptane, cyclooctane, benzene, toluene, ethylbenzene, mesitylene, durene, and xylene, more preferably one or more of hexane, hep tane, octane, cyclohexane, cycloheptane, cyclooctane, and benzene, more preferably one or more of hexane, cyclohexane, cycloheptane, and cyclooctane, wherein more preferably the non-polar liquid solvent system comprises, more preferably consists of, cyclohexane.
Further, it is preferred that the reactant mixture according to (II) comprises the non-polar liquid solvent system in an amount in the range of from 20 to 75 weight-%, more preferably in the range of from 30 to 65 weight-%, more preferably in the range of from 35 to 60 weight-%, more preferably in the range of from 40 to 55 weight-%, more preferably in the range of from 43 to 52 weight-%, more preferably in the range of from 45 to 50 weight-%, more preferably in the range of from 46.0 to 49.0 weight-%, more preferably in the range of from 47.0 to 48.0 weight-%.
As regards the chemical or physical nature of the one or more emulsifiers, no particular re striction applies. It is preferred that 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.
In the case where the one or more emulsifiers comprise ionic surfactants, it is preferred that the ionic surfactants comprise one or more anionic surfactants, more preferably one or more anion ic surfactants selected from the group consisting of salts of (C6-Cie)sulfate, (Ce- Cie)ethersulfate, (C6-Ci8)sulfonate, (C6-Ci8)sulfosuccinate (Ce-Ciejphosphate, (Ce- Cie)carboxylate, and mixtures of two or more thereof, more preferably from the group consisting of salts of (C8-Ci6)sulfate, (C8-Ci6)ethersulfate, (C8-Ci6)sulfonate, (C8-Ci6)sulfosuccinate, (Ce- Ci6)phosphate, (C8-Ci6)carboxylate, and mixtures of two or more thereof, more preferably from the group consisting of salts of (Cio-Ci4)sulfate, (Cio-Ci4)ethersulfate, (C«rCi4)sulfonate, (Cs- Ci4)sulfosuccinate, (C«rCi4)phosphate, (Cio-Ci4)carboxylate, and mixtures of two or more thereof, more preferably from the group consisting of salts of laurylsulfate, laurylsulfonate, dioc tyl sulfosuccinate, laurylphosphate, laurate, and mixtures of two or more thereof, wherein the counterion is preferably selected from the group consisting of H+, alkali metals, alkaline earth metals, ammonium, and combinations of two or more thereof, more preferably from the group consisting of H+, Li+, Na+, K+, ammonium, and combinations of two or more thereof, more pref erably from the group consisting of Na+, K+, ammonium, and combinations of two or more thereof, wherein even more preferably the counterion is Na+ and/or ammonium, preferably Na+.
Further in the case where the one or more emulsifiers comprise ionic surfactants, it is preferred that the ionic surfactants comprise one or more cationic surfactants, more 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 (C8-Ci8)trimethylammonium, (Cs- Ci8)pyridinium, benzalkonium, benzethonium, dimethyldioctadecylammonium, cetrimonium, dioctadecyldimethylammonium, and mixtures of two or more thereof, more preferably from the group consisting of salts of cetyltrimethylammonium, dodecyltrimethylammonium, cetylpyridini- um, benzalkonium, benzethonium, dimethyldioctadecylammonium, cetrimonium, dioctadecyl dimethylammonium, wherein the counterion is preferably selected from the group consisting of halides, carbonates, hydroxide, nitrate, phosphate, sulfate, and combinations of two or more thereof, more preferably from the group consisting of chloride, fluoride, bromide, hydrogen car bonate, hydroxide, nitrate, sulfate, and combinations of two or more thereof, wherein more pref erably the counterion is chloride and/or nitrate, preferably chloride.
Further in the case where the one or more emulsifiers comprise ionic surfactants, it is preferred that the ionic surfactants comprise one or more zwitterionic surfactants, more preferably one or more betaines, wherein more preferably the ionic surfactants comprise cocamidopropyl betaine or alkyldimethylaminoxide.
In the case where the one or more emulsifiers comprise nonionic surfactants, it is preferred that the nonionic surfactants are selected from the group consisting of (C8-C22)alcohols, (Ce- C2o)alcohol ethoxylates with 1 to 8 ethylene oxide units, (C6-C2o)alkyl polyglycosides, polyoxy ethylene glycol alkyl ethers, polyoxypropylene glycol alkyl ethers, glucoside alkyl ethers, poly oxyethylene glycol alkylphenol ethers, glycerol alkyl esters, sorbitan alkyl esters, polyoxyeth ylene glycol sorbitan alkyl esters, cocamide monoethanolamine, cocamide diethanolamine, do- decyldimethylamine oxide, block copolymers of polyethylene glycol and polypropylene glycol, polyethoxylated tallow amine, and mixtures of two or more thereof,
wherein more preferably the one or more nonionic surfactants are selected from the group con sisting of (Ci4-C2o)alcohols, (Ce-Ciejalcohol ethoxylates with 2 to 6 ethylene oxide units, (Ce- Cie)alkyl polyglycosides, octaethylene glycol monododecyl ether and/or pentaethylene glycol monododecyl ether, polyoxypropylene glycol alkyl ethers, decyl glucoside, lauryl glucoside, myristil glucoside, octyl glucoside, polyoxyethylene glycol octylphenol ethers, preferably triton X- 100, nonoxynol-9, glyceryl laurate, polyglycerol polyricinoleate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene (10) oleyl ether, polyoxyethylene (20) oleyl ether, cocamide monoethanolamine, cocamide diethanolamine, dodecyldimethylamine oxide, block copolymers of polyethylene glycol and polypropylene glycol, polyethoxylated tallow amine, and mixtures of two or more thereof,
wherein more preferably the one or more nonionic surfactants are selected from the group con sisting of (Ci6-Ci8)alcohols, (Ci6-Ci8)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 monopalmitate, sorbitan monostearate, sorbitan oleate, polyoxyethylene (20) sorbitan monolaurate, polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene (20) sorbitan monostearate, polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (10) oleyl ether, polyoxyethylene (20) oleyl ether, cocamide monoethanolamine, cocamide diethanolamine, dodecyldimethylamine oxide, block copolymers of polyethylene glycol and polypropylene glycol, polyethoxylated tallow amine, Stearyl-EC>2, polyglyceryl-2-dipolyhydroxystearate, polyglyceryl-distearate, C13/15 - PEG3, C13 - PEG2, glyceryl monooleate, C16/18 - PEG2, oleyl - PEG2, PEG20 - sorbitan monooleate, functionalized polyisobutene, C16/18 - PEGg, and mixtures of two or more thereof,
more preferably from the group consisting of polyglyceryl-2-dipolyhydroxystearate, diglyceryl- distearate, triglyceryl-distearate, C13/15 - PEG3, C13 - PEG2, glyceryl monooleate, sorbitan monooleate, polyglycerol-3-polyricinoleate, 016/18 - PEG2, oleyl - PEG2, PEG20 - sorbitan monooleate, functionalized polyisobutene, 016/18 - PEGg, polyoxyethylene (10) oleyl ether, polyoxyethylene (20) oleyl ether, and mixtures of two or more thereof,
more preferably from the group consisting of polyglyceryl-2-dipolyhydroxystearate, diglyceryl- distearate, triglyceryl-distearate, polyoxyethylene (10) oleyl ether, polyoxyethylene (20) oleyl ether, and mixtures of two or more thereof,
wherein it is even more preferred that the nonionic surfactant comprises polyoxyethylene (10) oleyl ether and/or polyoxyethylene (20) oleyl ether.
As regards the amount of the one or more emulsifiers in the reactant mixture according to (ii), no particular restriction applies. It is preferred that the reactant mixture according to (ii) compris es the one or more emulsifiers in an amount in the range from 20 to 75 weight-%, preferably in the range of from 30 to 65 weight-%, more preferably in the range of from 35 to 60 weight-%, more preferably in the range of from 40 to 55 weight-%, more preferably in the range of from 43 to 52 weight-%, more preferably in the range of from 45 to 50 weight-%, more preferably in the range of from 46.0 to 49.0 weight-%, more preferably in the range of from 47.0 to 48.0 weight- %.
As regards the amount of the mixture in the reactant mixture according to (ii), no particular re striction applies. It is preferred that the reactant mixture according to (ii) comprises the mixture in an amount in the range of from 2.0 to 7.5 weight-%, more preferably in the range of from 3.0 to 6.5 weight-%, more preferably in the range of from 3.5 to 6.0 weight-%, more preferably in the range of from 4.0 to 5.5 weight-%, more preferably in the range of from 4.3 to 5.2 weight-%, more preferably in the range of from 4.5 to 5.0 weight-%, more preferably in the range of from 4.60 to 4.90 weight-%, more preferably in the range of from 4.70 to 4.80 weight-%.
It is preferred that the reactant mixture according to (ii) is a gel.
The process of the present invention may comprise further process steps. It is preferred that the process further comprises after (i) and prior to (ii)
(a) providing a pre-mixture of one or more sources of YO2, optionally one or more sources of X2O3, seed crystals, a polar protic liquid solvent system, and one or more tetraalkylammonium cation containing compounds as structure directing agent;
(b) subjecting the pre-mixture obtained from (a) to pretreatment conditions to obtain the mix ture comprised in the reactant mixture according to (ii).
In the case where the process further comprises (a) and (b) after (i) and prior to (ii), it is pre ferred that (a) comprises
(a.1 ) providing a first mixture of the polar protic solvent and the one or more tetraalkylammoni um cation containing compounds as structure directing agent;
(a.2) optionally adding the one or more sources of X2O3 to obtain a second mixture and mixing of the second mixture;
(a.3) adding the one or more sources of YO2 to obtain a third mixture and mixing of the third mixture;
(a.4) adding of the seed crystals to obtain the pre-mixture.
Further in the case where the process further comprises (a) and (b) after (i) and prior to (ii), it is preferred that the pretreatment conditions in (b) comprise a temperature in the range of from 80 to 175 °C, more preferably in the range of from 90 to 170 °C, more preferably in the range of from 100 to 165 °C, more preferably in the range of from 110 to 160 °C, more preferably in the range of from 120 to 155 °C, and more preferably in the range of from 130 to 150 °C.
Further in the case where the process further comprises (a) and (b) after (i) and prior to (ii), it is preferred that the pretreatment conditions in (b) comprise hydrothermal conditions.
Further in the case where the process further comprises (a) and (b) after (i) and prior to (ii), it is preferred that the pretreatment conditions in (b) are applied for a duration in the range of from 1 to 72 h, more preferably in the range of from 6 to 60 h, more preferably in the range of from 12 to 54 h, more preferably in the range of from 14 to 42 h, more preferably in the range of from 16 to 36 h, more preferably in the range of from 18 to 32 h, and more preferably in the range of from 20 to 28 h.
As disclosed above, the process of the present invention may comprise further process steps. It is preferred that the process further comprises after (i) and prior to (ii) subjecting the reactant mixture to emulsifying conditions. In the case where the process further comprises after (i) and prior to (ii) subjecting the reactant mixture to emulsifying conditions, it is preferred that the emulsifying conditions comprise agita tion of the reactant mixture, more preferably by stirring and/or sonication, and more preferably by stirring.
Further in the case where the process further comprises after (i) and prior to (ii) subjecting the reactant mixture to emulsifying conditions, it is preferred that the emulsifying conditions com prise use of a homogenizes more preferably with a rotor-stator homogenizes with an ultrasonic homogenizes with a high pressure homogenizes by microfluidic systems, or by membrane emulsification, more preferably with an ultrasonic homogenizes
In the case where the process further comprises after (i) and prior to (ii) subjecting the reactant mixture to emulsifying conditions, it is preferred that the emulsifying conditions are applied for a period ranging from 0.1 to 15 min, preferably from 1 to 13 min, more preferably from 2 to 12 min, more preferably from 3 to 11 min, more preferably from 4 to 10 min, more preferably from 5 to 9 min, more preferably from 6.0 to 8.0 min, and more preferably from 6.5 to 7.5 min.
According to the process of the present invention, a reactant stream is continuously passed through the reaction zone according to (i), wherein the reactant stream comprises a reactant mixture, the reactant stream being subject to crystallization conditions in the reaction zone par ticularly effecting a conversion of at least a portion of the components comprised in the reactant stream to obtain a product stream. In this regard, it is preferred that no matter is added to and/or removed from the reactant stream during its passage through the reaction zone comprised in the flow reactor according to (i), wherein more preferably no matter is added, wherein more preferably no matter is added and no matter is removed from the reactant stream during its passage through the reaction zone comprised in the flow reactor according to (i).
As regards the crystallization conditions according to (iii), no particular restriction applies. It is preferred that the crystallization conditions according to (iii) comprise heating the reactant stream at a temperature in the range of from 160 to 320°C, preferably of from 170 to 300 °C, more preferably of from 175 to 295 °C, more preferably of from 190 to 290°C, more preferably of from 210 to 270°C, more preferably of from 220 to 260°C, more preferably of from 230 to 250°C, more preferably of from 235 to 245°C, and more preferably of from 237 to 243 °C.
Further, it is preferred that the crystallization conditions according to (iii) comprise autogenous pressure, more preferably a pressure in the range of from 17 to 25 MPa, preferably in the range of from 12 to 20 MPa, more preferably in the range of from 14 to 18 MPa, more preferably in the range of from 15.0 to 17.0 MPa, more preferably in the range of from 15.5 to 16.5 MPa.
It is preferred that the reactant stream is passed in the reactant zone with a flow rate in the range of from 0.01 to 20 ml/min, more preferably in the range of from 0.1 to 15 ml/min, more preferably in the range of from 0.15 to 11 ml/min, more preferably in the range of from 0.20 to 1.00 ml/min, more preferably in the range of from 0.35 to 0.80 ml/min, more preferably in the range of from 0.40 to 0.70 ml/min, more preferably in the range of from 0.50 to 0.65 ml/min, more preferably in the range of from 0.55 to 0.59 ml/min.
Further, it is preferred that the reactant stream is passed in the reactant zone with a liquid hour ly space velocity in the range of from 0.05 to 10 h 1 , more preferably in the range of from 0.1 to 5 IT1 , more preferably in the range of from 0.5 to 2.0 ir1, more preferably in the range of from 0.8 to 1.5 IT1 , more preferably in the range of from 1.0 to 1.3 ir1, more preferably in the range of from 1.1 to 1.2 IT1.
As disclosed above, the process of the present invention may comprise further process steps. It is preferred that after (i) and prior to (ii) the reactant stream is heated at a temperature in the range of from 45 to 135 °C, more preferably in the range of from 65 to 1 15 °C, more preferably in the range of from 75 to 105 °C, more preferably in the range of from 80 to 100 °C, more pref erably in the range of from 85 to 95 °C.
It is preferred that in (ii) the reactant stream is continuously fed into the flow reactor for a dura tion ranging from 0.1 h to 140 d, more preferably from 0.15 h to 100 d, more preferably from 0.2 h to 70 d, more preferably from 0.5 h to 50 d, more preferably from 1 h to 40 d, more preferably from 2 h to 35 d, more preferably from 5 h to 30 d, more preferably from 10 h to 25 d, more preferably from 15 h to 20 d, more preferably from 20 h to 15 d, and more preferably from 1 d to 10 d.
As disclosed above, the process of the present invention may comprise further process steps. It is preferred that the process further comprises
(iv) isolating the zeolitic material obtained in (iii);
and/or, preferably and,
(v) washing the zeolitic material obtained in (iii), or (iv);
and/or, preferably and,
(vi) drying the zeolitic material obtained in (iii), (iv), or (v);
and/or, preferably and,
(vii) calcining the zeolitic material obtained in (iii), (iv), (v), or (vi).
It is preferred that the process further comprises (iv). In the case where the process further comprises (iv), it is preferred that isolating in (iv) is achieved by filtration and/or centrifugation, more preferably by centrifugation.
It is preferred that the process further comprises (v). In the case where the process further com prises (v), it is preferred that washing in (v) is conducted with a solvent system comprising one or more solvents, wherein preferably the one or more solvents are selected from the group con sisting of polar protic solvents and mixtures thereof,
preferably from the group consisting of n-butanol, isopropanol, propanol, ethanol, methanol, water, and mixtures thereof, more preferably from the group consisting of ethanol, methanol, water, and mixtures thereof, wherein more preferably the solvent system comprises water, and wherein more preferably wa ter is used as the solvent system, preferably deionized water.
It is preferred that the process further comprises (vi). In the case where the process further comprises (vi), it is preferred that drying in (vi) is conducted at a temperature in the range of from 20 to 160 °C, more preferably in the range of from 30 to 140 °C, more preferably in the range of from 40 to 120 °C, more preferably in the range of from 50 to 1 10 °C, more preferably in the range of from 60 to 100 °C, more preferably in the range of from 70 to 90 °C, and more preferably in the range of from 75 to 85 °C.
It is preferred that the process further comprises (vii). In the case where the process further comprises (vii), it is preferred that the calcining in (vii) is effected at a temperature in the range from 300 to 750 °C, more preferably from 325 to 650 °C, more preferably from 350 to 600 °C, more preferably from 375 to 550 °C, more preferably from 400 to 500 °C, and more preferably from 425 to 475 °C.
As disclosed above, the process of the present invention may comprise further process steps. It is preferred that the process further comprises
(viii) subjecting the zeolitic material obtained in (iv), (v), (vi), or (vii) to an ion-exchange proce dure, wherein at least one ionic non-framework element or compound contained in the zeolitic material is ion-exchanged against one or more metal ions.
In the case where the process further comprises (viii), it is preferred that in (viii) the step of sub jecting the zeolitic material to an ion-exchange procedure includes the steps of
(viii. a) subjecting the zeolitic material obtained in (iv), (v), (vi), or (vii) to an ion-exchange procedure, wherein at least one ionic non-framework element or compound contained in the zeolitic material is ion-exchanged against NhV;
(viii.b) calcining the ion-exchanged zeolitic material obtained in (viii. a) for obtaining the in form of the zeolitic material;
(viii.c) subjecting the zeolitic material obtained in (viii.b) to an ion-exchange procedure, wherein H+ contained in the zeolitic material as ionic non-framework element is ion-exchanged against one or more metal ions.
In the case where the process further comprises (viii), it is preferred that the one or more metal ions are selected from the group consisting of ions of alkaline earth metal elements and/or tran sition metal elements, more preferably from the group consisting of ions of metals selected from group 4 and groups 6-1 1 of the Periodic Table of the Elements, more preferably from group 4 and groups 8-1 1 , wherein more preferably the one or more metal ions are selected from the group consisting of ions 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 ions of Ti, Cu, Fe, Rh, Pd, Pt, and mixtures of two or more thereof, wherein more preferably the at least one ionic non-framework element or compound contained in the zeolitic material is ion-exchanged against Cu and/or Fe, preferably against Cu.
Further in the case where the process further comprises (viii), it is preferred that in (viii) the zeo litic material is ion-exchanged such as to obtain a loading of the one or more metal ions in the zeolitic material ranging from 0.1 to 15 weight- % calculated as the element and based on 100 weight- % of SiC>2 contained in the zeolitic material, more preferably from 0.5 to 10 weight-%, more preferably from 1 to 8 weight-%, more preferably from 1.5 to 7 weight-%, more preferably from 2 to 6 weight-%, more preferably from 2.5 to 5.5 weight-%, more preferably from 3 to 5 weight-%, more preferably from 3.5 to 4.5 weight-%.
The zeolitic material obtained from crystallization in (ill) may have unique properties. The zeolitic material obtained from crystallization in (iii) may have a mean particle size D50 by volume as determined according to ISO 13320:2009 of at least 0.5 pm, preferably 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.
Further, the present invention relates to a zeolitic material obtainable and/or obtained according to the process of any one of the embodiments disclosed herein.
Further, the present invention relates to a use of a zeolitic material obtainable and/or obtained according to the process of 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 cata lyst support or a precursor thereof, more preferably as a catalyst or a precursor thereof, more preferably as a catalyst for the selective catalytic reduction (SCR) of nitrogen oxides NOx; for the storage and/or adsorption of CO2; for the oxidation of NH3, in particular for the oxidation of NH3 slip in diesel systems; for the decomposition of N2O; as an additive in fluid catalytic crack ing (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 olefin (MTO) catalysis; more preferably for the selective catalytic reduction (SCR) of nitrogen oxides NOx, and more preferably for the selective catalytic reduction (SCR) of nitrogen oxides NOx in exhaust gas from a combustion engine, preferably from a diesel engine or from a lean burn gasoline engine.
Embodiments
The present invention is further illustrated by the following set of embodiments and combina tions of embodiments resulting from the dependencies and back-references as indicated. In particular, it is noted that in each instance where a range of embodiments is mentioned, for ex ample in the context of a term such as "The process of any one of embodiments 1 to 4", every embodiment in this range is meant to be explicitly disclosed for the skilled person, i.e. the word ing of this term is to be understood by the skilled person as being synonymous to "The process of any one of embodiments 1 , 2, 3, and 4". Further, it is explicitly noted that the following set of embodiments is not the set of claims determining the extent of protection, but represents a suit ably structured part of the description directed to general and preferred aspects of the present invention.
1. A continuous process for preparing a zeolitic material comprising YO2 and optionally X2O3 in its framework structure, wherein Y is a tetravalent element and X is a trivalent element, said process comprising
(i) providing a flow reactor comprising a reaction zone;
(ii) continuously passing a reactant stream through the reaction zone according to (i), wherein the reactant stream comprises a reactant mixture comprising a non-polar liquid solvent system, one or more emulsifiers, and a mixture of one or more sources of YO2, optionally one or more sources of X2O3, seed crystals, a polar protic liquid solvent sys tem, and one or more tetraalkylammonium cation containing compounds as structure di recting agent;
(iii) subjecting the reactant stream to crystallization conditions in the reaction zone and removing a product stream from the reaction zone, wherein the product stream comprises the zeolitic material.
2. The process of embodiment 1 , wherein the zeolitic material has a framework structure type selected from the group consisting of AEI, AFX, ANA, BE A, BEC, CAN, CHA, CDO, EMT, ERI, EUO, FAU, FER, GME, HEU, ITH, ITW, KFI, LEV, MEI, MEL, MFI, MOR, MTN, MWW, OFF, RRO, RTH, SAV, SFW, SZR, TON, and a mixture of two or more thereof, preferably from the group consisting of CAN , AEI, EMT, SAV, SZR, KFI, ERI, OFF, RTH, GME, AFX, SFW, BE A, CHA, FAU, FER, HEU, LEV, MEI, MEL, MFI, MOR, MWW, and a mixture of two or more thereof, more preferably from the group consisting of AEI, BE A, CHA, ERI, FAU, FER, GME, LEV, MFI, MOR, MWW, and a mixture of two or more there of, more preferably from the group consisting of AEI, BE A, CHA, ERI and a mixture there of, wherein more preferably the zeolitic material has the CHA or the AEI framework struc ture type.
3. The process of embodiment 1 or 2, wherein Y is selected from the group consisting of Si, Ge, Sn, Ti, Zr, and combinations of two or more thereof, preferably from the group con sisting of Si, Ge, Ti, and combinations of two or more thereof, more preferably from the group consisting of Si, Ti, and a combination thereof, wherein more preferably Y is Si.
4. The process of any one of embodiments 1 to 3, wherein X is selected from the group con sisting of B, Al, Ga, In, and combinations of two or more thereof, preferably from the group consisting of B, Al, Ga, and combinations of two or more thereof, more preferably from the group consisting of Al, Ga, and a combination thereof, wherein more preferably X is Al. 5. The process of any one of embodiments 1 to 4, wherein the zeolitic material has the CHA framework structure type comprising YO2 and X2O3, wherein Y is Si and X is Al.
6. The process of any one of embodiments 1 to 4, wherein the zeolitic material has the AEI framework structure type comprising YO2 and X2O3, wherein Y is Si and X is Al.
7. The process of any one of embodiments 1 to 6, wherein the flow reactor according to (i) is selected among a tubular reactor, and a ring reactor, preferably among a plain tubular re actor, a tubular membrane reactor, a tubular reactor with Coanda effect, a ring reactor, and combinations thereof, wherein more preferably the flow reactor is a plain tubular reac tor and/or a ring reactor, wherein more preferably the flow reactor is a plain tubular reac tor.
8. The process of any one of embodiments 1 to 7, wherein the flow reactor according to (i) comprises a reaction zone having a volume in the range of from 5 to 5000 cm3, preferably in the range of from 5 to 2500 cm3, more preferably in the range of from 10 to 1000 cm3, more preferably in the range of from 10 to 100 cm3, more preferably in the range of from 20 to 50 cm3, more preferably in the range of from 20 to 30 cm3, more preferably in the range of from 25 to 30 cm3.
9. The process of any one of embodiments 1 to 8, wherein the flow reactor according to (i) comprises a reaction zone having a length in the range of from 0.2 to 100 m, preferably in the range of from 0.5 to 50 m, more preferably in the range of from 1.0 to 10 m, more preferably in the range of from 1.5 to 5.0 m, more preferably in the range of from 1.75 to 3.50 m, more preferably in the range of from 2.00 to 2.50 m.
10. The process of any one of embodiments 1 to 9, wherein the flow reactor according to (i) comprises a tubular reactor, and wherein at least a portion of the flow reactor is of a regu lar cylindrical form having a constant inner diameter perpendicular to the direction of flow, wherein the inner diameter is preferably in the range of from 0.1 to 100 mm, more prefer ably in the range of from 0.1 to 50 mm, more preferably in the range of from 0.2 to 25 mm, more preferably in the range of from 0.5 to 10 mm, more preferably in the range of from 0.5 to 5.0 mm, more preferably in the range of from 1.0 to 3.5 mm, more preferably in the range of from 1.5 to 2.5 mm, more preferably in the range of from 1.75 to 2.25 mm, more preferably in the range of from 1.95 to 2.05 mm.
1 1. The process of any one of embodiments 1 to 10, wherein the wall of the flow reactor ac cording to (i) reactor is made of a metallic material, wherein the metallic material compris es 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 consist- ing of Ta, Cr, Fe, Ni, Mo, and combinations and/or alloys of two or more thereof, prefera bly from the group consisting of Cr, Fe, Ni, Mo, and combinations and/or alloys of two or more thereof. The process of any one of embodiments 1 to 1 1 , wherein the surface of the inner wall of the flow reactor is lined with an organic polymer material, wherein 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 consisting 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 preferably the polymer material comprises poly(tetrafluoroethylene), where in more preferably the inner wall of the continuous flow reactor is lined with
poly(tetrafluoroethylene). The process of any one of embodiments 1 to 12, wherein the flow reactor is straight and/or comprises one or more curves with respect to the direction of flow, wherein prefer ably the continuous flow reactor is straight. The process of any one of embodiments 1 to 13, wherein the flow reactor consists of a single stage. The process of any one of embodiments 1 to 14, wherein the one or more sources of YO2 comprises one or more compounds selected from the group consisting of silicas, silicates, and mixtures thereof,
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,
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,
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
more preferably from the group consisting of water glass, colloidal silica, and mixtures thereof,
wherein more preferably the one or more sources of SiC>2 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. 16. The process of any one of embodiments 1 to 15, wherein the one or more sources of X2O3 comprises one or more aluminum salts, preferably an aluminate of an alkali metal and/or aluminum hydroxide, preferably aluminum hydroxide, wherein more preferably the one or more sources of X2O3 is an aluminate of an alkali metal and/or aluminum hydrox ide, preferably aluminum hydroxide,
wherein the alkali metal is preferably selected 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.
17. The process of any one of embodiments 1 to 16, wherein the seed crystals comprise a zeoltic material, wherein the zeolitic material comprises YO2 and optionally X2O3, wherein Y is a tetra valent element and X is a trivalent element, wherein preferably Y is selected from the group consisting of Si, Ge, Sn, Ti, Zr, and combinations of two or more thereof, preferably from the group consisting of Si, Ge, Ti, and combinations of two or more there of, more preferably from the group consisting of Si, Ti, and a combination thereof, wherein more preferably Y is Si, and wherein preferably X is selected from the group consisting of B, Al, Ga, In, and combinations of two or more thereof, preferably from the group consist ing of B, Al, Ga, and combinations of two or more thereof, more preferably from the group consisting of Al, Ga, and a combination thereof, wherein more preferably X is Al.
18. The process of any one of embodiments 1 to 17, wherein the zeolitic material comprised in the seed crystals has a framework structure selected from the group consisting of AEI, AFX, ANA, BEA, BEC, CAN, CHA, CDO, EMT, ERI, EUO, FAU, FER, GME, HEU, ITH, ITW, KFI, LEV, MEI, MEL, MFI, MOR, MTN, MWW, OFF, RRO, RTH, SAV, SFW, SZR, TON, and a mixture of two or more thereof, preferably from the group consisting of CAN, AEI, EMT, SAV, SZR, KFI, ERI, OFF, RTH, GME, AFX, SFW, BEA, CHA, FAU, FER, HEU, LEV, MEI, MEL, MFI, MOR, MWW, and a mixture of two or more thereof, more preferably from the group consisting of AEI, BEA, CHA, ERI, FAU, FER, GME, LEV, MFI, MOR, MWW, and a mixture of two or more thereof, more preferably from the group con sisting of AEI, BEA, CHA, ERI and a mixture thereof, wherein more preferably the zeolitic material comprised in the seed crystals has the CHA or the AEI framework structure type.
19. The process of any one of embodiments 1 to 18, wherein the zeolitic material comprised in the seed crystals has a CHA-type framework structure, wherein preferably the zeolitic material comprised in the seed crystals and having a CHA-type framework structure is se lected 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 , |Li-Na| [AI-Si-0]-CHA, (Ni(deta)2)-UT-6, SSZ-13, and SSZ-62, including mixtures of two or more thereof,
more preferably from the group consisting of ZYT-6, SAPO-47, Na-Chabazite, Chabazite, LZ-218, Linde D, Linde R, SAPO-34, ZK-14, K-Chabazite, Phi, DAF-5, UiO-21 , SSZ-13, and SSZ-62, including mixtures of two or more thereof, more preferably from the group consisting of Chabazite, Linde D, Linde R, SAPO-34, SSZ-13, and SSZ-62, including mixtures of two or more thereof,
more preferably from the group consisting of Chabazite, SSZ-13, and SSZ-62, including mixtures of two or three thereof,
wherein more preferably the zeolitic material comprised in the seed crystals and having a CHA-type framework structure comprises chabazite and/or SSZ-13, preferably chabazite, and wherein more preferably the zeolitic material comprised in the seed crystals and hav ing a CHA-type framework structure is chabazite and/or SSZ-13, preferably SSZ-13. The process of any one of embodiments 1 to 19, wherein the zeolitic material comprised in the seed crystals has a AEI-type framework structure, wherein preferably the zeolitic material comprised in the seed crystals and having a AEI-type framework structure is se lected from the group consisting of SSZ-39, SAPO-18, SIZ-8, including mixtures of two or more thereof, wherein more preferably the zeolitic material comprised in the seed crystals and having a AEI-type framework structure comprises SSZ-39, and wherein more prefer ably the zeolitic material comprised in the seed crystals and having a AEI-type framework structure is SSZ-39. The process of any one of embodiments 1 to 20, wherein the amount of seed crystals in the mixture according to (ii) is in the range of from 0.1 to 20 wt.-% based on 100 wt.-% of S1O2 contained in the mixture, preferably from 1 to 18 wt.-%, more preferably from 5 to 15 weight-%, more preferably from 7 to 13 weight-%, more preferably from 8 to 12 weight-%, more preferably from 9 to 11 weight-%, and more preferably from 9.5 to 10.5 weight-%. The process of any one of embodiments 1 to 21 , wherein the seed crystals are ground prior to (ii), wherein preferably grinding is carried out in a mill selected from the group consisting of a stirred media mill, a planetary ball mill, a ball mill, a roller mill, a kneader, a high shear mixer, and a mix muller,
preferably from the group consisting of a stirred media mill, a ball mill, a roller mill, a plan etary mill, and a high shear mixer,
and more preferably from the group consisting of a ball mill, a planetary ball mill, a high shear mixer, and a mix muller,
wherein more preferably grinding is carried out in a ball mill and/or a planetary ball mill, preferably in a ball mill. The process of any one of embodiments 1 to 22, wherein the seed crystals are ground prior to (ii), wherein preferably grinding is carried out in a ball mill and/or in a planetary ball mill, preferably in a ball mill, using balls made of a material selected from the group con sisting of stainless steel, ceramic, and rubber, preferably from the group consisting of chrome steel, flint, zirconia, silicon nitride, and lead antimony alloy, wherein more prefera- bly the balls of the ball mill are made of zirconia and/or silicon nitride, preferably of zirco- nia.
24. The process of embodiment 23, wherein grinding is carried out in a ball mill using grinding media, wherein the grinding media comprises grinding balls, preferably having a diameter in the range of from 50 to 1000 pm, more preferably of from 100 to 750 pm, more prefera bly of from 150 to 500 pm, more preferably of from 200 to 400 pm, and more preferably of from 250 to 350 pm.
25. The process of embodiment 24, wherein the grinding media further comprises a liquid solvent system, preferably water.
26. The process of any one of embodiments 23 to 25, wherein the filling degree of the grind ing balls in the ball mill is in the range of from 60 to 90%, preferably of from 70 to 80 %, and more preferably of from 73 to 77 %.
27. The process of any one of embodiments 23 to 26, wherein the ball mill is operated at a speed in the range of from 500 to 6,000 rpm, preferably of from 1 ,000 to 5,000 rpm, more preferably of from 2,000 to 4,500 rpm, more preferably of from 2,500 to 4,000 rpm, more preferably of from 2,600 to 3,800 rpm, more preferably of from 2,700 to 3,500 rpm, more preferably of from 2,800 to 3,200 rpm, and more preferably of from 2,900 to 3,100 rpm.
28. The process of any one of embodiments 1 to 27, wherein the one or more
tetraalkylammonium cation containing compounds comprise one or more tetraalkylammo- nium cation R1 R2R3R4N+-containing compounds, wherein R1, R2, and R3 independently from one another is alkyl, and wherein R4 is cycloalkyl, wherein preferably R1, R2, and R3 in the one or more tetraalkylammonium cation R1 R2R3R4N+-containing compounds inde pendently from one another stand for optionally branched (Ci-Ce)alkyl, preferably (Ci- Cejalkyl, more preferably (Ci-C4)alkyl, and more preferably for optionally branched (Ci- C3)alkyl, wherein more preferably R1, R2, and R3 independently from one another stand for methyl or ethyl, wherein more preferably R1, R2, and R3 stand for methyl.
29. The process of embodiment 28, wherein R4 stands for optionally branched and/or option ally cyclic (C1-C9) alkyl, preferably for optionally branched and/or optionally cyclic (Ci-Ce) alkyl, preferably for optionally branched and/or optionally cyclic (C1-C7) alkyl, more prefer ably for optionally branched and/or optionally cyclic (Ci-Ce) alkyl, wherein R4 more prefer ably stands 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 R4 stands for optionally heterocyclic 6-membered cycloalkyl, and more preferably for cyclohexyl. The process of embodiment 28 or 29, wherein R1, R2, and R3 in the one or more tetraalkylammonium cation R1 R2R3R4N+-containing compounds independently from one another stand for alkyl, and wherein R4 stands for cyclohexyl. The process of any one of embodiments 28 to 30, wherein the one or more
tetraalkylammonium cation R1R2R3R4N+-containing compounds comprise one or more A/,A/,/\/-tri(Ci-C4)alkyl-(C5-C7)cycloalkylammonium compounds, preferably one or more A/,A/,/V-th(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,A/,/V-tri(Ci-C2)alkyl-cyc!opentylammonium and/or one or more N,N,N- tri(Ci- C2)alkyl-cyclohexylammonium compounds, more preferably one or more compounds se lected from L/,/n,/V-triethyl-cyclohexylammonium, /V,A-diethyl-A/-methyl- cyclohexylammonium, /V,/V-dimethyl-//-ethyl-cyclohexylammonium, L L , /V-trimethyl- cyclohexylammonium compounds, and mixtures of two or more thereof, wherein more preferably the one or more tetraalkylammonium cation R1 R2R3R4N+-containing com pounds comprise one or more /V,/V-dimethyl-/V-ethyl-cyclohexylammonium and/or N,N,N- trimethyl-cyclohexylammonium compounds, more preferably one or more L/, /V, /V-trimethyl- cyclohexylammonium compounds. The process of any one of embodiments 1 to 31 , wherein the one or more
tetraalkylammonium cation containing compounds are selected from the group consisting of /V,/V-di(Ci-C4)alkyl-3,5-di(Ci-C4)alkylpyrrolidinium compounds, A,/V-di(Ci-C4)alkyl-3,5- di(Ci-C4)alkylpiperidinium compounds, A ,/V-di(Ci-C4)alkyl-3,5-di(Ci- C4)alkylhexahydroazepinium compounds, V,A/-di(Ci-C4)alkyl-2,6-di(Ci- C4)alkylpyrrolidinium compounds, A,/V-di(Ci-C4)alkyl-2,6-di(Ci-C4)alkylpiperidinium com pounds, /V,/V-di(Ci-C4)alkyl-2,6-di(Ci-C4)alkylhexahydroazepinium compounds, and mix tures of two or more thereof,
preferably from the group consisting of //,/V-di(Ci-C3)alkyl-3,5-di(Ci-C3)alkylpyrrolidinium compounds, /V,/\/-di(Ci-C3)alkyl-3,5-di(Ci-C3)alkylpipehdinium compounds, A,/V-di(Ci-
C3)alkyl-3,5-di(Ci-C3)alkylhexahydroazepinium compounds, /V,/V-di(Ci-C3)alkyl-2,6-di(Ci- C3)alkylpyrrolidinium compounds, A/,A/-di(Ci-C3)alkyl-2,6-di(Ci-C3)alkylpiperidinium com pounds, /V,/V-di(Ci-C3)alkyl-2,6-di(Ci-C3)alkylhexahydroazepinium compounds, and mix tures of two or more thereof,
more preferably from the group consisting of A/,/V-di(Ci-C2)alkyl-3,5-di(Ci- C2)alkylpyrrolidinium compounds, A,/V-di(Ci-C2)alkyl-3,5-di(Ci-C2)alkylpiperidinium com pounds, /V,/V-di(Ci-C2)alkyl-3,5-di(Ci-C2)alkylhexahydroazepinium compounds, N,N- di(Ci-C2)alkyl-2,6-di(Ci-C2)alkylpyrrolidinium compounds, /V,/V-di(Ci-C2)alkyl-2,6-di(Ci- C2)alkylpiperidinium compounds, L, LZ-d i (C i -C 2 )al kyl-2 , 6-d i (C 1 - C2)alkylhexahydroazepinium compounds, and mixtures of two or more thereof, more preferably from the group consisting of /V,/V-di(Ci-C2)alkyl-3,5-di(Ci- C2)alkylpiperidinium compounds, /V,/V-di(Ci-C2)alkyl-2,6-di(Ci-C2)alkylpiperidinium com pounds, and mixtures of two or more thereof, wherein more preferably the one or more tetraalkylammonium cation containing compounds comprise one or more A/,A/-dimethyl- 3,5-dimethylpiperidinium and/or /V,/V-diethyl-2,6-dimethylpiperidinium compounds, prefer ably one or more A,/V-dimethyl-3,5-dimethylpiperidinium compounds.
33. The process of embodiment 32, wherein the /V,A/-dialkyl-3,5-dialkylpyrrolidinium com
pounds, A/,/V-dialkyl-3,5-dialkylpiperidinium compounds, and/or A/,A/-dialkyl-3,5- dialkylhexahydroazepinium compounds display the os configuration, the trans configura tion, or contain a mixture of the c/s and trans isomers,
wherein preferably the L/, A/-d ia I ky 1-3 , 5-d i a I ky I py rrol i d i n i u m compounds, //,/V-dialkyl-3,5- dialkylpiperidinium compounds, and/or /\/,/V-dialkyl-3,5-dialkylhexahydroazepinium com pounds display the os configuration,
wherein more preferably the one or more ammonium cation R1R2R3R4N+-containing com pounds are selected from the group consisting of L/, A-d i (C i -C 2 )a I ky I- c/s-3 , 5-d i (C 1 - C2)alkylpiperidinium compounds, and mixtures of two or more thereof, wherein more pref erably the one or more ammonium cation containing compounds comprise one or more V,A-dimethyl-c/5-3,5-dimethylpiperidinium compounds.
34. The process of any one of embodiments 1 to 33, wherein the one or more
tetraalkylammonium cation containing compounds are salts, preferably 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 bromide, chloride, hydroxide, sulfate, and mixtures of two or more thereof, wherein more preferably the one or more tetraalkylammonium cation containing compounds are tetraalkylammoni um hydroxides and/or bromides, and more preferably tetraalkylammonium hydroxides.
35. The process of any one of embodiments 1 to 34, wherein the reactant mixture according to (ii) further contains one or more tetraalkylammonium cation R5R6R7R8N+-containing compounds, wherein R5, R6, R7, and R8, independently from one another stand for option ally substituted and/or optionally branched (Ci-Ce)alkyl, preferably (Ci-C5)alkyl, more preferably (Ci-C4)alkyl, more preferably (Ci-C3)alkyl, and even more preferably for op tionally substituted methyl or ethyl, wherein even more preferably R5, R6, R7, and R8 stand for optionally substituted methyl, preferably unsubstituted methyl.
36. The process of embodiment 35, wherein the one or more tetraalkylammonium cation
RSR6R7R8N+-containing compounds comprise one or more compounds selected from the group consisting of tetra(Ci-C6)alkylammonium compounds, preferably tetra(Ci- C5)alkylammonium compounds, more preferably tetra(Ci-C4)alkylammonium compounds, and more preferably tetra(Ci-C3)alkylammonium compounds, wherein independently from one another the alkyl substituents are optionally branched, and wherein more preferably the one or more tetraalkylammonium cation R5R6R7R8N+-containing compounds are se lected from the group consisting of optionally branched tetrapropylammonium compounds, ethyltripropylammonium compounds, diethyldipropylammonium compounds, triethylprop- ylammonium compounds, methyltripropylammonium compounds, dimethyldipropylammo- nium compounds, trimethylpropylammonium compounds, tetraethylammonium com pounds, triethylmethylammonium compounds, diethyldimethylammonium compounds, ethyltrimethylammonium compounds, tetramethylammonium compounds, and mixtures of two or more thereof, preferably from the group consisting of optionally branched tetrae thylammonium compounds, triethylmethylammonium compounds, diethyldimethylammo nium compounds, ethyltrimethylammonium compounds, tetramethylammonium com pounds, and mixtures of two or more thereof, preferably from the group consisting of tet ramethylammonium compounds, wherein more preferably the one or more
tetraalkylammonium cation R5R6R7R8N+-containing compounds consists of one or more tetramethylammonium compounds. The process of embodiment 35 or 36, wherein the one or more tetraalkylammonium cation R5R6R7R8N+-containing compounds are salts, preferably one or more salts selected from the group consisting of halides, preferably chloride and/or bromide, more preferably chlo ride, 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 tetraalkylammonium cation R5R6R7R8N+-containing compounds are tetraalkylammonium hydroxides and/or chlorides, and even more preferably tetraalkylammonium hydroxides. The process of any one of embodiments 35 to 37, wherein the one or more
tetraalkylammonium cation containing compounds comprise one or more tetraalkylammo nium cation R1 R2R3R4N+-containing compounds, wherein R1, R2, and R3 independently from one another is alkyl, and wherein R4 is cycloalkyl, wherein the molar ratio
R5R6R7R8N+ ; R1R2R3R4N+ of the one or more tetraalkylammonium cations R5R6R7R8N+ to the one or more tetraalkylammonium cations R1R2R3R4N+ in the mixture provided accord ing to step (i) is in the range of from 0.01 to 5, preferably from 0.05 to 2, more preferably from 0.1 to 1.5, more preferably from 0.2 to 1.2, more preferably from 0.3 to 1.1 , more preferably from 0.4 to 1.0, more preferably from 0.5 to 0.9, and even more preferably from 0.6 to 0.8. The process of any one of embodiments 1 to 38, wherein the one or more
tetraalkylammonium cation containing compounds comprise one or more tetraalkylammo nium cation R1 R2R3R4N+-containing compounds, wherein R1, R2, and R3 independently from one another is alkyl, and wherein R4 is cycloalkyl, wherein the molar ratio S1O2 : RI R2R3R4N+ of the one or more sources of S1O2 to the one or more tetraalkylammonium cation R1 R2R3R4N+-containing compounds in the mixture provided according to step (i) is in the range of from 0.1 to 20, preferably from 0.5 to 15.0, more preferably from 2.0 to
1 1.0, more preferably from 4.0 to 9.0, more preferably from 5.1 to 7.6, more preferably from 7.1 to 5.6, more preferably from 6.1 to 6.6, and even more preferably from 6.3 to 6.4. The process of any one of embodiments 1 to 39, wherein the mixture provided according to step (i) comprises one or more sources of X2O3 , wherein the molar ratio S1O2 : X2O3 of the one or more sources of YO2 to the one or more sources of X2O3 is in the range of from 5 to 40, preferably from 15 to 31 , more preferably from 20.0 to 26.0, more preferably from 24.0 to 32.0, more preferably from 26.0 to 30.0, more preferably from 26.7 to 28.8, more preferably from 27.2 to 28.3, and even more preferably from 27.7 to 27.8. The process of any one of embodiments 1 to 40, wherein the polar protic liquid solvent system comprises one or more of n-butanol, isopropanol, propanol, ethanol, methanol, and water, more preferably one or more of ethanol, methanol, and water, wherein more preferably the polar protic liquid solvent system comprises, more preferably consists of, water, more preferably deionized water. The process of any one of embodiments 1 to 41 , wherein the polar protic liquid solvent system comprises water, wherein the molar ratio S1O2 : H2O of the one or more sources of YO2 to water is in the range of from 0.1 to 50, preferably from 0.5 to 30, more prefera bly from 1 to 25, more preferably from 2 to 21 , more preferably from 5 to 18, more prefer ably from 8 to 15, more preferably from 10.0 to 13.0, and even more preferably from 11.0 to 12.0. The process of any one of embodiments 1 to 42, wherein the non-polar liquid solvent sys tem comprises one or more of (C5-Cio)alkanes, (Cs-Cio)aikenes, (Cs-Cio)aromatic organ ic compounds, (C4-C8)alkylethers, (Ci-C3)alkylhalides, or mixtures of two or more thereof, preferably from the group consisting of (C6-Cio)alkanes, (C6-Cio)alkenes, (C&- Cio)aromatic organic compounds, (C4-C6)alkylethers, (Ci-C2)alkylhalides, or mixtures of two or more thereof, preferably from the group consisting of (Ce-Cejalkanes, (Ce- Ce)alkenes, (Ce-Cejaromatic organic compounds, or mixtures of two or more thereof, wherein more preferably the non-polar liquid solvent system comprises one or more of hexane, heptane, octane, cyclohexane, cycloheptane, cyclooctane, benzene, toluene, ethylbenzene, mesitylene, durene, and xylene, more preferably one or more of hexane, heptane, octane, cyclohexane, cycloheptane, cyclooctane, and benzene, more preferably one or more of hexane, cyclohexane, cycloheptane, and cyclooctane, wherein more pref erably the non-polar liquid solvent system comprises, more preferably consists of, cyclo hexane. The process of any one of embodiments 1 to 43, wherein the reactant mixture according to (ii) comprises the non-polar liquid solvent system in an amount in the range of from 20 to 75 weight-%, preferably in the range of from 30 to 65 weight-%, more preferably in the range of from 35 to 60 weight-%, more preferably in the range of from 40 to 55 weight-%, more preferably in the range of from 43 to 52 weight-%, more preferably in the range of from 45 to 50 weight-%, more preferably in the range of from 46.0 to 49.0 weight-%, more preferably in the range of from 47.0 to 48.0 weight-%. The process of any one of embodiments 1 to 44, wherein the one or more emulsifiers are selected from the group consisting of ionic and nonionic surfactants, including mixtures thereof, preferably from the group consisting of nonionic surfactants. The process of embodiment 45, wherein 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 (C6-Cie)sulfate, (C6-Ci8)ethersulfate, (C6-Ci8)sulfonate, (Ce- Ci8)sulfosuccinate (Ce-Ci8)phosphate, (C6-Ci8)carboxylate, and mixtures of two or more thereof, more preferably from the group consisting of salts of (Cs-Ci6)sulfate, (Ce- Ci6)ethersulfate, (C8-Ci6)sulfonate, (C8-Ci6)sulfosuccinate, (C8-Ci6)phosphate, (Ce- Ci6)carboxylate, and mixtures of two or more thereof, more preferably from the group consisting of salts of (Cio-Ci4)sulfate, (Cio-Ci4)ethersulfate, (Cio-Ci4)sulfonate, (Ce- Ci4)sulfosuccinate, (Cio-Ci4)phosphate, (Cio-Ci4)carboxylate, and mixtures of two or more thereof, more preferably from the group consisting of salts of laurylsulfate, lau- rylsulfonate, dioctyl sulfosuccinate, laurylphosphate, laurate, and mixtures of two or more thereof, wherein the counterion is preferably selected from the group consisting of H+, al kali metals, alkaline earth metals, ammonium, and combinations of two or more thereof, more preferably from the group consisting of H+, Li+, Na+, K+, ammonium, and combina tions of two or more thereof, more preferably from the group consisting of Na+, K+, ammo nium, and combinations of two or more thereof, wherein even more preferably the coun terion is Na+ and/or ammonium, preferably Na+. The process of embodiment 45 or 46, wherein 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 (Ce-Cisjtrimethylammonium, (C8-Ci8)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, benzalkonium, benzethonium, dimethyldioctadecylammonium, cetrimonium, dioctadecyl- dimethylammonium, wherein the counterion is preferably selected from the group consist ing of halides, carbonates, hydroxide, nitrate, phosphate, sulfate, and combinations of two or more thereof, more preferably from the group consisting of chloride, fluoride, bromide, hydrogen carbonate, hydroxide, nitrate, sulfate, and combinations of two or more thereof, wherein more preferably the counterion is chloride and/or nitrate, preferably chloride. The process of any one of embodiments 45 to 47, wherein the ionic surfactants comprise one or more zwitterionic surfactants, preferably one or more betaines, wherein more pref erably the ionic surfactants comprise cocamidopropylbetaine or alkyldimethylaminoxide. The process of any one of embodiments 45 to 48, wherein the 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 gly col alkylphenol ethers, glycerol alkyl esters, sorbitan alkyl esters, polyoxyethylene glycol sorbitan alkyl esters, cocamide monoethanolamine, cocamide diethanolamine, dodecyl- dimethylamine oxide, block copolymers of polyethylene glycol and polypropylene glycol, polyethoxylated tallow amine, and mixtures of two or more thereof,
wherein more preferably the one or more nonionic surfactants are selected from the group consisting of (Ci4-C2o)alcohols, (Ce-Ci8)alcohol ethoxylates with 2 to 6 ethylene oxide units, (C8-Cis)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 monostearate, sorbitan monooleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmi tate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, poly oxyethylene (10) oleyl ether, polyoxyethylene (20) oleyl ether, cocamide monoethanola mine, cocamide diethanolamine, dodecyldimethylamine oxide, block copolymers of poly ethylene glycol and polypropylene glycol, polyethoxylated tallow amine, and mixtures of two or more thereof,
wherein more preferably the one or more nonionic surfactants are selected from the group consisting of (Ci6-Ci8)alcohols, (Ci6-Ci8)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 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
monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan oleate, polyoxy ethylene (20) sorbitan monolaurate, polyoxyethylene (20) sorbitan monopalmitate, poly oxyethylene (20) sorbitan monostearate, polyoxyethylene (20) sorbitan monooleate, pol yoxyethylene (10) oleyl ether, polyoxyethylene (20) oleyl ether, cocamide monoethanola mine, cocamide diethanolamine, dodecyldimethylamine oxide, block copolymers of poly ethylene glycol and polypropylene glycol, polyethoxylated tallow amine, Stearyl-EC>2, pol- yglyceryl-2-dipolyhydroxystearate, polyglyceryl-distearate, C13/15 - PEG3, C13 - PEG2, glyceryl monooleate, C16/18 - PEG2, oleyl - PEG2, PEG20 - sorbitan monooleate, func tionalized polyisobutene, C16/18 - PEGg, and mixtures of two or more thereof, more preferably from the group consisting of polyglyceryl-2-dipolyhydroxystearate, diglyc- eryl-distearate, triglyceryl-distearate, C13/15 - PEG3, C13 - PEG2, glyceryl monooleate, sorbitan monooleate, polyglycerol-3-polyricinoleate, C16/18 - PEG2, oleyl - PEG2, 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 polyglyceryl-2-dipolyhydroxystearate, diglyc- eryl-distearate, triglyceryl-distearate, polyoxyethylene (10) oleyl ether, polyoxyethylene (20) oleyl ether, and mixtures of two or more thereof,
wherein it is even more preferred that the nonionic surfactant comprises polyoxyethylene (10) oleyl ether and/or polyoxyethylene (20) oleyl ether.
50. The process of any one of embodiments 1 to 49, wherein the reactant mixture according to (ii) comprises the one or more emulsifiers in an amount in the range from 20 to 75 weight-%, preferably in the range of from 30 to 65 weight-%, more preferably in the range of from 35 to 60 weight-%, more preferably in the range of from 40 to 55 weight-%, more preferably in the range of from 43 to 52 weight-%, more preferably in the range of from 45 to 50 weight-%, more preferably in the range of from 46.0 to 49.0 weight-%, more prefera bly in the range of from 47.0 to 48.0 weight-%.
51. The process of any one of embodiments 1 to 50, wherein the reactant mixture according to (ii) comprises the mixture in an amount in the range of from 2.0 to 7.5 weight-%, prefer ably in the range of from 3.0 to 6.5 weight-%, more preferably in the range of from 3.5 to 6.0 weight-%, more preferably in the range of from 4.0 to 5.5 weight-%, more preferably in the range of from 4.3 to 5.2 weight-%, more preferably in the range of from 4.5 to 5.0 weight-%, more preferably in the range of from 4.60 to 4.90 weight-%, more preferably in the range of from 4.70 to 4.80 weight-%.
52. The process of any one of embodiments 1 to 51 , wherein the reactant mixture according to (ii) is a gel.
53. The process of any one of embodiments 1 to 52, further comprising after (i) and prior to (ii)
(a) providing a pre-mixture of one or more sources of YO2, optionally one or more sources of X2O3, seed crystals, a polar pro tic liquid solvent system, and one or more tetraalkylammonium cation containing compounds as structure directing agent;
(b) subjecting the pre-mixture obtained from (a) to pretreatment conditions to obtain the mixture comprised in the reactant mixture according to (ii).
54. The process of embodiment 53, wherein (a) comprises
(a.1 ) providing a first mixture of the polar protic solvent and the one or more
tetraalkylammonium cation containing compounds as structure directing agent;
(a.2) optionally adding the one or more sources of X2O3 to obtain a second mixture and mixing of the second mixture;
(a.3) adding the one or more sources of YO2 to obtain a third mixture and mixing of the third mixture;
(a.4) adding of the seed crystals to obtain the pre-mixture.
55. The process of embodiment 53 or 54, wherein the pretreatment conditions in (b) comprise a temperature in the range of from 80 to 175 °C, preferably in the range of from 90 to 170 °C, more preferably in the range of from 100 to 165 °C, more preferably in the range of from 110 to 160 °C, more preferably in the range of from 120 to 155 °C, and more prefer ably in the range of from 130 to 150 °C.
56. The process of any one of embodiments 53 to 55, wherein the pretreatment conditions in (b) comprise hydrothermal conditions.
57. The process of any one of embodiments 53 to 56, wherein the pretreatment conditions in (b) are applied for a duration in the range of from 1 to 72 h, more preferably in the range of from 6 to 60 h, more preferably in the range of from 12 to 54 h, more preferably in the range of from 14 to 42 h, more preferably in the range of from 16 to 36 h, more preferably in the range of from 18 to 32 h, and more preferably in the range of from 20 to 28 h.
58. The process of any one of embodiments 1 to 57, further comprising after (i) and prior to (ii) subjecting the reactant mixture to emulsifying conditions.
59. The process of embodiment 58, wherein the emulsifying conditions comprise agitation of the reactant mixture, preferably by stirring and/or sonication, and more preferably by stir ring.
60. The process of embodiment 58 or 59, wherein the emulsifying conditions comprise use of a homogenizer, preferably with a rotor-stator homogenizes with an ultrasonic homogeniz es with a high pressure homogenizer, by microfluidic systems, or by membrane emulsifi cation, more preferably with an ultrasonic homogenizer.
61. The process of any one of embodiments 58 to 60, wherein the emulsifying conditions are applied for a period ranging from 0.1 to 15 min, preferably from 1 to 13 min, more prefera bly from 2 to 12 min, more preferably from 3 to 11 min, more preferably from 4 to 10 min, more preferably from 5 to 9 min, more preferably from 6.0 to 8.0 min, and more preferably from 6.5 to 7.5 min.
62. The process of any one of embodiments 1 to 61 , wherein no matter is added to and/or removed from the reactant stream during its passage through the reaction zone com prised in the flow reactor according to (i), wherein preferably no matter is added, wherein more preferably no matter is added and no matter is removed from the reactant stream during its passage through the reaction zone comprised in the flow reactor according to
(i)·
63. The process of any one of embodiments 1 to 62, wherein the crystallization conditions according to (ill) comprise heating the reactant stream at a temperature in the range of from 160 to 320°C, preferably of from 170 to 300 °C, more preferably of from 175 to 295 °C, more preferably of from 190 to 290°C, more preferably of from 210 to 270°C, more preferably of from 220 to 260°C, more preferably of from 230 to 250°C, more preferably of from 235 to 245°C, and more preferably of from 237 to 243 °C.
64. The process of any one of embodiments 1 to 63, wherein the crystallization conditions according to (ill) comprise autogenous pressure, preferably a pressure in the range of from 17 to 25 MPa, preferably in the range of from 12 to 20 MPa, more preferably in the range of from 14 to 18 MPa, more preferably in the range of from 15.0 to 17.0 MPa, more preferably in the range of from 15.5 to 16.5 MPa.
65. The process of any one of embodiments 1 to 64, wherein the reactant stream is passed in the reactant zone with a flow rate in the range of from 0.01 to 20 ml/min, preferably in the range of from 0.1 to 15 ml/min, more preferably in the range of from 0.15 to 1 1 ml/min, more preferably in the range of from 0.20 to 1.00 ml/min, more preferably in the range of from 0.35 to 0.80 ml/min, more preferably in the range of from 0.40 to 0.70 ml/min, more preferably in the range of from 0.50 to 0.65 ml/min, more preferably in the range of from 0.55 to 0.59 ml/min.
66. The process of any one of embodiments 1 to 65, wherein the reactant stream is passed in the reactant zone with a liquid hourly space velocity in the range of from 0.05 to 10 IT1, preferably in the range of from 0.1 to 5 IT1, more preferably in the range of from 0.5 to 2.0 IT1, more preferably in the range of from 0.8 to 1.5 IT1, more preferably in the range of from 1.0 to 1.3 IT1, more preferably in the range of from 1.1 to 1.2 IT1.
67. The process of any one of embodiments 1 to 66, wherein after (i) and prior to (ii) the reac tant stream is heated at a temperature in the range of from 45 to 135 °C, preferably in the range of from 65 to 1 15 °C, more preferably in the range of from 75 to 105 °C, more pref erably in the range of from 80 to 100 °C, more preferably in the range of from 85 to 95 °C.
68. The process of any one of embodiments 1 to 67, wherein in (ii) the reactant stream is con tinuously fed into the flow reactor for a duration ranging from 0.1 h to 140 d, more prefera bly from 0.15 h to 100 d, more preferably from 0.2 h to 70 d, more preferably from 0.5 h to 50 d, more preferably from 1 h to 40 d, more preferably from 2 h to 35 d, more preferably from 5 h to 30 d, more preferably from 10 h to 25 d, more preferably from 15 h to 20 d, more preferably from 20 h to 15 d, and more preferably from 1 d to 10 d. The process of any one of embodiments 1 to 68, wherein the process further comprises
(iv) isolating the zeolitic material obtained in (iii);
and/or, preferably and,
(v) washing the zeolitic material obtained in (iii), or (iv);
and/or, preferably and,
(vi) drying the zeolitic material obtained in (iii), (iv), or (v);
and/or, preferably and,
(vii) calcining the zeolitic material obtained in (iii), (iv), (v), or (vi). The process of embodiment 69, wherein isolating in (iv) is achieved by filtration and/or centrifugation, preferably by centrifugation. The process of embodiment 69 or 70, wherein washing in (v) 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 solvents and mixtures thereof, preferably from the group consisting of n-butanol, isopropanol, propanol, ethanol, metha nol, water, and mixtures thereof,
more preferably from the group consisting of ethanol, methanol, water, and mixtures thereof,
wherein more preferably the solvent system comprises water, and wherein more prefera bly water is used as the solvent system, preferably deionized water. The process of any one of embodiments 69 to 71 , wherein drying in (vi) is conducted at a temperature in the range of from 20 to 160 °C, preferably in the range of from 30 to 140 °C, more preferably in the range of from 40 to 120 °C, more preferably in the range of from 50 to 110 °C, more preferably in the range of from 60 to 100 °C, more preferably in the range of from 70 to 90 °C, and more preferably in the range of from 75 to 85 °C. The process of any one of embodiments 69 to 72, wherein the calcining in (vii) is effected at a temperature in the range from 300 to 750 °C, more preferably from 325 to 650 °C, more preferably from 350 to 600 °C, more preferably from 375 to 550 °C, more preferably from 400 to 500 °C, and more preferably from 425 to 475 °C. The process of any one of embodiments 69 to 73 wherein the process further comprises (viii) subjecting the zeolitic material obtained in (iv), (v), (vi), or (vii) to an ion-exchange procedure, wherein at least one ionic non-framework element or compound contained in the zeolitic material is ion-exchanged against one or more metal ions. 75. The process of embodiment 74, wherein in (viii) the step of subjecting the zeolitic material to an ion-exchange procedure includes the steps of
(viii. a) subjecting the zeolitic material obtained in (iv), (v), (vi), or (vii) to an ion- exchange procedure, wherein at least one ionic non-framework element or compound contained in the zeolitic material is ion-exchanged against NhU ;
(viii.b) calcining the ion-exchanged zeolitic material obtained in (viii. a) for obtaining the H-form of the zeolitic material;
(viii.c) subjecting the zeolitic material obtained in (viii.b) to an ion-exchange proce dure, wherein H+ contained in the zeolitic material as ionic non-framework element is ion- exchanged against one or more metal ions.
76. The process of embodiment 74 or 75, wherein the one or more metal ions are selected from the group consisting of ions of alkaline earth metal elements and/or transition metal elements, preferably from the group consisting of ions of metals selected from group 4 and groups 6-1 1 of the Periodic Table of the Elements, more preferably from group 4 and groups 8-1 1 , wherein more preferably the one or more metal ions are selected from the group consisting of ions 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 ions of Ti, Cu, Fe, Rh, Pd, Pt, and mixtures of two or more thereof, wherein more preferably the at least one ionic non-framework element or compound contained in the zeolitic mate rial is ion-exchanged against Cu and/or Fe, preferably against Cu.
77. The process of any one of embodiments 74 to 76, wherein in (viii) the zeolitic material is ion-exchanged such as to obtain a loading of the one or more metal ions in the zeolitic material ranging from 0.1 to 15 weight- % calculated as the element and based on 100 weight- % of S1O2 contained in the zeolitic material, preferably from 0.5 to 10 weight-%, more preferably from 1 to 8 weight-%, more preferably from 1.5 to 7 weight-%, more pref erably from 2 to 6 weight-%, more preferably from 2.5 to 5.5 weight-%, more preferably from 3 to 5 weight-%, more preferably from 3.5 to 4.5 weight-%.
78. The process of any one of embodiments 1 to 77, wherein the mean particle size D50 by volume as determined according to ISO 13320:2009 of the zeolitic material obtained from crystallization in (iii) is of at least 0.5 pm, and is preferably 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.
79. A zeolitic material obtainable and/or obtained according to the process of any one of em bodiments 1 to 78.
80. Use of a zeolitic material according to embodiment 79 as a molecular sieve, as an adsor bent, 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 reduction (SCR) of nitrogen oxides NOx; for the storage and/or adsorption of CO2; for the oxidation of NH3, in particular for the oxi dation of NH3 slip in diesel systems; for the decomposition of N2O; 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 ole fin (MTO) catalysis; more preferably for the selective catalytic reduction (SCR) of nitrogen oxides NOx, and more preferably for the selective catalytic reduction (SCR) of nitrogen ox ides NOx in exhaust gas from a combustion engine, preferably from a diesel engine or from a lean burn gasoline engine.
DESCRIPTION OF THE FIGURES
Figure 1 : shows the X-ray diffraction pattern (measured using Cu K alpha- 1 radiation) of the zeolitic materials obtained according to Example 1 before (see Flow_1_220°C- 240°C _before) and after (see Flow_J __220°C-240°C after) applying the inventive process on a reaction mixture according to Reference example 1. In the figure, the angle 2 theta in ° is shown along the abscissa and the intensity is plotted along the ordinate in arbitrary units.
EXPERIMENTAL SECTION
Examples
Reference example 1 : Preparation of reaction mixture
First, 2.51 g of an aqueous solution of cyclohexyltrimetylammonium hydroxide (CHTMAOH, 20 weight- % in water) and 0.827 g of an aqueous solution of tetramethylammonium hydroxide (TMAOH, 25 weight- % in water) were mixed. Then, 0.112 g of aluminum hydroxide was slowly added under stirring. After dispersion of aluminum hydroxide for 30 min, 3.00 g of colloidal silica (colloidal solution of silica comprising 40 weight- % silica in water; Ludox AS-40) was added.
The resulting mixture had a molar ratio Si02 : AI2O3 : CHTMAOH : TMAOH : H2O of silica to alumina to cyclohexyltrimetylammonium hydroxide to tetramethylammonium hydroxide to water of 1 : 0.036 : 0.158 : 0.1 13 : 11.5. Said mixture was further stirred for 10 min before the addition of 0.120 g of CHA seed crystals. The seed crystals were milled prior to use in a bead-milling apparatus (LMZ015, Ashizawa Finetech Ltd.) whereby 10 g of the source of the seed crystals were dispersed in 300 ml of water and milled with the bead-milling apparatus for 120 min at 3000 rpm using zirconia beads with a diameter of 300 pm. In the vessel, 75% of the volume were filled with zirconia beads. After the milling treatment, the slurry was centrifuged, and the residual solid was recovered. The seed crystals thus obtained had a crystallinity of 43 % as de- termined according to reference example 3. The mixture was then charged to a 23ml Teflon- lined autoclave for aging at 140 °C for 24 h with 20 rpm tumbling. 6.57 g of the aged gel were mixed with 6.57 g of cyclohexane and 0.657 g of polyoxyethylene(10)oleyiether. The mixture was homogenized using a ultrasonic homogenizer (Hielscher UP400S) for 7 min for obtaining a gel.
Reference example 2: Determination of X-ray diffraction pattern and the crystallinity
The powder X-ray diffraction (XRD) patterns were collected using a diffractometer (Rigaku Ulti ma IV) equipped with a D/Tex Ultra detector operated with Cu Ka monochromatized radiation at 40 kV and 40 mA. A scan step was 0.02° at a scan speed of 207min. Crystallinity was calculat ed using integrated peak areas of the peaks in 2theta range of 20° to 35°.
Reference example 3: Determination of X-ray diffraction pattern and the crystallinity
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.
Computing crystallinity: The crystallinity of the samples was determined using the software DIF- F RAC. EVA provided by Bruker AXS GmbH, Karlsruhe. The method is described on page 121 of the user manual. The default parameters for the calculation were used.
Computing phase composition: The phase composition was computed against the raw data using the modelling software DIFFRAC.TOPAS provided by Bruker AXS GmbH, Karlsruhe. 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°
2Theta, while the variable divergence slit was set to an angle of 0.1 °. The crystalline content describes the intensity of the crystalline signal to the total scattered intensity. (User Manual for DIFFRAC.EVA, Bruker AXS GmbH, Karlsruhe.)
Example 1 : Process for the continuous preparation of a zeolitic material having the CHA framework structure type
The flow reactor for testing the continuous preparation of a zeolitic material having the CHA framework structure type comprised a stainless synthesis tube lined with Teflon having an inner diameter of 2.0 mm, a pump for providing the reactant stream comprising the reactant mixture, a reactant mixture tank, eight sequentially arranged heaters for heating a reaction zone, and a product tank. The temperature of the tube was regulated by hot/cold water.
The gel obtained from Reference Example 1 was charged into the flow reactor and crystallized at a temperature 240 °C for 920 s, whereby the gel was first heated by a first heater to a tem perature T1 of 220 °C and then by the following seven heaters to a temperature T2 of 240 °C. The conditions as listed in tables 1 and 2 were applied during said time.
Samples were collected using centrifugation at 14000 rpm and washed with water until the pH became about 7-8. The solid product was dried at 80 °C.
As can be gathered from figure 1 showing the X-ray diffraction pattern of the zeolitic material obtained from Example 1 , a zeolitic material was obtained having the CHA framework structure type with a crystallinity of 51.5 % after a reaction time of 920 s compared to a crystallinity of 4.1 % before applying the inventive process, whereby the crystallinity was determined according to Reference Example 2.
Table 1
Conditions applied during the continuous process
Figure imgf000040_0001
Table 2
Conditions applied during the continuous process
Figure imgf000040_0002
Cited prior art
- WO 2015/185625 A
- Wakihara et al. in Reaction Chemistry and Engineering 2018, volume 00, pages 1-5, DOI:
10.1039/c8re00139a
- WO 201 1/064186 A1
- EP 2 325 143 A2
- Zones et al. "A Study of Guest/Host Energetics for the Synthesis of Cage Structures NON and CHA" in Studies in Surface Science and Catalysis, Vol. 84, pp. 29-36, Elsevier Sci ence B.V. (1994) - WO 2013/182974 A

Claims

Claims
1. A continuous process for preparing a zeolitic material comprising YO2 and optionally X2O3 in its framework structure, wherein Y is a tetravalent element and X is a trivalent element, said process comprising
(i) providing a flow reactor comprising a reaction zone;
(ii) continuously passing a reactant stream through the reaction zone according to (i), wherein the reactant stream comprises a reactant mixture comprising a non-polar liquid solvent system, one or more emulsifiers, and a mixture of one or more sources of YO2, optionally one or more sources of X2O3, seed crystals, a polar protic liquid solvent sys tem, and one or more tetraalkylammonium cation containing compounds as structure di recting agent;
(ill) subjecting the reactant stream to crystallization conditions in the reaction zone and removing a product stream from the reaction zone, wherein the product stream comprises the zeolitic material.
2. The process of claim 1 , wherein the zeolitic material has a framework structure type se lected from the group consisting of AEI, AFX, ANA, BE A, BEC, CAN, CHA, CDO, EMT, ERI, EUO, FAU, FER, GME, HEU, ITH, ITW, KFI, LEV, MEI, MEL, MFI, MOR, MTN, MWW, OFF, RRO, RTH, SAV, SFW, SZR, TON, and a mixture of two or more thereof.
3. The process of claim 1 or 2, wherein Y is selected from the group consisting of Si, Ge, Sn, Ti, Zr, and combinations of two or more thereof.
4. The process of any one of claims 1 to 3, wherein X is selected from the group consisting of B, Al, Ga, In, and combinations of two or more thereof.
5. The process of any one of claims 1 to 4, wherein the seed crystals comprise a zeoltic ma terial, wherein the zeolitic material comprises YO2 and optionally X2O3, wherein Y is a tet ravalent element and X is a trivalent element.
6. The process of any one of claims 1 to 5, wherein the one or more tetraalkylammonium cation containing compounds comprise one or more tetraalkylammonium cation
R1R2R3R4N+-containing compounds, wherein R1, R2, and R3 independently from one an other is alkyl, and wherein R4 is cycloalkyl.
7. The process of any one of claims 1 to 6, wherein the reactant mixture according to (ii) further contains one or more tetraalkylammonium cation R5R6R7R8N+-containing com pounds, wherein R5, R6, R7, and R8, independently from one another stand for optionally substituted and/or optionally branched (Ci-C6)alkyl.
8. The process of any one of claims 1 to 7, wherein the polar protic liquid solvent system comprises one or more of n-butanol, isopropanol, propanol, ethanol, methanol, and water.
9. The process of any one of claims 1 to 8, wherein the non-polar liquid solvent system com prises one or more of (C5-Cio)alkanes, (Cs-Cio)alkenes, (Cs-Cio)aromatic organic com pounds, (C4-C8)alkylethers, (Ci-C3)alkylhalides, or mixtures of two or more thereof.
10. The process of any one of claims 1 to 9, wherein the one or more emulsifiers are selected from the group consisting of ionic and nonionic surfactants, including mixtures thereof.
1 1. The process of any one of claims 1 to 10, further comprising after (i) and prior to (ii)
(a) providing a pre-mixture of one or more sources of YO2, optionally one or more sources of X2O3, seed crystals, a polar pro tic liquid solvent system, and one or more tetraalkylammonium cation containing compounds as structure directing agent;
(b) subjecting the pre-mixture obtained from (a) to pretreatment conditions to obtain the mixture comprised in the reactant mixture according to (ii).
12. The process of any one of claims 1 to 11 , further comprising after (i) and prior to (ii) sub jecting the reactant mixture to emulsifying conditions.
13. The process of any one of claims 1 to 12, wherein the process further comprises
(iv) isolating the zeolitic material obtained in (iii);
and/or,
(v) washing the zeolitic material obtained in (iii), or (iv);
and/or,
(vi) drying the zeolitic material obtained in (iii), (iv), or (v);
and/or,
(vii) calcining the zeolitic material obtained in (iii), (iv), (v), or (vi).
14. A zeolitic material obtainable and/or obtained according to the process of any one of claims 1 to 13.
15. Use of the zeolitic material according to claim 14 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.
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Citations (5)

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WO2011064186A1 (en) 2009-11-24 2011-06-03 Basf Se Process for the preparation of zeolites having cha structure
WO2013182974A1 (en) 2012-06-04 2013-12-12 Basf Se Cha type zeolitic materials and methods for their preparation using cycloalkylammonium compounds
WO2015185625A2 (en) 2014-06-05 2015-12-10 Basf Se Cha type zeolitic materials and methods for their preparation using combinations of cycloalkyl- and tetraalkylammonium compounds
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WO2011064186A1 (en) 2009-11-24 2011-06-03 Basf Se Process for the preparation of zeolites having cha structure
WO2013182974A1 (en) 2012-06-04 2013-12-12 Basf Se Cha type zeolitic materials and methods for their preparation using cycloalkylammonium compounds
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JIE ZHU ET AL: "Supporting Information Addressing the Viscosity Challenge: Ultrafast, Stable-Flow Synthesis of Zeolites with An Emulsion Method Contents", REACTION CHEMISTRY & ENGINEERING., 3 October 2018 (2018-10-03), XP055718619 *
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