WO2021203963A1 - Zeolite of a new framework structure type and production thereof - Google Patents

Zeolite of a new framework structure type and production thereof Download PDF

Info

Publication number
WO2021203963A1
WO2021203963A1 PCT/CN2021/082430 CN2021082430W WO2021203963A1 WO 2021203963 A1 WO2021203963 A1 WO 2021203963A1 CN 2021082430 W CN2021082430 W CN 2021082430W WO 2021203963 A1 WO2021203963 A1 WO 2021203963A1
Authority
WO
WIPO (PCT)
Prior art keywords
range
crystalline material
unit cell
group
mixtures
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2021/082430
Other languages
English (en)
French (fr)
Inventor
Andrei-Nicolae PARVULESCU
Ulrich Mueller
Trees Maria DE BAERDEMAEKER
Ute KOLB
Bernd Marler
Feng-Shou Xiao
Toshiyuki Yokoi
Weiping Zhang
Dirk De Vos
Xiangju MENG
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Advanced Chemicals Co Ltd
BASF SE
Original Assignee
BASF Advanced Chemicals Co Ltd
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF Advanced Chemicals Co Ltd, BASF SE filed Critical BASF Advanced Chemicals Co Ltd
Priority to JP2022564485A priority Critical patent/JP2023522754A/ja
Priority to EP21784111.3A priority patent/EP4132884A4/en
Priority to KR1020227038236A priority patent/KR20220164536A/ko
Priority to CN202180025058.XA priority patent/CN115335325A/zh
Priority to US17/917,331 priority patent/US20230150827A1/en
Publication of WO2021203963A1 publication Critical patent/WO2021203963A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
    • C01B39/12—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the replacing atoms being at least boron atoms
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
    • C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/74—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by peak-intensities or a ratio thereof only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/76—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by a space-group or by other symmetry indications
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams

Definitions

  • the present invention relates to a novel zeolite, in particular to a zeolitic material designated as COE-11 and having a novel framework structure.
  • a simple criterion for distinguishing zeolites and zeolite-like materials from denser tectosilicates is based on the framework density (FD) , the number of tetrahedrally coor-dinated framework atoms (T-atoms) per
  • the synthesis of a zeolitic material can generally be performed using one or more source mate-rials for the framework structure and one or more of a structure directing agent and a seed crys-tal.
  • the reaction mixture is typically a synthesis gel having a specific molar ratio of the one or more source materials to the one or more of a structure directing agent and a seed crystal.
  • hydrothermal conditions are then applied on the reaction mixture for the crystallizing a zeolitic material.
  • a novel zeolitic material in particular a zeolitic material having characteristic features, especially a novel framework structure type.
  • Fur-ther it was an object to provide a process for preparation of such a zeolitic material.
  • a novel zeolitic material can be provided particularly characterized in that it has a novel and unique framework structure type.
  • the present invention relates to a crystalline material having a framework structure comprising O and one or more tetravalent elements Y, and optionally comprising one or more trivalent ele- ments X, wherein the crystalline material displays a crystallographic unit cell of the monoclinic space group C2, wherein the unit cell parameter a is in the range of from 14.5 to the unit cell parameter b is in the range of from 14.5 to the unit cell parameter c in the range of from 11.5 to and the unit cell parameter ⁇ is in the range of from 109 to 118°, wherein the framework density is in the range of from 11 to 23 wherein the framework structure comprises 12 membered rings, and wherein the framework structure displays a 2-dimensional channel dimensionality of 12 membered ring channels.
  • the unit cell parameter a is in the range of from 15.5 to more prefera-bly in the range of from 16.5 to more preferably in the range of from 17 to more preferably in the range of from 17.3 to more preferably in the range of from 17.33 to
  • the unit cell parameter b is in the range of from 15.5 to more prefera-bly in the range of from 16.5 to more preferably in the range of from 17 to more preferably in the range of from 17.2 to more preferably in the range of from 17.31 to
  • the unit cell parameter c is in the range of from 12.5 to more prefera-bly in the range of from 13.5 to more preferably in the range of from 14 to more preferably in the range of from 14.2 to more preferably in the range of from 14.31 to
  • the unit cell parameter ⁇ is in the range of from 110 to 117°, more preferably in the range of from 111 to 116°, more preferably in the range of from 112 to 115°, more prefer-ably in the range of from 113.0 to 114.4° more preferably in the range of from 113.5 to 113.9°.
  • the framework density is in the range of from 13 to 21 more preferably in the range of from 14 to 20 more preferably in the range of from 15.6 to 18.1 more preferably in the range of from 16.6 to 17.1 more preferably in the range of from 16.6 to 16.8
  • the crystalline material displays an X-ray diffraction pattern comprising at least the following reflections:
  • the crystalline material more preferably displays an X-ray diffraction pattern com-prising at least the following reflections:
  • the framework structure comprises one or more of composite building units bea, mor, and bik, wherein the framework structure preferably comprises composite building units bea, mor, and bik.
  • framework structure further comprises 4-, 5-, and 6-membered rings.
  • the framework structure comprises a two dimensional pore system.
  • the framework structure comprises an elliptical pore, more preferably an ellip-tical pore having a first pore diameter in the range of from 7.0 to more preferably in the range of from 7.8 to more preferably in the range of from 8.0 to and a second pore diameter in the range of from 4.0 to preferably in the range of from 5.0 to more preferably in the range of from 5.2 to
  • T-atoms in the framework structure of the crystalline material are located at the following sites of the unit cell:
  • T 5 4 0.5199 0.1144 0.3516 T 6 4 0.6287 0.8721 0.5053 T 7 4 0.7942 0.8164 0.6628 T 8 4 0.6071 0.0523 0.216 T 9 2 1 0.2405 0.5 T 10 4 0.7071 0.9256 0.3638 T 11 4 0.8306 0.8013 0.356 T 12 4 0.7361 0.181 0.2119 T 13 4 0.9012 0.1203 0.3477 T 14 4 1.0987 0.7417 0.7765 T 15 4 0.9714 0.87 0.7841 T 16 4 0.976 0.9994 0.6561 T 17 4 0.6278 0.2027 -0.0074 T 18 2 0.5 0.0771 0 T 19 2 0.5 0.3323 0
  • x, y, and z refer to the axes of the unit cell.
  • coordination sequences and the vertex symbols of the T-atoms in the framework structure of the crystalline material are as follows:
  • Vertex Symbol refers to the size and number of the shortest ring on each an-gle of the T-atom, according to M. O’Keeffe and S. T. Hyde, Zeolites 19, 370 (1997) .
  • the Y : X molar ratio of the framework structure is in the range of from 1 to 100, more preferably in the range of from 5 to 30, more preferably in the range of from 10 to 21, more preferably in the range of from 13 to 18, more preferably in the range of from 14.5 to 16.5, more preferably in the range of from 15.2 to 15.8, more preferably in the range of from 15.4 to 15.6.
  • the one or more tetravalent elements Y are selected from the group consist-ing of Si, Sn, Ti, Zr, Ge, and mixtures of two or more thereof, Y more preferably being Si.
  • the optional one or more trivalent elements X are selected from the group consisting of Al, B, In, Ga, and mixtures of two or more thereof, X more preferably being Al and/or B, wherein more preferably X is B.
  • the crystalline material contains one or more metals as non-framework ele-ments, more preferably at the ion-exchange sites of the crystalline material, wherein the one or more metals are selected from the group consisting of one or more alkali metals, one or more alkaline earth metals, and one or more transition metals, including mixtures of two or more thereof, wherein preferably the crystalline material contains one or more transition metals as non-framework elements, including mixtures of two or more thereof.
  • the one or more transition metals are selected from the group consisting of Zr, Cr, Mo, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, and mixtures of two or more thereof.
  • the one or more alkali metals are selected from the group consisting of Li, Na, K, Rb, Cs, and mixtures of two or more thereof, wherein more preferably the one or more alkali metals comprise Na and/or K.
  • the one or more alkaline earth metals are selected from the group consisting of Mg, Ba, Sr, and mixtures of two or more thereof, wherein more preferably the one or more alkaline earth metals comprise Mg and/or Sr.
  • the crystalline material contains H + and/or NH 4 + as non-framework elements, more preferably at the ion-exchange sites of the crystalline material.
  • the crystalline material is a zeolite.
  • the crystalline material has a BET specific surface area in the range of from 300 to 530 m 2 /g, more preferably in the range of from 350 to 480 m 2 /g, more preferably in the range of from 400 to 430 m 2 /g, wherein the BET specific surface area is preferably determined as described in Reference Example 2.
  • the crystalline material has a micropore volume in the range of from 0.12 to 0.24 cm 3 /g, more preferably in the range of from 0.15 to 0.21 cm 3 /g, more preferably in the range of from 0.17 to 0.19 cm 3 /g, wherein the micropore volume is preferably determined as described in Reference Example 3.
  • the present invention relates to a method for the production of a crystalline material, preferably of a crystalline material according to any one of the embodiments disclosed herein, said method comprising
  • R 1 , R 2 , R 3 , and R 4 independently from one another stand for alkyl.
  • R 1 , R 2 , R 3 , and R 4 independently from one another stand for optionally substi-tuted and/or optionally branched (C 1 -C 6 ) alkyl, more preferably (C 1 -C 5 ) alkyl, more preferably (C 1 -C 4 ) alkyl, more preferably (C 2 -C 3 ) alkyl, and even more preferably for optionally substituted ethyl or propyl, wherein even more preferably R 1 , R 2 , R 3 , and R 4 , stand for optionally substituted ethyl, preferably unsubstituted ethyl.
  • the one or more tetraalkylammonium cation R 1 R 2 R 3 R 4 N + -containing com-pounds comprise one or more compounds selected from the group consisting of tetra (C 1 -C 6 ) alkylammonium compounds, more preferably tetra (C 1 -C 5 ) alkylammonium compounds, more preferably tetra (C 1 -C 4 ) alkylammonium compounds, and more preferably tetra (C 2 -C 3 ) alkylammonium compounds, wherein independently from one another the alkyl substituents are optionally substituted and/or optionally branched, and wherein more preferably the one or more tetraalkylammonium cation R 1 R 2 R 3 R 4 N + -containing compounds are selected from the group consisting of optionally substituted and/or optionally branched tetrapropylammonium compounds, ethyltripropylammonium compounds,
  • the one or more tetraalkylammonium cation R 1 R 2 R 3 R 4 N + -containing com-pounds are salts, more preferably one or more salts selected from the group consisting of hal-ides, 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 prefer-ably the one or more tetraalkylammonium cation R 1 R 2 R 3 R 4 N + -containing compounds are tetraalkylammonium hydroxides and/or chlorides, and even more preferably tetraalkylammoni-um hydroxides.
  • a molar ratio R 1 R 2 R 3 R 4 N + : YO 2 of the one or more tetraalkylammonium cati-ons to the one or more sources of YO 2 calculated as YO 2 in the mixture provided according to (a) is comprised in the range of from 0.001 to 10, more preferably in the range of from 0.01 to 5, more preferably in the range of from 0.1 to 1, more preferably in the range of from 0.25 to 0.5, more preferably in the range of from 0.3 to 0.36, more preferably in the range of from 0.32 to 0.34.
  • the tetravalent element Y is selected from the group consisting of Si, Sn, Ti, Zr, Ge, and mixtures of two or more thereof, Y more preferably being Si.
  • the trivalent element X is selected from the group consisting of Al, B, In, Ga, and mixtures of two or more thereof, X preferably being Al and/or B, wherein more preferably X is B.
  • a YO 2 : X 2 O 3 molar ratio of the one or more sources of YO 2 calculated as YO 2 to the one or more sources of X 2 O 3 calculated as X 2 O 3 in the mixture prepared in (a) is in the range of from 1 to 50, more preferably in the range of from 6 to 40, more preferably in the range of from 11 to 30, more preferably in the range of from 16 to 25, more preferably in the range of from 18 to 22, more preferably in the range of from 19 to 21.
  • the tetravalent element Y is Si
  • the at least one source of YO 2 com-prises one or more compounds selected from the group consisting of fumed silica, silica hydro-sols, reactive amorphous solid silicas, silica gel, silicic acid, water glass, sodium metasilicate hydrate, sesquisilicate, disilicate, colloidal silica, silicic acid esters, and mixtures of two or more thereof, more preferably from the group consisting of fumed silica, silica hydrosols, reactive amorphous solid silicas, silica gel, silicic acid, colloidal silica, silicic acid esters, and mixtures of two or more thereof, more preferably from the group consisting of fumed silica, silica hydrosols, reactive amorphous solid silicas, silica gel, colloidal silica, and mixtures of two or more thereof, wherein even more preferably the one or more sources for YO 2 comprises fu
  • the trivalent element X is B
  • the at least one source of X 2 O 3 comprises one or more compounds selected from the group consisting of free boric acid, borates, boric esters, and mixtures of two or more thereof, wherein more prefer-ably the at least one source of X 2 O 3 comprises boric acid.
  • the trivalent element X is Al
  • the one or more sources for X 2 O 3 comprises one or more compounds selected from the group consisting of alumina, aluminates, aluminum salts, and mixtures of two or more thereof, more preferably from the group consisting of alumina, aluminum salts, and mixtures of two or more thereof, more preferably from the group consisting of alumina, aluminum tri (C 1 -C 5 ) alkoxide, AlO (OH) , Al (OH) 3 , aluminum halides, preferably aluminum fluoride and/or chloride and/or bromide, more preferably aluminum fluoride and/or chloride, and even more preferably aluminum chloride, aluminum sul-fate, aluminum phosphate, aluminum fluorosilicate, and mixtures of two or more thereof, more preferably from the group consisting of aluminum tri (C 2 -C 4 ) alkoxide, AlO (OH) , Al (OH) 3 , alumi-num chlor
  • the seed crystals comprise one or more crystalline materials according to any one of the embodiments disclosed herein.
  • the mixture prepared in (a) further comprises a solvent system containing one or more solvents, wherein the solvent system more preferably comprises one or more solvents selected from the group consisting 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.
  • the solvent system more preferably comprises one or more solvents selected from the group consisting 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
  • the mixture prepared in (a) comprises water as the solvent system, wherein a H 2 O : YO 2 molar ratio of H 2 O to the one or more sources of YO 2 calculated as YO 2 in the mix-ture prepared in (a) is in the range of from 0.1 to 100, more preferably in the range of from 1 to 50, more preferably in the range of from 5 to 30, more preferably in the range of from 10 to 22, more preferably in the range of from 13 to 19, more preferably in the range of from 15 to 17.
  • the mixture prepared in (a) further comprises at least one source for OH - , wherein said at least one source for OH - more preferably comprises a metal hydroxide, more preferably a hydroxide of an alkali metal, even more preferably sodium and/or potassium hy-droxide.
  • a OH - : YO 2 molar ratio of hydroxide to the one or more sources of YO 2 cal-culated as YO 2 in mixture prepared in (a) is in the range of from 0.01 to 10, more preferably in the range of from 0.05 to 2, more preferably in the range of from 0.1 to 0.9, more preferably in the range of from 0.3 to 0.7, more preferably in the range of from 0.4 to 0.65, more preferably in the range of from 0.45 to 0.60.
  • the mixture prepared in (a) is heated to a temperature comprised in the range of from 130 to 190 °C, more preferably in the range of from 140 to 180 °C, more prefera-bly in the range of from 145 to 175 °C, more preferably in the range of from 150 to 170 °C, more preferably in the range of from 155 to 165 °C.
  • the heating in (b) is conducted under autogenous pressure, more preferably under solvothermal conditions, and more preferably under hydrothermal conditions.
  • the heating in (b) is conducted for a period comprised in the range of from 1 to 15 d, more preferably in the range of from 3 to 11 d, more preferably in the range of from 5 to 9 d, more preferably in the range of from 6 to 8 d.
  • heating in (b) comprises heating the mixture prepared in (a) at a first temperature T 1 for a first duration and subsequently increasing the first tempera-ture T 1 to a second temperature T 2 for a second duration, wherein T 1 ⁇ T 2 , and wherein the total duration of heating is comprised in the range of from 1 to 15 d, more preferably in the range of from 3 to 11 d, more preferably in the range of from 5 to 9 d, more preferably in the range of from 6 to 8 d.
  • heating in (b) comprises heating the mixture prepared in (a) at a first tem-perature T 1 for a first duration and subsequently increasing the first temperature T 1 to a second temperature T 2 for a second duration
  • the first temperature T 1 is in the range of from 130 to 180 °C, more preferably in the range of from 140 to 170 °C, more preferably in the range of from 145 to 165 °C, more preferably in the range of from 150 to 160 °C.
  • heating in (b) comprises heating the mixture prepared in (a) at a first temperature T 1 for a first duration and subsequently increasing the first temperature T 1 to a sec-ond temperature T 2 for a second duration
  • the first duration is comprised in the range of from 1 h to 8 d, more preferably in the range of from 6 h to 6 d, more preferably in the range of from 12 h to 5 d, more preferably in the range of from 1 to 4 d.
  • heating in (b) comprises heating the mixture prepared in (a) at a first temperature T 1 for a first duration and subsequently increasing the first temperature T 1 to a sec-ond temperature T 2 for a second duration
  • the second temperature T 2 is in the range of from 140 to 190 °C, more preferably in the range of from 150 to 180 °C, more prefera-bly in the range of from 155 to 175 °C, more preferably in the range of from 160 to 170 °C.
  • heating in (b) comprises heating the mixture prepared in (a) at a first temperature T 1 for a first duration and subsequently increasing the first temperature T 1 to a sec-ond temperature T 2 for a second duration
  • the second duration is comprised in the range of from 12 h to 10 d, more preferably in the range of from 1 d to 8 d, more prefera-bly in the range of from 2 d to 7 d, more preferably in the range of from 3 to 6 d.
  • the crystallization in (b2) involves agitating the mixture, more preferably by stirring.
  • washing the crystalline material obtained in (b) or (c) is performed using a solvent system containing one or more solvents, wherein the solvent system preferably com-prises one or more solvents selected from the group consisting of polar protic solvents and mix-tures thereof,
  • n-butanol preferably from the group consisting of n-butanol, isopropanol, propanol, ethanol, methanol, water, and mixtures thereof,
  • the solvent system comprises water, and wherein more preferably wa-ter is used as the solvent system, preferably deionized water.
  • drying the crystalline material obtained in (b) , (c) , or (d) is performed in a gas atmosphere having a temperature in the range of from 5 to 200 °C, more preferably in the range of from 15 to 100 °C, more preferably in the range of from 20 to 25 °C.
  • the gas atmosphere comprises one or more of nitrogen and oxygen, wherein the gas atmos-phere preferably comprises air.
  • the method may comprise further process steps. It is preferred that the method further com-prises
  • the one or more metal cations are selected from the group consisting of one or more alkali metal cations, one or more alkaline earth metal cations, and one or more transition metal cations, including mixtures of two or more thereof, wherein more preferably the one or more metal cations comprise one or more transition metal cations as non-framework elements, including mixtures of two or more thereof.
  • the one or more transition metal cations are selected from the group consisting of cations of Zr, Cr, Mo, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, and mixtures of two or more thereof.
  • the one or more alkali metal cations are selected from the group consisting of cations of Li, Na, K, Rb, Cs, and mixtures of two or more thereof, wherein more preferably the one or more alkali metal cations comprise cations of Na and/or K.
  • the one or more alkaline earth metal cations are selected from the group consisting of cations of Mg, Ba, Sr, and mixtures of two or more thereof, wherein more preferably the one or more alkaline earth metal cations comprise cations of Mg and/or Sr.
  • the method may comprise further process steps. It is preferred that the method further comprises
  • the present invention relates to a crystalline material obtainable or obtained accord-ing to the process of any one of the embodiments disclosed herein.
  • the present invention relates to a use of a crystalline material according to any one of the embodiments disclosed herein as a molecular sieve, for ion-exchange, as an adsorbent, as an absorbent, as a catalyst or as a catalyst component, more preferably as a catalyst or as a catalyst component, more preferably as a Lewis acid catalyst or a Lewis acid catalyst compo-nent, as a catalyst for the selective catalytic reduction (SCR) of nitrogen oxides NO x , for the oxidation of NH 3 , in particular for the oxidation of NH 3 slip in diesel systems, for the decomposi-tion of N 2 O, as an additive in fluid catalytic cracking (FCC) processes, as an isomerization cata-lyst or as an isomerization catalyst component, as an oxidation catalyst or as an oxidation cata-lyst component, as a hydrocracking catalyst, as an alkylation catalyst, as an aldol condensation catalyst or as an aldo
  • the unit bar (abs) refers to an absolute pressure of 10 5 Pa and the unit Angstrom refers to a length of 10 -10 m.
  • the present invention relates to a crystalline material having a framework structure comprising O and one or more tetravalent elements Y, and optionally com-prising one or more trivalent elements X, wherein the crystalline material displays a crystallo-graphic unit cell of the monoclinic space group C2, wherein the unit cell parameter a is in the range of from 14.5 to the unit cell parameter b is in the range of from 14.5 to the unit cell parameter c in the range of from 11.5 to and the unit cell parameter ⁇ is in the range of from 109 to 118°, wherein the framework density is in the range of from 11 to 23 wherein the framework structure comprises 12 membered rings, and wherein the framework structure displays a 2-dimensional channel dimensionality of 12 membered ring channels.
  • a preferred embodiment (2) concretizing embodiment (1) relates to said crystalline material, wherein the unit cell parameter a is in the range of from 15.5 to preferably in the range of from 16.5 to more preferably in the range of from 17 to more preferably in the range of from 17.3 to more preferably in the range of from 17.33 to
  • a further preferred embodiment (3) concretizing embodiment (1) or (2) relates to said crystalline material, wherein the unit cell parameter b is in the range of from 15.5 to preferably in the range of from 16.5 to more preferably in the range of from 17 to more prefera-bly in the range of from 17.2 to more preferably in the range of from 17.31 to
  • a further preferred embodiment (4) concretizing any one of embodiments (1) to (3) relates to said crystalline material, wherein the unit cell parameter c is in the range of from 12.5 to preferably in the range of from 13.5 to more preferably in the range of from 14 to more preferably in the range of from 14.2 to more preferably in the range of from 14.31 to
  • a further preferred embodiment (5) concretizing any one of embodiments (1) to (4) relates to said crystalline material, wherein the unit cell parameter ⁇ is in the range of from 110 to 117°, preferably in the range of from 111 to 116°, more preferably in the range of from 112 to 115°, more preferably in the range of from 113.0 to 114.4° more preferably in the range of from 113.5 to 113.9°.
  • a further preferred embodiment (6) concretizing any one of embodiments (1) to (5) relates to said crystalline material, wherein the framework density is in the range of from 13 to 21 preferably in the range of from 14 to 20 more preferably in the range of from 15.6 to 18.1 more preferably in the range of from 16.6 to 17.1 more preferably in the range of from 16.6 to 16.8
  • a further preferred embodiment (7) concretizing any one of embodiments (1) to (6) relates to said crystalline material, wherein the crystalline material displays an X-ray diffraction pattern comprising at least the following reflections:
  • the crystalline material preferably displays an X-ray diffraction pattern comprising at least the following reflections:
  • a further preferred embodiment (8) concretizing any one of embodiments (1) to (7) relates to said crystalline material, wherein the framework structure comprises one or more of composite building units bea, mor, and bik, wherein the framework structure preferably comprises compo-site building units bea, mor, and bik.
  • a further preferred embodiment (9) concretizing any one of embodiments (1) to (8) relates to said crystalline material, wherein the framework structure further comprises 4-, 5-, and 6-membered rings.
  • a further preferred embodiment (10) concretizing any one of embodiments (1) to (9) relates to said crystalline material, wherein the framework structure comprises a two dimensional pore system.
  • a further preferred embodiment (11) concretizing any one of embodiments (1) to (10) relates to said crystalline material, wherein the framework structure comprises an elliptical pore, prefera-bly an elliptical pore having a first pore diameter in the range of from 7.0 to more prefera-bly in the range of from 7.8 to more preferably in the range of from 8.0 to and a second pore diameter in the range of from 4.0 to preferably in the range of from 5.0 to more preferably in the range of from 5.2 to
  • a further preferred embodiment (12) concretizing any one of embodiments (1) to (11) relates to said crystalline material, wherein the T-atoms in the framework structure of the crystalline mate-rial are located at the following sites of the unit cell:
  • T-atom name Site Multiplicity x y z T 1 2 1 0.8801 0.5 T 2 4 0.6904 0.1943 0.4939 T 3 2 0.5 0.9983 0.5 T 4 4 0.8179 0.0629 0.5032 T 5 4 0.5199 0.1144 0.3516 T 6 4 0.6287 0.8721 0.5053 T 7 4 0.7942 0.8164 0.6628 T 8 4 0.6071 0.0523 0.216 T 9 2 1 0.2405 0.5 T 10 4 0.7071 0.9256 0.3638
  • T 11 4 0.8306 0.8013 0.356 T 12 4 0.7361 0.181 0.2119 T 13 4 0.9012 0.1203 0.3477 T 14 4 1.0987 0.7417 0.7765 T 15 4 0.9714 0.87 0.7841 T 16 4 0.976 0.9994 0.6561 T 17 4 0.6278 0.2027 -0.0074 T 18 2 0.5 0.0771 0 T 19 2 0.5 0.3323 0
  • x, y, and z refer to the axes of the unit cell.
  • a further preferred embodiment (13) concretizing any one of embodiments (1) to (12) relates to said crystalline material, wherein the coordination sequences and the vertex symbols of the T-atoms in the framework structure of the crystalline material are as follows:
  • Vertex Symbol refers to the size and number of the shortest ring on each an-gle of the T-atom, according to M. O’Keeffe and S. T. Hyde, Zeolites 19, 370 (1997) .
  • a further preferred embodiment (14) concretizing any one of embodiments (1) to (13) relates to said crystalline material, wherein the Y : X molar ratio of the framework structure is in the range of from 1 to 100, preferably in the range of from 5 to 30, more preferably in the range of from 10 to 21, more preferably in the range of from 13 to 18, more preferably in the range of from 14.5 to 16.5, more preferably in the range of from 15.2 to 15.8, more preferably in the range of from 15.4 to 15.6.
  • a further preferred embodiment (15) concretizing any one of embodiments (1) to (14) relates to said crystalline material, wherein the one or more tetravalent elements Y are selected from the group consisting of Si, Sn, Ti, Zr, Ge, and mixtures of two or more thereof, Y preferably being Si.
  • a further preferred embodiment (16) concretizing any one of embodiments (1) to (15) relates to said crystalline material, wherein the optional one or more trivalent elements X are selected from the group consisting of Al, B, In, Ga, and mixtures of two or more thereof, X preferably be-ing Al and/or B, wherein more preferably X is B.
  • a further preferred embodiment (17) concretizing any one of embodiments (1) to (16) relates to said crystalline material, wherein the crystalline material contains one or more metals as non-framework elements, preferably at the ion-exchange sites of the crystalline material, wherein the one or more metals are selected from the group consisting of one or more alkali metals, one or more alkaline earth metals, and one or more transition metals, including mixtures of two or more thereof, wherein preferably the crystalline material contains one or more transition metals as non-framework elements, including mixtures of two or more thereof.
  • a further preferred embodiment (18) concretizing any one of embodiments (1) to (17) relates to said crystalline material, wherein the one or more transition metals are selected from the group consisting of Zr, Cr, Mo, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, and mixtures of two or more thereof.
  • a further preferred embodiment (19) concretizing any one of embodiments (1) to (18) relates to said crystalline material, wherein the one or more alkali metals are selected from the group con-sisting of Li, Na, K, Rb, Cs, and mixtures of two or more thereof, wherein preferably the one or more alkali metals comprise Na and/or K.
  • a further preferred embodiment (20) concretizing any one of embodiments (1) to (19) relates to said crystalline material, wherein the one or more alkaline earth metals are selected from the group consisting of Mg, Ba, Sr, and mixtures of two or more thereof, wherein preferably the one or more alkaline earth metals comprise Mg and/or Sr.
  • a further preferred embodiment (21) concretizing any one of embodiments (1) to (20) relates to said crystalline material, wherein the crystalline material contains H + and/or NH 4 + as non-framework elements, preferably at the ion-exchange sites of the crystalline material.
  • a further preferred embodiment (22) concretizing any one of embodiments (1) to (21) relates to said crystalline material, wherein the crystalline material is a zeolite.
  • a further preferred embodiment (23) concretizing any one of embodiments (1) to (22) relates to said crystalline material, wherein the crystalline material has a BET specific surface area in the range of from 300 to 530 m 2 /g, preferably in the range of from 350 to 480 m 2 /g, more preferably in the range of from 400 to 430 m 2 /g, preferably determined as described in Reference Example 2.
  • a further preferred embodiment (24) concretizing any one of embodiments (1) to (23) relates to said crystalline material, wherein the crystalline material has a micropore volume in the range of from 0.12 to 0.24 cm 3 /g, preferably in the range of from 0.15 to 0.21 cm 3 /g, more preferably in the range of from 0.17 to 0.19 cm 3 /g, preferably determined as described in Reference Example 3.
  • An embodiment (25) of the present invention relates to a method for the production of a crystal-line material, preferably of a crystalline material according to any one of embodiments (1) to (24) , said method comprising
  • a preferred embodiment (26) concretizing embodiment (25) relates to said method, wherein R 1 , R 2 , R 3 , and R 4 independently from one another stand for optionally substituted and/or optionally branched (C 1 -C 6 ) alkyl, preferably (C 1 -C 5 ) alkyl, more preferably (C 1 -C 4 ) alkyl, more preferably (C 2 -C 3 ) alkyl, and even more preferably for optionally substituted ethyl or propyl, wherein even more preferably R 1 , R 2 , R 3 , and R 4 , stand for optionally substituted ethyl, preferably unsubstitut-ed ethyl.
  • a further preferred embodiment (27) concretizing embodiment (25) or (26) relates to said meth-od, wherein the one or more tetraalkylammonium cation R 1 R 2 R 3 R 4 N + -containing compounds comprise one or more compounds selected from the group consisting of tetra (C 1 -C 6 ) alkylammonium compounds, preferably tetra (C 1 -C 5 ) alkylammonium compounds, more pref-erably tetra (C 1 -C 4 ) alkylammonium compounds, and more preferably tetra (C 2 -C 3 ) alkylammonium compounds, wherein independently from one another the alkyl substituents are optionally sub-stituted and/or optionally branched, and wherein more preferably the one or more tetraalkylammonium cation R 1 R 2 R 3 R 4 N + -containing compounds are selected from the group consisting of optionally substituted and/or optionally branched
  • a further preferred embodiment (28) concretizing any one of embodiments (25) to (27) relates to said method, wherein the one or more tetraalkylammonium cation R 1 R 2 R 3 R 4 N + -containing com-pounds are salts, preferably one or more salts selected from the group consisting of halides, preferably chloride and/or bromide, more preferably chloride, hydroxide, sulfate, nitrate, phos-phate, 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 1 R 2 R 3 R 4 N + -containing compounds are tetraalkylammonium hydroxides and/or chlorides, and even more preferably tetraalkylammoni-um hydroxides.
  • a further preferred embodiment (29) concretizing any one of embodiments (25) to (28) relates to said method, wherein a molar ratio R 1 R 2 R 3 R 4 N + : YO 2 of the one or more tetraalkylammonium cations to the one or more sources of YO 2 calculated as YO 2 in the mixture provided according to (a) is comprised in the range of from 0.001 to 10, preferably in the range of from 0.01 to 5, more preferably in the range of from 0.1 to 1, more preferably in the range of from 0.25 to 0.5, more preferably in the range of from 0.3 to 0.36, more preferably in the range of from 0.32 to 0.34.
  • a further preferred embodiment (30) concretizing any one of embodiments (25) to (29) relates to said method, wherein the tetravalent element Y is selected from the group consisting of Si, Sn, Ti, Zr, Ge, and mixtures of two or more thereof, Y preferably being Si.
  • a further preferred embodiment (31) concretizing any one of embodiments (25) to (30) relates to said method, wherein the trivalent element X is selected from the group consisting of Al, B, In, Ga, and mixtures of two or more thereof, X preferably being Al and/or B, wherein more prefera-bly X is B.
  • a further preferred embodiment (32) concretizing any one of embodiments (25) to (31) relates to said method, wherein a YO 2 : X 2 O 3 molar ratio of the one or more sources of YO 2 calculated as YO 2 to the one or more sources of X 2 O 3 calculated as X 2 O 3 in the mixture prepared in (a) is in the range of from 1 to 50, preferably in the range of from 6 to 40, more preferably in the range of from 11 to 30, more preferably in the range of from 16 to 25, more preferably in the range of from 18 to 22, more preferably in the range of from 19 to 21.
  • a further preferred embodiment (33) concretizing any one of embodiments (25) to (32) relates to said method, wherein the tetravalent element Y is Si, and the at least one source of YO 2 com-prises one or more compounds selected from the group consisting of fumed silica, silica hydro-sols, reactive amorphous solid silicas, silica gel, silicic acid, water glass, sodium metasilicate hydrate, sesquisilicate, disilicate, colloidal silica, silicic acid esters, and mixtures of two or more thereof, preferably from the group consisting of fumed silica, silica hydrosols, reactive amor-phous solid silicas, silica gel, silicic acid, colloidal silica, silicic acid esters, and mixtures of two or more thereof, more preferably from the group consisting of fumed silica, silica hydrosols, re-active amorphous solid silicas, silica gel, colloidal silica, and mixture
  • a further preferred embodiment (34) concretizing any one of embodiments (25) to (33) relates to said method, wherein the trivalent element X is B, and the at least one source of X 2 O 3 compris-es one or more compounds selected from the group consisting of free boric acid, borates, boric esters, and mixtures of two or more thereof, wherein preferably the at least one source of X 2 O 3 comprises boric acid.
  • a further preferred embodiment (35) concretizing any one of embodiments (25) to (33) relates to said method, wherein the trivalent element X is Al, and the one or more sources for X 2 O 3 com-prises one or more compounds selected from the group consisting of alumina, aluminates, alu-minum salts, and mixtures of two or more thereof, preferably from the group consisting of alumi-na, aluminum salts, and mixtures of two or more thereof, more preferably from the group con-sisting of alumina, aluminum tri (C 1 -C 5 ) alkoxide, AlO (OH) , Al (OH) 3 , aluminum halides, preferably aluminum fluoride and/or chloride and/or bromide, more preferably aluminum fluoride and/or chloride, and even more preferably aluminum chloride, aluminum sulfate, aluminum phosphate, aluminum fluorosilicate, and mixtures of two or more thereof, more preferably from the group consisting of aluminum tri (C 2 -C
  • a further preferred embodiment (36) concretizing any one of embodiments (25) to (35) relates to said method, wherein the seed crystals comprise one or more crystalline materials according to any one of embodiments (1) to (24) or (60) .
  • a further preferred embodiment (37) concretizing any one of embodiments (25) to (36) relates to said method, wherein the mixture prepared in (a) further comprises a solvent system containing one or more solvents, wherein the solvent system preferably comprises one or more solvents selected from the group consisting 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.
  • the solvent system preferably comprises one or more solvents selected from the group consisting 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
  • a further preferred embodiment (38) concretizing any one of embodiments (25) to (37) relates to said method, wherein the mixture prepared in (a) comprises water as the solvent system, wherein a H 2 O : YO 2 molar ratio of H 2 O to the one or more sources of YO 2 calculated as YO 2 in the mixture prepared in (a) is in the range of from 0.1 to 100, preferably in the range of from 1 to 50, more preferably in the range of from 5 to 30, more preferably in the range of from 10 to 22, more preferably in the range of from 13 to 19, more preferably in the range of from 15 to 17.
  • a further preferred embodiment (39) concretizing any one of embodiments (25) to (38) relates tosaid method, wherein the mixture prepared in (a) further comprises at least one source for OH - , wherein said at least one source for OH - preferably comprises a metal hydroxide, more prefer-ably a hydroxide of an alkali metal, even more preferably sodium and/or potassium hydroxide.
  • a further preferred embodiment (40) concretizing any one of embodiments (25) to (39) relates tosaid method, wherein a OH - : YO 2 molar ratio of hydroxide to the one or more sources of YO 2 calculated as YO 2 in mixture prepared in (a) is in the range of from 0.01 to 10, preferably in the range of from 0.05 to 2, more preferably in the range of from 0.1 to 0.9, more preferably in the range of from 0.3 to 0.7, more preferably in the range of from 0.4 to 0.65, more preferably in the range of from 0.45 to 0.60.
  • a further preferred embodiment (41) concretizing any one of embodiments (25) to (40) relates to said method, wherein in (b) the mixture prepared in (a) is heated to a temperature comprised in the range of from 130 to 190 °C, preferably in the range of from 140 to 180 °C, more preferably in the range of from 145 to 175 °C, more preferably in the range of from 150 to 170 °C, more preferably in the range of from 155 to 165 °C.
  • a further preferred embodiment (42) concretizing any one of embodiments (25) to (41) relates to said method, wherein the heating in (b) is conducted under autogenous pressure, preferably under solvothermal conditions, and more preferably under hydrothermal conditions.
  • a further preferred embodiment (43) concretizing any one of embodiments (25) to (42) relates to said method, wherein the heating in (b) is conducted for a period comprised in the range of from 1 to 15 d, preferably in the range of from 3 to 11 d, more preferably in the range of from 5 to 9 d, more preferably in the range of from 6 to 8 d.
  • heating in (b) comprises heating the mixture prepared in (a) at a first tempera-ture T 1 for a first duration and subsequently increasing the first temperature T 1 to a second tem-perature T 2 for a second duration, wherein T 1 ⁇ T 2 , and wherein the total duration of heating is comprised in the range of from 1 to 15 d, preferably in the range of from 3 to 11 d, more prefer-ably in the range of from 5 to 9 d, more preferably in the range of from 6 to 8 d.
  • a further preferred embodiment (45) concretizing embodiment (44) relates to said method, wherein the first temperature T 1 is in the range of from 130 to 180 °C, preferably in the range of from 140 to 170 °C, more preferably in the range of from 145 to 165 °C, more preferably in the range of from 150 to 160 °C.
  • a further preferred embodiment (46) concretizing embodiment (44) or (45) relates to said meth-od, wherein the first duration is comprised in the range of from 1 h to 8 d, preferably in the range of from 6 h to 6 d, more preferably in the range of from 12 h to 5 d, more preferably in the range of from 1 to 4 d.
  • a further preferred embodiment (47) concretizing any one of embodiments (44) to (46) relates to said method, wherein the second temperature T 2 is in the range of from 140 to 190 °C, prefera-bly in the range of from 150 to 180 °C, more preferably in the range of from 155 to 175 °C, more preferably in the range of from 160 to 170 °C.
  • a further preferred embodiment (48) concretizing any one of embodiments (44) to (47) relates to said method, wherein the second duration is comprised in the range of from 12 h to 10 d, pref-erably in the range of from 1 d to 8 d, more preferably in the range of from 2 d to 7 d, more pref-erably in the range of from 3 to 6 d.
  • a further preferred embodiment (49) concretizing any one of embodiments (25) to (48) relates to said method, wherein the crystallization in (b2) involves agitating the mixture, preferably by stir-ring.
  • a further preferred embodiment (50) concretizing any one of embodiments (25) to (49) relates to said method, wherein in (c) isolating the crystalline material obtained in (b) is performed via fil-tration or centrifugation.
  • a further preferred embodiment (51) concretizing any one of embodiments (25) to (50) relates to said method, wherein in (d) washing the crystalline material obtained in (b) or (c) is performed using a solvent system containing one or more solvents, wherein the solvent system preferably comprises one or more solvents selected from the group consisting of polar protic solvents and mixtures thereof,
  • n-butanol preferably from the group consisting of n-butanol, isopropanol, propanol, ethanol, methanol, water, and mixtures thereof,
  • the solvent system comprises water, and wherein more preferably wa-ter is used as the solvent system, preferably deionized water.
  • a further preferred embodiment (52) concretizing any one of embodiments (25) to (51) relates to said method, wherein in (e) drying the crystalline material obtained in (b) , (c) , or (d) is performed in a gas atmosphere having a temperature in the range of from 5 to 200 °C, preferably in the range of from 15 to 100 °C, more preferably in the range of from 20 to 25 °C.
  • a further preferred embodiment (51) concretizing any one of embodiments (25) to (52) relates to said method, wherein in (e) calcining the crystalline material obtained in (b) , (c) , or (d) is per-formed in a gas atmosphere having a temperature in the range of from 450 to 750 °C, preferably in the range of from 500 to 700 °C, more preferably in the range of from 575 to 625 °C, more preferably in the range of from 590 to 610 °C.
  • a further preferred embodiment (54) concretizing embodiment (52) to (53) relates to said meth-od, wherein the gas atmosphere comprises one or more of nitrogen and oxygen, wherein the gas atmosphere preferably comprises air.
  • a further preferred embodiment (55) concretizing any one of embodiments (25) to (54) relates to said method, wherein the method further comprises
  • a further preferred embodiment (56) concretizing embodiment (55) relates to said method, wherein the one or more metal cations are selected from the group consisting of one or more alkali metal cations, one or more alkaline earth metal cations, and one or more transition metal cations, including mixtures of two or more thereof, wherein preferably the one or more metal cations comprise one or more transition metal cations as non-framework elements, including mixtures of two or more thereof.
  • a further preferred embodiment (57) concretizing embodiment (55) or (56) relates to said meth-od, wherein the one or more transition metal cations are selected from the group consisting of cations of Zr, Cr, Mo, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, and mixtures of two or more thereof.
  • a further preferred embodiment (58) concretizing any one of embodiments (55) to (57) relates to said method, wherein the one or more alkali metal cations are selected from the group consist-ing of cations of Li, Na, K, Rb, Cs, and mixtures of two or more thereof, wherein preferably the one or more alkali metal cations comprise cations of Na and/or K.
  • a further preferred embodiment (59) concretizing any one of embodiments (55) to (58) relates to said method, wherein the one or more alkaline earth metal cations are selected from the group consisting of cations of Mg, Ba, Sr, and mixtures of two or more thereof, wherein preferably the one or more alkaline earth metal cations comprise cations of Mg and/or Sr.
  • a further preferred embodiment (60) concretizing any one of embodiments (25) to (59) relates to said method, wherein the method further comprises
  • An embodiment (61) of the present invention relates to a crystalline material obtainable or ob-tained according to the process of any one of embodiments (25) to (60) .
  • An embodiment (62) of the present invention relates to a use of a crystalline material according to any one of embodiments (1) to (24) or (61) as a molecular sieve, for ion-exchange, as an adsorbent, as an absorbent, as a catalyst or as a catalyst component, preferably as a catalyst or as a catalyst component, more preferably as a Lewis acid catalyst or a Lewis acid catalyst com-ponent, as a catalyst for the selective catalytic reduction (SCR) of nitrogen oxides NO x , for the oxidation of NH 3 , in particular for the oxidation of NH 3 slip in diesel systems, for the decomposi-tion of N 2 O, as an additive in fluid catalytic cracking (FCC) processes, as an isomerization cata-lyst or as an isomerization catalyst component, as an oxidation catalyst or as an oxidation cata-lyst component, as a hydrocracking catalyst, as an alkylation catalyst, as an aldol condensation catalyst or as
  • Reference Example 1 Determination of the unit cell parameters via automated electron diffrac-tion tomography (ADT)
  • a powdered sample of the zeolitic material obtained from Example 2 was dispersed in ethanol using an ultrasonic bath and sprayed onto a carbon-coated copper grid using a sonifier for transmission electron microscopy (TEM) and automated electron diffraction tomography (ADT) investigations.
  • the sonifier used is described in E. Mugnaioli et al., Ultramicroscopy, 109 (2009) 758–765.
  • TEM, EDX and ADT measurements were carried out with an FEI TECNAI F30 S-TWIN transmission electron microscope equipped with a field emission gun and working at 300 kV.
  • TEM images and nano electron diffraction (NED) patterns were taken with a CCD camera (16-bit 4,096 x 4,096 pixel GATAN ULTRASCAN4000) and acquired by Gatan Digital Micro-graph software.
  • Scanning transmission electron microscopy (STEM) images were collected by a FISCHIONE high-angular annular dark field (HAADF) detector and acquired by Emispec ES Vision software.
  • Three-dimensional electron diffraction data were collected using an automated acquisition module developed for FEI microscopes according to the procedure described in U. Kolb et al., Ultramicroscopy, 107 (2007) 507–513. For high tilt experiments, all acquisitions were performed with a FISCHIONE tomography holder.
  • a condenser aperture of 10 ⁇ m and mild illu-mination settings were used in order to produce a semi-parallel beam of 200 nm in diameter on the sample (21 e - /nm 2 s) .
  • Crystal position tracking was performed in microprobe STEM mode and NED patterns were acquired sequentially in steps of 1°.
  • Tilt series were collected within a total tilt range up to 120°, occasionally limited by overlapping of sur-rounding crystals or grid edges.
  • ADT data were collected with electron beam precession (pre-cession electron diffraction, PED) according to the procedure described in R. Vincent et al., Ul-tramicroscopy, 53 (1994) 271–282.
  • PED was used in order to improve reflection intensity inte-gration quality as described in E. Mugnaioli et al., Ultramicroscopy, 109 (2009) 758–765. PED was performed using a Digistar unit developed by NanoMEGAS SPRL. The precession angle was kept at 1.0°.
  • the eADT software package was used for three-dimensional electron diffrac-tion data processing as described in U. Kolb et al., Cryst. Res. Technol., 46 (2011) 542–554. Ab initio structure solution was performed assuming the kinematic approximation I ⁇
  • the structure was solved by direct method approach in SIR2014 with a coverage of 79%of the possible independent reflections (details listed in table 1 below) .
  • Ab initio structure solution converged to a final residual R F of 0.226.
  • the network with 66 Si and 128 O was found directly, as shown in figure 2 (left hand side) .
  • the potential of the missing O can be clearly seen and is indicated with a green circle.
  • the strongest maxima of the electron density map correspond to 19 silicon and 33 oxygen positions and two additional positions (0.79 and ) showing high Biso, which have been not taken into account.
  • the following 8 weakest maxima from 0.61 to ) were also not taken into ac-count.
  • the derived crystal structure was refined with isotropic Debye-Waller factors and stayed stable with no constraints. In order to optimize the network geometry the Si-O distances were finally constraint to
  • Table 1 Crystallographic information about ADT measurements and structure solution of COE-11 with SIR2014 and structure refinement using SHELXL.
  • the BET specific surface area was determined via nitrogen physisorption at 77 K according to the method disclosed in DIN 66131.
  • micropore volume was determined according to ISO 15901-1: 2016.
  • the Teflon beaker was filled to about 2/3 with the reaction mixture.
  • the Teflon beaker was then equipped with a Teflon lid and put in a steel autoclave as reaction vessel.
  • the reaction took place in an oven under static conditions (see table 2 below) .
  • the autoclave was transferred after a specific period of time from a first oven having temperature T1 to a second oven having temperature T2 within seconds and remained there for another specific period of time.
  • the autoclaves were taken from the oven and cooled to room temperature within about 1 hour in water having a temperature of approximately 15 °C.
  • the solid remainder in the Teflon beaker was separated and subsequently washed with de-ionized water. Then, the solid product was dried in air at room temperature overnight.
  • Calcination of the solid product was done in an oven in air under static conditions. To this effect, the oven was heated from room temperature to 600 °C with a heating ramp of 1 K/min. The final temperature was hold for 10 h.
  • Examples 2, 3, and 4 were prepared similarly with the exception that different conditions for effecting crystallization were applied (see table 2 below) .
  • a Teflon beaker having a total volume of about 45 ml, 5.00 ml of tetraethylammonium hydrox-ide (35 weight-%in water) were mixed with 2.05 ml of de-ionized water. 0.71 g NaOH pellets are added and dissolved. 7.5 g of colloidal silica (30 weight-%in water; Ludox HS-30) are add-ed under stirring. Finally, 0.25 g boric acid are added under stirring.
  • the Teflon beaker was filled to about 1/3 with the reaction mixture.
  • the Teflon beaker was then equipped with a Teflon lid and put in a steel autoclave as reaction vessel.
  • the reaction took place in an oven under static conditions (see table 2 below) .
  • the autoclave was transferred after a specific period of time from a first oven having temperature T1 to a second oven having temperature T2 within seconds and remained there for another specific period of time.
  • the autoclaves were taken from the oven and cooled to room temperature within about 1 hour in water having a temperature of approximately 15 °C.
  • the solid remainder in the Teflon beaker was separated and subsequently washed with de-ionized water. Then, the solid product was dried in air at room temperature overnight.
  • Calcination of the solid product was done in an oven in air under static conditions. To this effect, the oven was heated from room temperature to 600 °C with a heating ramp of 1 K/min. The final temperature was hold for 10 h.
  • calcination of the solid product can be done in an oven by heating from room tem-perature to 490 °C with a heating ramp of 2 K/min and then holding said temperature for 5 h.
  • a thus obtained sample was found to have a BET specific surface area of 416 m 2 /g and a mi-cropore volume of 0.18 cm 3 /g.
  • Example 5 Characterization of the products obtained in Examples 1-4
  • the crystalline products obtained according to examples 1 to 4 were respectively analyzed by automated diffraction tomography (ADT) and by powder X-ray diffraction and revealed to be a zeolite of a new framework structure type which was designated as COE-11. Zeolite beta was identified as a side-product in the product mixture.
  • the resulting zeolitic materials obtained from the examples were respectively charac-terized by x-ray diffraction spectroscopy.
  • a space group symmetry C2 was found. Said unit cell dimensions are identical to those of Beta Polymorph B, indicating a structural similarity to zeolite Beta.
  • the chemical composition for the zeolitic material of Example 2 was found as being approxi-mately [N (C 2 H 5 ) 4 ] 4 [B 4 Si 62 O 132 ] , including a chemical composition of the framework of approxi-mately [B 4 Si 62 O 132 ] , wherein the framework density comprising B was found as being 16.7
  • the chemical composition of the framework of zeolite beta pol-ymorph B is [T 64 O 128 ] , wherein the framework density comprising B is 16.2
  • Table 2 The composition of the reaction mixtures, the reaction parameters, and the analysis of the respective product of Examples 1 to 4.
  • the invention provides a new zeolitic material designated as COE-11, wherein said new material displays a new framework type structure.
  • Figure 2 illustrates the crystal structure of COE-11 drawn with the atomic potential after struc-ture solution.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Catalysts (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
PCT/CN2021/082430 2020-04-07 2021-03-23 Zeolite of a new framework structure type and production thereof Ceased WO2021203963A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP2022564485A JP2023522754A (ja) 2020-04-07 2021-03-23 新規フレームワーク構造タイプのゼオライトおよびその生成
EP21784111.3A EP4132884A4 (en) 2020-04-07 2021-03-23 ZEOLITE OF A NEW TYPE OF NETWORK STRUCTURE AND ITS PRODUCTION
KR1020227038236A KR20220164536A (ko) 2020-04-07 2021-03-23 새로운 프레임워크 구조 유형의 제올라이트 및 이의 제조
CN202180025058.XA CN115335325A (zh) 2020-04-07 2021-03-23 具有新型骨架结构类型的沸石及其生产
US17/917,331 US20230150827A1 (en) 2020-04-07 2021-03-23 Zeolite of a new framework structure type and production thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CNPCT/CN2020/083520 2020-04-07
CN2020083520 2020-04-07

Publications (1)

Publication Number Publication Date
WO2021203963A1 true WO2021203963A1 (en) 2021-10-14

Family

ID=78022935

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/082430 Ceased WO2021203963A1 (en) 2020-04-07 2021-03-23 Zeolite of a new framework structure type and production thereof

Country Status (6)

Country Link
US (1) US20230150827A1 (https=)
EP (1) EP4132884A4 (https=)
JP (1) JP2023522754A (https=)
KR (1) KR20220164536A (https=)
CN (1) CN115335325A (https=)
WO (1) WO2021203963A1 (https=)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003020641A1 (en) * 2001-08-30 2003-03-13 Chevron U.S.A. Inc. Small crystallite zeolite cha
CN106660024A (zh) * 2014-06-05 2017-05-10 巴斯夫欧洲公司 Cha型沸石材料和使用环烷基‑和四烷基铵化合物的组合制备它们的方法
CN108529641A (zh) * 2018-06-13 2018-09-14 北京航空航天大学 一种具有多级孔道的沸石分子筛及其制备方法
CN109790038A (zh) * 2016-09-27 2019-05-21 巴斯夫欧洲公司 沸石材料的高效固热合成

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4229424A (en) * 1979-04-09 1980-10-21 Mobil Oil Corporation Crystalline zeolite product constituting ZSM-5/ZSM-11 intermediates
US4788169A (en) * 1987-10-26 1988-11-29 Mobil Oil Corporation Low acidity alumina-bound zeolites containing tetrahedral boron, gallium, indium and/or thallium
JP4992214B2 (ja) * 2005-09-16 2012-08-08 東ソー株式会社 β型ゼオライトを含んでなる窒素酸化物の浄化触媒およびそれを用いた窒素酸化物の浄化方法
CN102040233B (zh) * 2009-10-16 2012-06-27 中国石油化工股份有限公司 一种含硼β沸石的合成方法
ES2899827T3 (es) * 2015-12-08 2022-03-14 Basf Se Material zeolítico que contiene estaño y que tiene una estructura de marco BEA
CN110759352A (zh) * 2019-11-15 2020-02-07 广西师范大学 一种晶种加模板剂合成Beta分子筛的方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003020641A1 (en) * 2001-08-30 2003-03-13 Chevron U.S.A. Inc. Small crystallite zeolite cha
CN106660024A (zh) * 2014-06-05 2017-05-10 巴斯夫欧洲公司 Cha型沸石材料和使用环烷基‑和四烷基铵化合物的组合制备它们的方法
CN109790038A (zh) * 2016-09-27 2019-05-21 巴斯夫欧洲公司 沸石材料的高效固热合成
CN108529641A (zh) * 2018-06-13 2018-09-14 北京航空航天大学 一种具有多级孔道的沸石分子筛及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4132884A4 *

Also Published As

Publication number Publication date
CN115335325A (zh) 2022-11-11
EP4132884A4 (en) 2024-05-01
JP2023522754A (ja) 2023-05-31
US20230150827A1 (en) 2023-05-18
EP4132884A1 (en) 2023-02-15
KR20220164536A (ko) 2022-12-13

Similar Documents

Publication Publication Date Title
JP7449948B2 (ja) ゼオライトの中の焼結抵抗性金属種
EP2753579B1 (en) Synthesis of zeolitic materials using n,n-dimethyl organotemplates
US20250170564A1 (en) Process for the production of a zeolitic material having an aei-type framework structure via solvent-free interzeolitic conversion
EP0796821A1 (en) ERS-10 Zeolite and process for its preparation
JP6702759B2 (ja) チタンを含有するａｅｉ型ゼオライト及びその製造方法
JP7109023B2 (ja) Ｒｈｏ型ゼオライト及びその製造方法
JP2021533075A (ja) 骨格型ｆｅｒを有するゼオライト材料の製造方法
CN117062777A (zh) 具有aft骨架结构的沸石材料的合成和包含该沸石材料的scr催化剂
JP2021511274A (ja) Ｃｈａ型骨格構造を有するゼオライト材料の高速バッチ式製造方法
EP3466879B1 (en) Chabazite zeolite with high hydrothermal resistance and method for producing same
US20250197230A1 (en) Process for the production of the cha-aft zeolite intergrowth coe-10 and use thereof in heterogeneous catalysis
WO2021203963A1 (en) Zeolite of a new framework structure type and production thereof
US5064629A (en) Titanium-boron-oxide, synthetic materials based thereon and method of preparing the same
EP4045461A1 (en) Isomorphous substitution of metals on synthesized zeolite framework
JP7794619B2 (ja) Ｃｈａ型ゼオライトの製造方法
KR102835708B1 (ko) Cha형 제올라이트 물질 및 이의 제조 방법
JP2023138071A (ja) プロピレン製造用ゼオライト触媒の製造方法
WO2017213022A1 (ja) 高耐水熱性チャバザイト型ゼオライトおよびその製造方法
EP3702029A1 (en) Ternary intermetallic compound catalyst supported on zeolite
JP2025022008A (ja) Ｚｓｍ－４８ファミリーに属するゼオライトおよびその製造方法
GB2637742A (en) Molecular sieve, method of synthesizing molecular sieve, and methods and uses thereof
EP0490543A2 (en) Titanium-boron-oxide, synthetic materials based thereon and method of preparing the same

Legal Events

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

Ref document number: 21784111

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2022564485

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20227038236

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2021784111

Country of ref document: EP

Effective date: 20221107

WWW Wipo information: withdrawn in national office

Ref document number: 2021784111

Country of ref document: EP