US20230093140A1 - Molecular sieve ssz-122, its synthesis and use - Google Patents
Molecular sieve ssz-122, its synthesis and use Download PDFInfo
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- US20230093140A1 US20230093140A1 US18/056,483 US202218056483A US2023093140A1 US 20230093140 A1 US20230093140 A1 US 20230093140A1 US 202218056483 A US202218056483 A US 202218056483A US 2023093140 A1 US2023093140 A1 US 2023093140A1
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 46
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000003786 synthesis reaction Methods 0.000 title description 7
- 230000015572 biosynthetic process Effects 0.000 title description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 46
- 239000000377 silicon dioxide Substances 0.000 claims description 23
- 229910052681 coesite Inorganic materials 0.000 claims description 20
- 229910052906 cristobalite Inorganic materials 0.000 claims description 20
- 229910052682 stishovite Inorganic materials 0.000 claims description 20
- 229910052905 tridymite Inorganic materials 0.000 claims description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 18
- 229910052593 corundum Inorganic materials 0.000 claims description 14
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 18
- 238000000034 method Methods 0.000 abstract description 14
- -1 1-adamantyl-3-propylimidazolium cations Chemical class 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 150000002894 organic compounds Chemical class 0.000 abstract description 6
- 239000010457 zeolite Substances 0.000 description 30
- 229910021536 Zeolite Inorganic materials 0.000 description 22
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- 239000011541 reaction mixture Substances 0.000 description 13
- 239000013078 crystal Substances 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 150000001342 alkaline earth metals Chemical class 0.000 description 9
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- 238000000634 powder X-ray diffraction Methods 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 239000003513 alkali Substances 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 6
- 239000000499 gel Substances 0.000 description 6
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 6
- 239000012265 solid product Substances 0.000 description 6
- 238000007669 thermal treatment Methods 0.000 description 6
- GNVDZTZVJKZHBV-UHFFFAOYSA-M 1-(1-adamantyl)-3-propylimidazol-3-ium hydroxide Chemical compound CCCN1C=[N+](C2(CC(C3)C4)CC4CC3C2)C=C1.[OH-] GNVDZTZVJKZHBV-UHFFFAOYSA-M 0.000 description 5
- 239000004809 Teflon Substances 0.000 description 5
- 229920006362 Teflon® Polymers 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000001354 calcination Methods 0.000 description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001144 powder X-ray diffraction data Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical group O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000012084 conversion product Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 229910001649 dickite Inorganic materials 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Images
Classifications
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
-
- 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
-
- 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
- C01B39/026—After-treatment
-
- 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
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Definitions
- This disclosure relates to a novel synthetic crystalline molecular sieve of BOG framework type, designated SSZ-122, its synthesis, and its use in organic compound conversion and sorption processes.
- Molecular sieves are a commercially important class of materials that have distinct crystal structures with defined pore structures that are shown by distinct X-ray diffraction (XRD) patterns and have specific chemical compositions.
- the crystal structure defines cavities and pores that are characteristic of the specific type of molecular sieve.
- Molecular sieves are classified by the Structure Commission of the International Zeolite Association according to the rules of the IUPAC Commission on Zeolite Nomenclature. According to this classification, framework-type zeolites and other crystalline microporous molecular sieves, for which a unique structure has been established, are assigned a three-letter code and are described, for example, in the “ Atlas of Zeolite Framework Types ” by Ch. Baerlocher, L. B. McCusker and D. H. Olson (Elsevier, Sixth Revised Edition, 2007).
- Natural mineral boggsite is a molecular sieve material having a unique three-dimensional channel system of 10- and 12-rings.
- the framework structure of boggsite has been assigned the three-letter code BOG by the Structure Commission of the International Zeolite Association.
- an aluminosilicate molecular sieve of BOG framework type designated SSZ-122, has now been synthesized using 1-adamantyl propylimidazolium cations as a structure directing agent.
- an aluminosilicate molecular sieve of BOG framework type wherein the aluminosilicate molecular sieve has a molar ratio of SiO 2 /Al 2 O 3 of at least 10.
- an aluminosilicate molecular sieve of BOG framework type and, in its as-synthesized form, comprising 1-adamantyl-3-propylimidazolium cations in its pores.
- a method of synthesizing an aluminosilicate molecular sieve of BOG framework type comprising (1) preparing a reaction mixture comprising: (a) a FAU framework type zeolite; (b) a source of an alkali or alkaline earth metal (M); (c) a structure directing agent comprising 1-adamantyl-3-propylimidazolium cations (Q); (d) a source of hydroxide ions; and (e) water; and (2) subjecting the reaction mixture to crystallization conditions sufficient to form crystals of the aluminosilicate molecular sieve.
- a reaction mixture comprising: (a) a FAU framework type zeolite; (b) a source of an alkali or alkaline earth metal (M); (c) a structure directing agent comprising 1-adamantyl-3-propylimidazolium cations (Q); (d) a source of hydroxide ions; and (e) water; and (2) subject
- a process of converting a feedstock comprising an organic compound to a conversion product which comprises contacting the feedstock at organic compound conversion conditions with a catalyst comprising an aluminosilicate molecular sieve of BOG framework type, wherein the aluminosilicate molecular sieve has a molar ratio of SiO 2 /Al 2 O 3 of at least 10.
- FIG. 1 is a Scanning Electron Micrograph (SEM) image of the as-synthesized SSZ-122 of Example 1.
- FIG. 2 compares the powder X-ray diffraction (XRD) patterns of as-synthesized SSZ-122 of Example 1 (bottom pattern) and calcined SSZ-122 of Example 6 (top pattern).
- XRD powder X-ray diffraction
- zeolite refers herein to a molecular sieve having a framework constructed of TO4 tetrahedra and the T-atoms are silicon and aluminum atoms.
- frame type has the meaning described in the “ Atlas of Zeolite Framework Types ” by Ch. Baerlocher, L. B. McCusker and D. H. Olson (Elsevier, Sixth Revised Edition, 2007).
- as-synthesized refers to a molecular sieve in its form after crystallization, prior to removal of the structure directing agent.
- anhydrous refers to a molecular sieve substantially devoid of both physically adsorbed and chemically adsorbed water.
- SiO 2 /Al 2 O 3 molar ratio may be abbreviated as “SAR”.
- Molecular sieve SSZ-122 can be synthesized by: (1) preparing a reaction mixture comprising (a) a FAU framework type zeolite; (b) a source of an alkali or alkaline earth metal (M); (c) a structure directing agent comprising 1-adamantyl-3-propylimidazolium cations (Q); (d) a source of hydroxide ions; and (e) water; and (2) subjecting the reaction mixture to crystallization conditions sufficient to form crystals of the aluminosilicate molecular sieve.
- a reaction mixture comprising (a) a FAU framework type zeolite; (b) a source of an alkali or alkaline earth metal (M); (c) a structure directing agent comprising 1-adamantyl-3-propylimidazolium cations (Q); (d) a source of hydroxide ions; and (e) water; and (2) subjecting the reaction mixture to crystallization conditions sufficient to form crystals
- the reaction mixture can have a composition, in terms of molar ratios, within the ranges set forth in Table 1:
- the FAU framework type zeolite can be ammonium-form zeolites or hydrogen-form zeolites (e.g., NH 4 -form zeolite Y, H-form zeolite Y).
- Examples of the FAU framework type zeolite include zeolite Y (e.g., CBV712, CBV720, CBV760, CBV780, HSZ-HUA385, and HSZ-HUA390).
- the FAU framework type zeolite is zeolite Y.
- Zeolite Y can have an SiO 2 /Al 2 O 3 molar ratio of about 12 to about 500.
- the FAU framework type zeolite can comprise two or more zeolites. Typically, the two or more zeolites are zeolites Y having different silica-to-alumina molar ratios.
- the FAU framework type zeolite can also be the only silicon and aluminum source to form SSZ-122.
- the alkali or alkaline earth metal (M) is typically introduced into the reaction mixture in conjunction with the source of hydroxide ions.
- examples of such metals include sodium and/or potassium, and also lithium, rubidium, cesium, magnesium, and calcium.
- the phrase “alkali or alkaline earth metal” does not mean the alkali metals and alkaline earth metals are used in the alternative, but instead that one or more alkali metals can be used alone or in combination with one or more alkaline earth metals and that one or more alkaline earth metals can be used alone or in combination with one or more alkali metals.
- the structure directing agent used in preparing SSZ-122 comprises 1-adamantyl-3-propylimidazolium cations (Q), represented by the following structure (1):
- Suitable sources of Q are the hydroxides, chlorides, bromides, and/or other salts of the quaternary ammonium compound.
- the reaction mixture may contain seeds of a crystalline material, such as SSZ-122 from a previous synthesis, desirably in an amount of from 0.01 to 10,000 ppm (e.g., 100 to 5000 ppm) by weight of the reaction mixture. Seeding can be advantageous to improve selectivity for SSZ-122 and/or to shorten the crystallization process.
- a crystalline material such as SSZ-122 from a previous synthesis
- reaction mixture components can be supplied by more than one source. Also, two or more reaction components can be provided by one source.
- the reaction mixture can be prepared either batchwise or continuously.
- Crystallization of the molecular sieve from the above reaction mixture can be carried out under either static, tumbled or stirred conditions in a suitable reactor vessel, such as polypropylene jars or Teflon-lined or stainless-steel autoclaves, at a temperature of from 120° C. to 200° C. (e.g., 140° C. to 180° C.) for a time sufficient for crystallization to occur at the temperature used (e.g., from 1 day to 21 days, or from 3 days to 16 days). Crystallization is usually conducted in an autoclave so that the reaction mixture is subject to autogenous pressure.
- a suitable reactor vessel such as polypropylene jars or Teflon-lined or stainless-steel autoclaves
- the solid product is separated from the reaction mixture by standard separation techniques such as filtration or centrifugation.
- the recovered crystals are water-washed and then dried, for several seconds to a few minutes (e.g., from 5 seconds to 10 minutes for flash drying) or several hours (e.g., from 4 to 24 hours for oven drying at 75° C. to 150° C.), to obtain as-synthesized SSZ-122 crystals having at least a portion of the organic cation within its pores.
- the drying step can be performed at atmospheric pressure or under vacuum.
- the as-synthesized molecular sieve may be subjected to thermal treatment, ozone treatment, or other treatment to remove part or all of the structure directing agent used in its synthesis. Removal of the structure directing agent may be carried out by thermal treatment (i.e., calcination) in which the as-synthesized molecular sieve is heated in air or inert gas at a temperature sufficient to remove part or all of the structure directing agent. While sub-atmospheric pressure may be used for the thermal treatment, atmospheric pressure is desired for reasons of convenience.
- the thermal treatment may be performed at a temperature at least 370° C. for at least a minute and generally not longer than 20 hours (e.g., from 1 to 12 hours).
- the thermal treatment can be performed at a temperature of up to 925° C. For example, the thermal treatment may be conducted at a temperature of 400° C. to 600° C. in air for approximately 1 to 8 hours.
- Any extra-framework metal cations in the molecular sieve can be replaced in accordance with techniques well known in the art (e.g., by ion exchange) with hydrogen, ammonium, or any desired metal cation.
- molecular sieve SSZ-122 can have a chemical composition, in terms of molar ratios, within the ranges set forth in Table 2:
- molecular sieve SSZ-122 can have a chemical composition comprising the following molar relationship:
- n is at least 10 (e.g., 10 to 100, 10 to 60, 20 to 100, or 20 to 60).
- the framework structure of SSZ-122 can be free or substantially free of T-atoms (tetrahedral atoms) other than silicon and aluminum.
- the term “substantially free of” means that the molecular sieve contains less than 0.1% or 0.01% of the named framework impurity.
- Powder XRD patterns representative of BOG framework type molecular sieves can be referenced in the “Collection of Simulated XRD Powder Patterns for Zeolites” by M. M. J. Treacy and J. B. Higgins (Elsevier, Fifth Revised Edition, 2007).
- the powder XRD patterns presented herein were collected by standard techniques. Minor variations in the diffraction pattern can result from variations in the mole ratios of the framework species of the particular sample due to changes in lattice constants. In addition, sufficiently small crystals will affect the shape and intensity of peaks, leading to significant peak broadening. Minor variations in the diffraction pattern can also result from variations in the organic compound used in the preparation. Calcination can also cause minor shifts in the XRD pattern. Notwithstanding these minor perturbations, the basic crystal lattice structure remains unchanged.
- Molecular sieve SSZ-122 (where part or all of the structure directing agent is removed) may be used as a sorbent or as a catalyst to catalyze a wide variety of organic compound conversion processes including many of present commercial/industrial importance.
- Examples of organic conversion processes which may be catalyzed by SSZ-122 may include cracking, hydrocracking, disproportionation, alkylation, oligomerization, and isomerization.
- SSZ-122 with another material resistant to the temperatures and other conditions employed in organic conversion processes.
- materials include active and inactive materials and synthetic or naturally occurring zeolites as well as inorganic materials such as clays, silica and/or metal oxides such as alumina.
- the latter may be either naturally occurring, or in the form of gelatinous precipitates or gels, including mixtures of silica and metal oxides.
- Use of a material in conjunction with SSZ-122 i.e., combined therewith or present during synthesis of the new material which is active, tends to change the conversion and/or selectivity of the catalyst in certain organic conversion processes.
- Inactive materials suitably serve as diluents to control the amount of conversion in a given process so that products can be obtained in an economic and orderly manner without employing other means for controlling the rate of reaction.
- These materials may be incorporated into naturally occurring clays (e.g., bentonite and kaolin) to improve the crush strength of the catalyst under commercial operating conditions.
- These materials i.e., clays, oxides, etc.
- These clay and/or oxide binders have been employed normally only for the purpose of improving the crush strength of the catalyst.
- Naturally occurring clays which can be composited with SSZ-122 include the montmorillonite and kaolin family, which families include the sub-bentonites, and the kaolins commonly known as Dixie, McNamee, Georgia and Florida clays or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite, or anauxite. Such clays can be used in the raw state as originally mined or initially subjected to calcination, acid treatment or chemical modification. Binders useful for compositing with SSZ-122 also include inorganic oxides, such as silica, zirconia, titania, magnesia, beryllia, alumina, and mixtures thereof.
- SSZ-122 can be composited with a porous matrix material such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia silica-alumina-magnesia and silica-magnesia-zirconia.
- a porous matrix material such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia silica-alumina-magnesia and silica-magnesia-zirconia.
- the relative proportions of SSZ-122 and inorganic oxide matrix may vary widely, with the SSZ-122 content ranging from 1 to 90 wt. % (e.g., 2 to 80 wt. %) of the composite.
- the resulting product was analyzed by SEM and powder XRD.
- a SEM image is shown in FIG. 1 and indicates a uniform field of crystals.
- the powder XRD pattern of the as-synthesized material is shown in FIG. 2 and is consistent with the material having the BOG framework type structure.
- the product had a SiO 2 /Al 2 O 3 molar ratio of 24.2, as determined by Inductively Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES) elemental analysis.
- ICP-AES Inductively Coupled Plasma-Atomic Emission Spectroscopy
- the resulting product was identified by SEM and powder XRD as a pure aluminosilicate molecular sieve having the BOG framework type structure.
- the product had a SiO 2 /Al 2 O 3 molar ratio of 25.5, as determined by ICP-AES elemental analysis.
- the resulting product was identified by powder XRD and SEM as a pure aluminosilicate molecular sieve having the BOG framework type structure.
- the product has a SAR of 48.8, as determined by ICP-AES elemental analysis.
- the resulting product was identified by powder XRD and SEM as a pure aluminosilicate molecular sieve having the BOG framework type structure.
- the product had a SiO 2 /Al 2 O 3 molar ratio of 24.7, as determined by ICP-AES elemental analysis.
- the resulting product was identified by powder XRD and SEM as a pure aluminosilicate molecular sieve having the BOG framework type structure.
- the product had a SiO 2 /Al 2 O 3 molar ratio of 12.7, as determined by ICP-AES elemental analysis.
- the as-synthesized molecular sieve product from Example 1 was calcined inside a muffle furnace under a flow of air heated to 540° C. at a rate of 1° C./minute and held at 540° C. for 5 hours, cooled and then analyzed by powder XRD.
- the powder XRD of the calcined material is shown in FIG. 2 and indicates that the material remains stable after calcination to remove the structure directing agent.
- the calcined material from Example 5 was treated with 10 mL (per g of molecular sieve) of a 1 N ammonium nitrate solution at 95° C. for 2 hours. The solution was cooled, decanted off and the same process repeated. After drying, the ammonium form product was subjected to a micropore volume analysis using N 2 as adsorbate and via the BET method. The molecular sieve exhibited a micropore volume of 0.21 cm 3 /g.
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Abstract
An aluminosilicate molecular sieve material of BOG framework type, designated SSZ-122, is provided. SSZ-122 can be synthesized using 1-adamantyl-3-propylimidazolium cations as a structure directing agent. SSZ-122 may be used in organic compound conversion and/or sorptive processes.
Description
- The present application is a Continuation of U.S. patent application Ser. No. 17/324,206, filed May 19, 2021, which claims priority to U.S. Provisional Application No. 63/054,330, filed Jul. 21, 2020, the complete disclosures of which are incorporated herein by reference in their entireties.
- This disclosure relates to a novel synthetic crystalline molecular sieve of BOG framework type, designated SSZ-122, its synthesis, and its use in organic compound conversion and sorption processes.
- Molecular sieves are a commercially important class of materials that have distinct crystal structures with defined pore structures that are shown by distinct X-ray diffraction (XRD) patterns and have specific chemical compositions. The crystal structure defines cavities and pores that are characteristic of the specific type of molecular sieve.
- Molecular sieves are classified by the Structure Commission of the International Zeolite Association according to the rules of the IUPAC Commission on Zeolite Nomenclature. According to this classification, framework-type zeolites and other crystalline microporous molecular sieves, for which a unique structure has been established, are assigned a three-letter code and are described, for example, in the “Atlas of Zeolite Framework Types” by Ch. Baerlocher, L. B. McCusker and D. H. Olson (Elsevier, Sixth Revised Edition, 2007).
- Natural mineral boggsite is a molecular sieve material having a unique three-dimensional channel system of 10- and 12-rings. The framework structure of boggsite has been assigned the three-letter code BOG by the Structure Commission of the International Zeolite Association.
- According to the present disclosure, an aluminosilicate molecular sieve of BOG framework type, designated SSZ-122, has now been synthesized using 1-adamantyl propylimidazolium cations as a structure directing agent.
- In a first aspect, there is provided an aluminosilicate molecular sieve of BOG framework type, wherein the aluminosilicate molecular sieve has a molar ratio of SiO2/Al2O3 of at least 10.
- In a second aspect, there is provided an aluminosilicate molecular sieve of BOG framework type and, in its as-synthesized form, comprising 1-adamantyl-3-propylimidazolium cations in its pores.
- In a third aspect, there is provided a method of synthesizing an aluminosilicate molecular sieve of BOG framework type, the method comprising (1) preparing a reaction mixture comprising: (a) a FAU framework type zeolite; (b) a source of an alkali or alkaline earth metal (M); (c) a structure directing agent comprising 1-adamantyl-3-propylimidazolium cations (Q); (d) a source of hydroxide ions; and (e) water; and (2) subjecting the reaction mixture to crystallization conditions sufficient to form crystals of the aluminosilicate molecular sieve.
- In a fourth aspect, there is provided a process of converting a feedstock comprising an organic compound to a conversion product which comprises contacting the feedstock at organic compound conversion conditions with a catalyst comprising an aluminosilicate molecular sieve of BOG framework type, wherein the aluminosilicate molecular sieve has a molar ratio of SiO2/Al2O3 of at least 10.
-
FIG. 1 is a Scanning Electron Micrograph (SEM) image of the as-synthesized SSZ-122 of Example 1. -
FIG. 2 compares the powder X-ray diffraction (XRD) patterns of as-synthesized SSZ-122 of Example 1 (bottom pattern) and calcined SSZ-122 of Example 6 (top pattern). - The term “zeolite” refers herein to a molecular sieve having a framework constructed of TO4 tetrahedra and the T-atoms are silicon and aluminum atoms.
- The term “framework type” has the meaning described in the “Atlas of Zeolite Framework Types” by Ch. Baerlocher, L. B. McCusker and D. H. Olson (Elsevier, Sixth Revised Edition, 2007).
- The term “as-synthesized” refers to a molecular sieve in its form after crystallization, prior to removal of the structure directing agent.
- The term “anhydrous” refers to a molecular sieve substantially devoid of both physically adsorbed and chemically adsorbed water.
- The term “SiO2/Al2O3 molar ratio” may be abbreviated as “SAR”.
- Synthesis of the Molecular Sieve
- Molecular sieve SSZ-122 can be synthesized by: (1) preparing a reaction mixture comprising (a) a FAU framework type zeolite; (b) a source of an alkali or alkaline earth metal (M); (c) a structure directing agent comprising 1-adamantyl-3-propylimidazolium cations (Q); (d) a source of hydroxide ions; and (e) water; and (2) subjecting the reaction mixture to crystallization conditions sufficient to form crystals of the aluminosilicate molecular sieve.
- The reaction mixture can have a composition, in terms of molar ratios, within the ranges set forth in Table 1:
-
TABLE 1 Reactants Broadest Typical SiO2/Al2O3 ≥10 20 to 60 M/SiO2 0.05 to 0.50 0.10 to 0.40 Q/SiO2 0.01 to 0.30 0.05 to 0.20 OH/SiO2 0.20 to 0.60 0.30 to 0.50 H2O/ SiO 215 to 60 20 to 40
wherein M is an alkali or alkaline earth metal and Q comprises 1-adamantyl-3-propylimidazolium cations. - The FAU framework type zeolite can be ammonium-form zeolites or hydrogen-form zeolites (e.g., NH4-form zeolite Y, H-form zeolite Y). Examples of the FAU framework type zeolite include zeolite Y (e.g., CBV712, CBV720, CBV760, CBV780, HSZ-HUA385, and HSZ-HUA390). Preferably, the FAU framework type zeolite is zeolite Y. Zeolite Y can have an SiO2/Al2O3 molar ratio of about 12 to about 500. The FAU framework type zeolite can comprise two or more zeolites. Typically, the two or more zeolites are zeolites Y having different silica-to-alumina molar ratios. The FAU framework type zeolite can also be the only silicon and aluminum source to form SSZ-122.
- The alkali or alkaline earth metal (M) is typically introduced into the reaction mixture in conjunction with the source of hydroxide ions. Examples of such metals include sodium and/or potassium, and also lithium, rubidium, cesium, magnesium, and calcium. As used herein, the phrase “alkali or alkaline earth metal” does not mean the alkali metals and alkaline earth metals are used in the alternative, but instead that one or more alkali metals can be used alone or in combination with one or more alkaline earth metals and that one or more alkaline earth metals can be used alone or in combination with one or more alkali metals.
- The structure directing agent used in preparing SSZ-122 comprises 1-adamantyl-3-propylimidazolium cations (Q), represented by the following structure (1):
- Suitable sources of Q are the hydroxides, chlorides, bromides, and/or other salts of the quaternary ammonium compound.
- The reaction mixture may contain seeds of a crystalline material, such as SSZ-122 from a previous synthesis, desirably in an amount of from 0.01 to 10,000 ppm (e.g., 100 to 5000 ppm) by weight of the reaction mixture. Seeding can be advantageous to improve selectivity for SSZ-122 and/or to shorten the crystallization process.
- It is noted that the reaction mixture components can be supplied by more than one source. Also, two or more reaction components can be provided by one source. The reaction mixture can be prepared either batchwise or continuously.
- Crystallization and Post-Synthesis Treatment
- Crystallization of the molecular sieve from the above reaction mixture can be carried out under either static, tumbled or stirred conditions in a suitable reactor vessel, such as polypropylene jars or Teflon-lined or stainless-steel autoclaves, at a temperature of from 120° C. to 200° C. (e.g., 140° C. to 180° C.) for a time sufficient for crystallization to occur at the temperature used (e.g., from 1 day to 21 days, or from 3 days to 16 days). Crystallization is usually conducted in an autoclave so that the reaction mixture is subject to autogenous pressure.
- Once the desired molecular sieve crystals have formed, the solid product is separated from the reaction mixture by standard separation techniques such as filtration or centrifugation. The recovered crystals are water-washed and then dried, for several seconds to a few minutes (e.g., from 5 seconds to 10 minutes for flash drying) or several hours (e.g., from 4 to 24 hours for oven drying at 75° C. to 150° C.), to obtain as-synthesized SSZ-122 crystals having at least a portion of the organic cation within its pores. The drying step can be performed at atmospheric pressure or under vacuum.
- The as-synthesized molecular sieve may be subjected to thermal treatment, ozone treatment, or other treatment to remove part or all of the structure directing agent used in its synthesis. Removal of the structure directing agent may be carried out by thermal treatment (i.e., calcination) in which the as-synthesized molecular sieve is heated in air or inert gas at a temperature sufficient to remove part or all of the structure directing agent. While sub-atmospheric pressure may be used for the thermal treatment, atmospheric pressure is desired for reasons of convenience. The thermal treatment may be performed at a temperature at least 370° C. for at least a minute and generally not longer than 20 hours (e.g., from 1 to 12 hours). The thermal treatment can be performed at a temperature of up to 925° C. For example, the thermal treatment may be conducted at a temperature of 400° C. to 600° C. in air for approximately 1 to 8 hours.
- Any extra-framework metal cations in the molecular sieve can be replaced in accordance with techniques well known in the art (e.g., by ion exchange) with hydrogen, ammonium, or any desired metal cation.
- Characterization of the Molecular Sieve
- In its as-synthesized and anhydrous form, molecular sieve SSZ-122 can have a chemical composition, in terms of molar ratios, within the ranges set forth in Table 2:
-
TABLE 2 Broadest Typical SiO2/Al2O3 ≥10 20 to 60 Q/SiO2 >0 to 0.1 >0 to 0.1 M/SiO2 >0 to 0.1 >0 to 0.1
wherein Q comprises 1-adamantyl-3-propylimidazolium cations and M is an alkali or alkaline earth metal. - In its calcined form, molecular sieve SSZ-122 can have a chemical composition comprising the following molar relationship:
-
Al2O3:(n)SiO2 - wherein n is at least 10 (e.g., 10 to 100, 10 to 60, 20 to 100, or 20 to 60).
- The framework structure of SSZ-122 can be free or substantially free of T-atoms (tetrahedral atoms) other than silicon and aluminum. As used herein, the term “substantially free of” means that the molecular sieve contains less than 0.1% or 0.01% of the named framework impurity.
- Powder XRD patterns representative of BOG framework type molecular sieves can be referenced in the “Collection of Simulated XRD Powder Patterns for Zeolites” by M. M. J. Treacy and J. B. Higgins (Elsevier, Fifth Revised Edition, 2007).
- The powder XRD patterns presented herein were collected by standard techniques. Minor variations in the diffraction pattern can result from variations in the mole ratios of the framework species of the particular sample due to changes in lattice constants. In addition, sufficiently small crystals will affect the shape and intensity of peaks, leading to significant peak broadening. Minor variations in the diffraction pattern can also result from variations in the organic compound used in the preparation. Calcination can also cause minor shifts in the XRD pattern. Notwithstanding these minor perturbations, the basic crystal lattice structure remains unchanged.
- Molecular sieve SSZ-122 (where part or all of the structure directing agent is removed) may be used as a sorbent or as a catalyst to catalyze a wide variety of organic compound conversion processes including many of present commercial/industrial importance. Examples of chemical conversion processes which are effectively catalyzed by SSZ-122, by itself or in combination with one or more other catalytically active substances including other crystalline catalysts, include those requiring a catalyst with acid activity. Examples of organic conversion processes which may be catalyzed by SSZ-122 may include cracking, hydrocracking, disproportionation, alkylation, oligomerization, and isomerization.
- As in the case of many catalysts, it may be desirable to incorporate SSZ-122 with another material resistant to the temperatures and other conditions employed in organic conversion processes. Such materials include active and inactive materials and synthetic or naturally occurring zeolites as well as inorganic materials such as clays, silica and/or metal oxides such as alumina. The latter may be either naturally occurring, or in the form of gelatinous precipitates or gels, including mixtures of silica and metal oxides. Use of a material in conjunction with SSZ-122 (i.e., combined therewith or present during synthesis of the new material) which is active, tends to change the conversion and/or selectivity of the catalyst in certain organic conversion processes. Inactive materials suitably serve as diluents to control the amount of conversion in a given process so that products can be obtained in an economic and orderly manner without employing other means for controlling the rate of reaction. These materials may be incorporated into naturally occurring clays (e.g., bentonite and kaolin) to improve the crush strength of the catalyst under commercial operating conditions. These materials (i.e., clays, oxides, etc.) function as binders for the catalyst. It is desirable to provide a catalyst having good crush strength because in commercial use it is desirable to prevent the catalyst from breaking down into powder-like materials. These clay and/or oxide binders have been employed normally only for the purpose of improving the crush strength of the catalyst.
- Naturally occurring clays which can be composited with SSZ-122 include the montmorillonite and kaolin family, which families include the sub-bentonites, and the kaolins commonly known as Dixie, McNamee, Georgia and Florida clays or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite, or anauxite. Such clays can be used in the raw state as originally mined or initially subjected to calcination, acid treatment or chemical modification. Binders useful for compositing with SSZ-122 also include inorganic oxides, such as silica, zirconia, titania, magnesia, beryllia, alumina, and mixtures thereof.
- In addition to the foregoing materials, SSZ-122 can be composited with a porous matrix material such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia silica-alumina-magnesia and silica-magnesia-zirconia.
- The relative proportions of SSZ-122 and inorganic oxide matrix may vary widely, with the SSZ-122 content ranging from 1 to 90 wt. % (e.g., 2 to 80 wt. %) of the composite.
- The following illustrative examples are intended to be non-limiting.
- 2.18 g of deionized water, 0.20 g of a 45% KOH solution, 1.55 g of a 13.62% 1-adamantyl-3-propylimidazolium hydroxide solution and 0.50 g of Zeolyst CBV720 Y-zeolite powder (SAR=30) were mixed together in a Teflon liner. The resulting gel was stirred until it became homogeneous. The liner was then capped and placed within a Parr Steel autoclave reactor. The autoclave was then put in an oven heated at 150° C. for 10 days with tumbling at 43 rpm. The solid products were recovered from the cooled reactor by centrifugation, washed with deionized water and dried at 95° C.
- The resulting product was analyzed by SEM and powder XRD. A SEM image is shown in
FIG. 1 and indicates a uniform field of crystals. The powder XRD pattern of the as-synthesized material is shown inFIG. 2 and is consistent with the material having the BOG framework type structure. - The product had a SiO2/Al2O3 molar ratio of 24.2, as determined by Inductively Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES) elemental analysis.
- 4.35 g of deionized water, 0.40 g of a 45% KOH solution, 3.01 g of a 13.62% 1-adamantyl-3-propylimidazolium hydroxide solution and 1.00 g of Zeolyst CBV720 Y-zeolite powder (SAR=30) were mixed together in a Teflon liner. The gel was stirred until it became homogeneous. The liner was then capped and placed within a Parr Steel autoclave reactor. The autoclave was then put in an oven heated at 160° C. for 14 days under static conditions. The solid products were recovered from the cooled reactor by centrifugation, washed with deionized water and dried at 95° C.
- The resulting product was identified by SEM and powder XRD as a pure aluminosilicate molecular sieve having the BOG framework type structure.
- The product had a SiO2/Al2O3 molar ratio of 25.5, as determined by ICP-AES elemental analysis.
- 1.31 g of deionized water, 0.12 g of a 50% NaOH solution, 0.93 g of a 13.62% 1-adamantyl-3-propylimidazolium hydroxide solution and 0.30 g of Zeolyst CB V760 Y-zeolite powder (SAR=60) were mixed together in a Teflon liner. The resulting gel was stirred until it became homogeneous. The liner was then capped and placed within a Parr Steel autoclave reactor. The autoclave was then put in an oven heated at 150° C. for 10 days under static conditions. The solid products were recovered from the cooled reactor by centrifugation, washed with deionized water and dried at 95° C.
- The resulting product was identified by powder XRD and SEM as a pure aluminosilicate molecular sieve having the BOG framework type structure.
- The product has a SAR of 48.8, as determined by ICP-AES elemental analysis.
- 0.50 g of deionized water, 0.12 g of a 45% KOH solution, 1.86 g of 13.62% 1-adamantyl-3-propylimidazolium hydroxide solution and 0.30 g of Zeolyst CBV720 Y-zeolite powder (SAR=30) were mixed together in a Teflon liner. The gel was stirred until it became homogeneous. The liner was then capped and placed within a Parr Steel autoclave reactor. The autoclave was then put in an oven heated at 150° C. for 16 days under static conditions. The solid products were recovered from the cooled reactor by centrifugation, washed with deionized water and dried at 95° C.
- The resulting product was identified by powder XRD and SEM as a pure aluminosilicate molecular sieve having the BOG framework type structure.
- The product had a SiO2/Al2O3 molar ratio of 24.7, as determined by ICP-AES elemental analysis.
- 0.51 g of deionized water, 0.20 g of a 45% KOH solution, 2.33 g of 13.62% 1-adamantyl-3-propylimidazolium hydroxide solution, 0.50 g of Zeolyst CBV712 Y-zeolite powder (SAR=12), and 0.08 g of as-synthesized SSZ-122 seed crystals from Example 1 were mixed together in a Teflon liner. The gel was stirred until it became homogeneous. The liner was then capped and placed within a Parr Steel autoclave reactor. The autoclave was then put in an oven heated at 150° C. for 7 days with tumbling at 43 rpm. The solid products were recovered from the cooled reactor by centrifugation, washed with deionized water and dried at 95° C.
- The resulting product was identified by powder XRD and SEM as a pure aluminosilicate molecular sieve having the BOG framework type structure.
- The product had a SiO2/Al2O3 molar ratio of 12.7, as determined by ICP-AES elemental analysis.
- The as-synthesized molecular sieve product from Example 1 was calcined inside a muffle furnace under a flow of air heated to 540° C. at a rate of 1° C./minute and held at 540° C. for 5 hours, cooled and then analyzed by powder XRD. The powder XRD of the calcined material is shown in
FIG. 2 and indicates that the material remains stable after calcination to remove the structure directing agent. - The calcined material from Example 5 was treated with 10 mL (per g of molecular sieve) of a 1 N ammonium nitrate solution at 95° C. for 2 hours. The solution was cooled, decanted off and the same process repeated. After drying, the ammonium form product was subjected to a micropore volume analysis using N2 as adsorbate and via the BET method. The molecular sieve exhibited a micropore volume of 0.21 cm3/g.
Claims (5)
1. A calcined aluminosilicate molecular sieve of BOG framework structure having a molar ratio of SiO2/Al2O3 of at least 10, wherein the molecular sieve does not comprise a structure directing agent.
2. The calcined aluminosilicate molecular sieve of claim 1 , wherein the molar ratio of SiO2/Al2O3 is in a range of from 10 to 60.
3. The calcined aluminosilicate molecular sieve of claim 1 , wherein the molar ratio of SiO2/Al2O3 is in a range of from 20 to 60.
4. The calcined aluminosilicate molecular sieve of claim 1 , further comprising an exchanged metal.
5. A catalyst composition comprising the calcined aluminosilicate molecular sieve of claim 1 .
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- 2021-05-19 KR KR1020237002933A patent/KR20230040999A/en active Search and Examination
- 2021-05-19 CN CN202180061475.XA patent/CN116133988A/en active Pending
- 2021-05-19 WO PCT/IB2021/054300 patent/WO2022018526A1/en unknown
- 2021-05-19 JP JP2023504280A patent/JP2023534714A/en active Pending
- 2021-05-19 EP EP21728303.5A patent/EP4185406A1/en active Pending
- 2021-05-19 US US17/324,206 patent/US11524900B2/en active Active
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2022
- 2022-11-17 US US18/056,483 patent/US20230093140A1/en not_active Abandoned
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1525915A (en) * | 1923-11-26 | 1925-02-10 | Burton R Charles | Heating device |
US2511178A (en) * | 1944-02-26 | 1950-06-13 | Fairchild Camera Instr Co | Magnetostrictive stress-responsive device and system embodying the same |
Non-Patent Citations (1)
Title |
---|
Translation of EP 1525915 (Year: 2004) * |
Also Published As
Publication number | Publication date |
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EP4185406A1 (en) | 2023-05-31 |
WO2022018526A1 (en) | 2022-01-27 |
US20220024775A1 (en) | 2022-01-27 |
JP2023534714A (en) | 2023-08-10 |
US11524900B2 (en) | 2022-12-13 |
CN116133988A (en) | 2023-05-16 |
KR20230040999A (en) | 2023-03-23 |
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