US20150353364A1 - Method for making molecular sieve ssz-99 - Google Patents
Method for making molecular sieve ssz-99 Download PDFInfo
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- US20150353364A1 US20150353364A1 US14/296,370 US201414296370A US2015353364A1 US 20150353364 A1 US20150353364 A1 US 20150353364A1 US 201414296370 A US201414296370 A US 201414296370A US 2015353364 A1 US2015353364 A1 US 2015353364A1
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 64
- 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 64
- 238000000034 method Methods 0.000 title claims abstract description 30
- -1 methylethyldiisopropylammonium cation Chemical class 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims description 30
- 239000011541 reaction mixture Substances 0.000 claims description 25
- 230000000737 periodic effect Effects 0.000 claims description 19
- 238000002425 crystallisation Methods 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 14
- 230000008025 crystallization Effects 0.000 claims description 13
- 238000002441 X-ray diffraction Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910001868 water Inorganic materials 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 229910052733 gallium Inorganic materials 0.000 claims description 5
- 229910052738 indium Inorganic materials 0.000 claims description 5
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 33
- 239000000377 silicon dioxide Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 15
- 229910052681 coesite Inorganic materials 0.000 description 13
- 229910052906 cristobalite Inorganic materials 0.000 description 13
- 229910052682 stishovite Inorganic materials 0.000 description 13
- 229910052905 tridymite Inorganic materials 0.000 description 13
- 238000001144 powder X-ray diffraction data Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000011148 porous material Substances 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000010457 zeolite Substances 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- PFEOZHBOMNWTJB-UHFFFAOYSA-N 3-methylpentane Chemical compound CCC(C)CC PFEOZHBOMNWTJB-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 150000001242 acetic acid derivatives Chemical class 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 150000003891 oxalate salts Chemical class 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000005216 hydrothermal crystallization Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- BCUPRSGLHYWGKH-UHFFFAOYSA-N CC[N+](C)(C(C)C)C(C)C Chemical compound CC[N+](C)(C(C)C)C(C)C BCUPRSGLHYWGKH-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 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
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229940077464 ammonium ion Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- YPVLAZPJUJVKNQ-UHFFFAOYSA-M ethyl-methyl-di(propan-2-yl)azanium hydroxide Chemical compound [OH-].C[N+](C(C)C)(C(C)C)CC YPVLAZPJUJVKNQ-UHFFFAOYSA-M 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000017 hydrogel Substances 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
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 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
- 229910052742 iron Inorganic materials 0.000 description 1
- 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 1
- 238000002386 leaching Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052605 nesosilicate Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000000243 solution 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
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- GXMNGLIMQIPFEB-UHFFFAOYSA-N tetraethoxygermane Chemical compound CCO[Ge](OCC)(OCC)OCC GXMNGLIMQIPFEB-UHFFFAOYSA-N 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
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
- C01B39/46—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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/305—Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
- B01J20/3057—Use of a templating or imprinting material ; filling pores of a substrate or matrix followed by the removal of the substrate or matrix
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B01J35/02—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/038—Precipitation; Co-precipitation to form slurries or suspensions, e.g. a washcoat
-
- 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
Definitions
- This disclosure relates a new molecular sieve designated SSZ-99, a method for preparing SSZ-99 using a methylethyldiisopropylammonium cation as a structure directing agent, and uses for SSZ-99.
- molecular sieve materials both natural and synthetic, have been demonstrated in the past to be useful as adsorbents and to have catalytic properties for various types of hydrocarbon conversion reactions.
- Certain molecular sieves such as zeolites, aluminophosphates, and mesoporous materials, are ordered, porous crystalline materials having a definite crystalline structure as determined by X-ray diffraction (XRD).
- XRD X-ray diffraction
- Within the crystalline molecular sieve material there are a large number of cavities which may be interconnected by a number of channels or pores. These cavities and pores are uniform in size within a specific molecular sieve material. Because the dimensions of these pores are such as to accept for adsorption molecules of certain dimensions while rejecting those of larger dimensions, these materials have come to be known as “molecular sieves” and are utilized in a variety of industrial processes.
- New molecular sieves can contain novel internal pore architectures, providing enhanced selectivities in these processes.
- molecular sieve SSZ-99 molecular sieve SSZ-99
- SSZ-99 molecular sieve SSZ-99
- a molecular sieve having a mole ratio of from 5 to 50 of (1) at least one oxide of at least one tetravalent element to (2) one or more oxides selected from the group consisting of oxides of trivalent elements, pentavalent elements, and mixtures thereof, and having, in its as-synthesized form, the X-ray diffraction lines of Table 5.
- a method of preparing a crystalline molecular sieve by contacting under crystallization conditions (1) at least one source of at least one oxide of a tetravalent element; (2) one or more sources of one or more oxides selected from the group consisting of oxides of trivalent elements, pentavalent elements, and mixtures thereof; (3) at least one source of an element selected from Groups 1 and 2 of the Periodic Table; (4) hydroxide ions; and (5) a methylethyldiisopropylammonium cation.
- the present disclosure also provides SSZ-99 having a composition, as-synthesized and in the anhydrous state, in terms of mole ratios, as follows:
- T is selected from the group consisting of tetravalent elements from Groups 4-14 of the Periodic Table, and mixtures thereof;
- X is selected from the group consisting of trivalent and pentavalent elements from Groups 3-13 of the Periodic Table, and mixtures thereof;
- Q is a methylethyldiisopropylammonium cation;
- M is selected from the group consisting of elements from Groups 1 and 2 of the Periodic Table.
- FIG. 1 is a powder XRD pattern of the as-synthesized molecular sieve prepared in Example 1.
- FIG. 2 is a powder XRD pattern of the calcined molecular sieve prepared in Example 2.
- molecular sieve includes (a) intermediate and (b) final or target molecular sieves and molecular sieves produced by (1) direct synthesis or (2) post-crystallization treatment (secondary synthesis).
- Secondary synthesis techniques allow for the synthesis of a target material from an intermediate material by heteroatom lattice substitution or other techniques.
- an aluminosilicate can be synthesized from an intermediate borosilicate by post-crystallization heteroatom lattice substitution of the boron for aluminum.
- Such techniques are known, for example as described in U.S. Pat. No. 6,790,433.
- a methylethyldiisopropylammonium cation is used as a structure directing agent (“SDA”), also known as a crystallization template.
- SDA structure directing agent
- the SDA useful for making SSZ-99 is represented by the following structure (1):
- the SDA cation is associated with anions which can be any anion that is not detrimental to the formation of the molecular sieve.
- Representative anions include elements from Group 17 of the Periodic Table (e.g., fluoride, chloride, bromide and iodide), hydroxide, acetate, sulfate, tetrafluoroborate, carboxylate, and the like.
- SSZ-99 is prepared by: (a) preparing a reaction mixture containing (1) at least one source of an oxide of at least one tetravalent element; (2) one or more sources of one or more oxides selected from the group consisting of oxides of trivalent elements, pentavalent elements, and mixtures thereof; (3) at least one source of an element selected from Groups 1 and 2 of the Periodic Table; (4) hydroxide ions; (5) a methylethyldiisopropylammonium cation; and (6) water; and (b) subjecting the reaction mixture to crystallization conditions sufficient to form crystals of the molecular sieve.
- composition of the reaction mixture from which the molecular sieve is formed in terms of mole ratios, is identified in Table 1 below, wherein compositional variables T, X, M and Q and stoichiometric variable b are as described herein above.
- composition of the reaction mixture from which SSZ-99 is formed in terms of mole ratios, is identified in Table 2 below, wherein compositional variables M and Q are as described herein above.
- T is selected from the group consisting of tetravalent elements from Groups 4-14 of the Periodic Table.
- T is selected from the group consisting of silicon (Si), germanium (Ge), titanium (Ti), and mixtures thereof.
- T is selected from the group consisting of Si, Ge, and mixtures thereof.
- T is Si.
- Sources of elements selected for composition variable T include oxides, hydroxides, acetates, oxalates, ammonium salts and sulfates of the element(s) selected for T.
- each source(s) of the element(s) selected for compositional variable T is an oxide.
- T is Si
- sources useful for Si include fumed silica, precipitated silicates, silica hydrogel, silicic acid, colloidal silica, tetra-alkyl orthosilicates (e.g., tetraethyl orthosilicate), and silica hydroxides.
- Sources useful herein for Ge include germanium oxide and germanium ethoxide.
- X is selected from the group consisting of trivalent and pentavalent elements from Groups 3-13 of the Periodic Table.
- X is selected from the group consisting of boron (B), aluminum (Al), gallium (Ga), indium (In), iron (Fe), and mixtures thereof.
- B aluminum
- Ga gallium
- In iron
- X is selected from the group consisting of B, Al, Ga, In, and mixtures thereof.
- X is Al.
- Sources of elements selected for compositional variable X include oxides, hydroxides, acetates, oxalates, ammonium salts and sulfates of the element(s) selected for X.
- sources useful for Al include aluminates, alumina, and aluminum compounds such as AlCl 3 , Al 2 (SO 4 ) 3 , Al(OH) 3 , kaolin clays, and other zeolites.
- An example of the source of aluminum oxide is Na-Y zeolite. Boron, gallium, indium, titanium, and iron can be added in forms corresponding to their aluminum and silicon counterparts.
- the reaction mixture can be formed using at least one source of an element selected from Groups 1 and 2 of the Periodic Table (referred to herein as M).
- M an element selected from Groups 1 and 2 of the Periodic Table
- the reaction mixture is formed using a source of an element from Group 1 of the Periodic Table.
- the reaction mixture is formed using a source of sodium (Na). Any M-containing compound which is not detrimental to the crystallization process is suitable.
- Sources for such Groups 1 and 2 elements include oxides, hydroxides, nitrates, sulfates, halides, oxalates, citrates and acetates thereof.
- the molecular sieve reaction mixture 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 batch wise or continuously. Crystal size, morphology and crystallization time of the molecular sieve described herein can vary with the nature of the reaction mixture and the crystallization conditions.
- the molecular sieve is prepared by: (a) preparing a reaction mixture as described herein above; and (b) subjecting the reaction mixture to crystallization conditions sufficient to form crystals of the molecular sieve.
- the reaction mixture is maintained at an elevated temperature until the crystals of the molecular sieve are formed.
- the hydrothermal crystallization is usually conducted under pressure, and usually in an autoclave so that the reaction mixture is subject to autogenous pressure, at a temperature between 125° C. and 200° C.
- the reaction mixture can be subjected to mild stirring or agitation during the crystallization step.
- impurities such as amorphous materials, unit cells having framework topologies which do not coincide with the molecular sieve, and/or other impurities (e.g., organic hydrocarbons).
- the molecular sieve crystals can be allowed to nucleate spontaneously from the reaction mixture.
- the use of crystals of the molecular sieve as seed material can be advantageous in decreasing the time necessary for complete crystallization to occur.
- seeding can lead to an increased purity of the product obtained by promoting the nucleation and/or formation of the molecular sieve over any undesired phases.
- seed crystals are added in an amount between 1% and 10% of the weight of the source for compositional variable T used in the reaction mixture.
- the solid product is separated from the reaction mixture by standard mechanical separation techniques such as filtration.
- the crystals are water-washed and then dried to obtain the as-synthesized molecular sieve crystals.
- the drying step can be performed at atmospheric pressure or under vacuum.
- the molecular sieve can be used as-synthesized, but typically will be thermally treated (calcined).
- the term “as-synthesized” refers to the molecular sieve in its form after crystallization, prior to removal of the SDA cation.
- the SDA can be removed by thermal treatment (e.g., calcination), preferably in an oxidative atmosphere (e.g., air, gas with an oxygen partial pressure of greater than 0 kPa) at a temperature readily determinable by the skilled artisan sufficient to remove the SDA from the molecular sieve.
- an oxidative atmosphere e.g., air, gas with an oxygen partial pressure of greater than 0 kPa
- the SDA can also be removed by photolysis techniques (e.g., exposing the SDA-containing molecular sieve product to light or electromagnetic radiation that has a wavelength shorter than visible light under conditions sufficient to selectively remove the organic compound from the molecular sieve) as described in U.S. Pat. No. 6,960,327.
- photolysis techniques e.g., exposing the SDA-containing molecular sieve product to light or electromagnetic radiation that has a wavelength shorter than visible light under conditions sufficient to selectively remove the organic compound from the molecular sieve
- the molecular sieve can subsequently be calcined in steam, air or inert gas at temperatures ranging from 200° C. to 800° C. for periods of time ranging from 1 to 48 hours, or more.
- the target molecular sieve formed is an intermediate material
- the target molecular sieve can be achieved using post-synthesis techniques such as heteroatom lattice substitution techniques.
- the target molecular sieve can also be achieved by removing heteroatoms from the lattice by known techniques such as acid leaching.
- the molecular sieve made from the process disclosed herein can be formed into a wide variety of physical shapes.
- the molecular sieve can be in the form of a powder, a granule, or a molded product, such as extrudate having a particle size sufficient to pass through a 2-mesh (Tyler) screen and be retained on a 400-mesh (Tyler) screen.
- the molecular sieve can be extruded before drying or dried (or partially dried) and then extruded.
- the molecular sieve can be composited with other materials resistant to the temperatures and other conditions employed in organic conversion processes.
- matrix materials include active and inactive materials and synthetic or naturally occurring zeolites as well as inorganic materials such as clays, silica and metal oxides. Examples of such materials and the manner in which they can be used are disclosed in U.S. Pat. Nos. 4,910,006 and 5,316,753.
- compositions as-synthesized and in the anhydrous state, as described in Table 3 (in terms of mole ratios), wherein compositional variables T, X, Q and M and stoichiometric variable b are as described herein above:
- the molecular sieves made by the process disclosed herein have a composition, as-synthesized and in the anhydrous state, as described in Table 4 (in terms of mole ratios), wherein compositional variables Q and M are as described herein above:
- Molecular sieves synthesized by the process disclosed herein are characterized by their XRD pattern.
- the powder XRD pattern lines of Table 5 are representative of as-synthesized SSZ-99 made in accordance with the present disclosure.
- 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.
- 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.
- the X-ray diffraction pattern lines of Table 6 are representative of calcined SSZ-99 made in accordance with the present disclosure.
- the powder X-ray diffraction patterns presented herein were collected by standard techniques.
- the radiation was CuK ⁇ radiation.
- the peak heights and the positions, as a function of 20 where 0 is the Bragg angle, were read from the relative intensities of the peaks (adjusting for background), and d, the interplanar spacing corresponding to the recorded lines, can be calculated.
- SSZ-99 is useful as an adsorbent for gas separations.
- SSZ-99 can also be used as a catalyst for converting oxygenates (e.g., methanol) to olefins and for making small amines.
- SSZ-99 can be used to reduce oxides of nitrogen in a gas streams, such as automobile exhaust.
- SSZ-99 can also be used to as a cold start hydrocarbon trap in combustion engine pollution control systems.
- SSZ-99 is particularly useful for trapping C 3 fragments.
- the composition of the reaction mixture in terms of mole ratios, is reported in Table 7.
- the Teflon liner was then capped and sealed within a steel Parr autoclave.
- the autoclave was placed on a spit within a convection oven at 135° C.
- the autoclave was tumbled at 43 rpm for 6 days in the heated oven.
- the autoclave was then removed and allowed to cool to room temperature.
- the solids were then recovered by filtration and washed thoroughly with deionized water. The solids were allowed to dry at room temperature.
- the powder XRD pattern of the resulting product is shown in FIG. 1 .
- the resulting product was calcined inside a muffle furnace under a flow of air heated to 595° C. at a rate of 1° C/minute and held at 595° C. for 5 hours, cooled and then analyzed by powder XRD.
- the powder XRD pattern of the resulting product is shown in FIG. 2 .
- the powder XRD pattern indicates that the material remains stable after calcination to remove the organic SDA.
- Calcined SSZ-99 was subjected to a micropore volume analysis using N 2 as adsorbate and via the BET method.
- the zeolite exhibited a considerable void volume with a micropore volume of 0.17 cm 3 /g.
- SSZ-99 exhibited no uptake of n-hexane at room temperature indicating that SSZ-99 is a small pore molecular sieve (i.e., a molecular sieve having a pore size of from 3 ⁇ to less than 5.0 ⁇ ).
- the Na + form of calcined SSZ-99 was converted to the NH 4 + form of SSZ-99 by heating the material in an aqueous solution of NH 4 NO 3 (typically, 1 g of NH 4 NO 3 /1 g of SSZ-99 in 20 mL of H 2 O) at 95° C. for 2-3 hours. The mixture was then filtered and the step was repeated as many times as desired (usually 2-3 times). After filtration, the obtained NH 4 + -exchanged product was washed with deionized water and air dried. The NH 4 + form of SSZ-99 can be converted to the H + form by calcination to 540° C.
- the H + form of SSZ-99 prepared per Example 4 was pelletized at 4 kpsi, crushed and granulated to 20-40 mesh. A 0.6 g sample of the granulated material was calcined in air at 540° C. for 4 hours and cooled in a desiccator to ensure dryness. Then, 0.5 g of material was packed into a 1 ⁇ 4 inch stainless steel tube with alundum on both sides of the molecular sieve bed. A furnace (Applied Test Systems, Inc.) was used to heat the reactor tube. Nitrogen was introduced into the reactor tube at 9.4 mL/min and at atmospheric pressure. The reactor was heated to about 600° F.
- the catalyst After 15 minutes on stream (600° F.), the catalyst converted about 40% of the n-hexane feed and none of the 3-methylpentane feed, indicating that SSZ-99 is a small pore shape-selective molecular sieve.
- the term “include” and its grammatical variants are intended to be non-limiting, such that recitation of items in a list is not to the exclusion of other like items that can be substituted or added to the listed items.
- the term “comprising” means including elements or steps that are identified following that term, but any such elements or steps are not exhaustive, and an embodiment can include other elements or steps.
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Abstract
Description
- This disclosure relates a new molecular sieve designated SSZ-99, a method for preparing SSZ-99 using a methylethyldiisopropylammonium cation as a structure directing agent, and uses for SSZ-99.
- Molecular sieve materials, both natural and synthetic, have been demonstrated in the past to be useful as adsorbents and to have catalytic properties for various types of hydrocarbon conversion reactions. Certain molecular sieves, such as zeolites, aluminophosphates, and mesoporous materials, are ordered, porous crystalline materials having a definite crystalline structure as determined by X-ray diffraction (XRD). Within the crystalline molecular sieve material there are a large number of cavities which may be interconnected by a number of channels or pores. These cavities and pores are uniform in size within a specific molecular sieve material. Because the dimensions of these pores are such as to accept for adsorption molecules of certain dimensions while rejecting those of larger dimensions, these materials have come to be known as “molecular sieves” and are utilized in a variety of industrial processes.
- Although many different crystalline molecular sieves have been discovered, there is a continuing need for new molecular sieves with desirable properties for gas separation and drying, hydrocarbon conversion reactions, and other applications. New molecular sieves can contain novel internal pore architectures, providing enhanced selectivities in these processes.
- The present disclosure is directed to a new family of molecular sieves with unique properties, referred to herein as “molecular sieve SSZ-99” or simply “SSZ-99.”
- In one aspect, there is provided a molecular sieve having a mole ratio of from 5 to 50 of (1) at least one oxide of at least one tetravalent element to (2) one or more oxides selected from the group consisting of oxides of trivalent elements, pentavalent elements, and mixtures thereof, and having, in its as-synthesized form, the X-ray diffraction lines of Table 5.
- In another aspect, there is provided a method of preparing a crystalline molecular sieve by contacting under crystallization conditions (1) at least one source of at least one oxide of a tetravalent element; (2) one or more sources of one or more oxides selected from the group consisting of oxides of trivalent elements, pentavalent elements, and mixtures thereof; (3) at least one source of an element selected from Groups 1 and 2 of the Periodic Table; (4) hydroxide ions; and (5) a methylethyldiisopropylammonium cation.
- In yet another aspect, there is provided a process for preparing a crystalline molecular sieve having, in its as-synthesized form, the X-ray diffraction lines of Table 5, by: (a) preparing a reaction mixture containing: (1) at least one source of at least one oxide of a tetravalent element; (2) one or more sources of one or more oxides selected from the group consisting of oxides of trivalent elements, pentavalent elements, and mixtures thereof; (3) at least one source of an element selected from Groups 1 and 2 of the Periodic Table; (4) hydroxide ions; (5) a methylethyldiisopropylammonium cation, and (6) water; and (b) subjecting the reaction mixture to crystallization conditions sufficient to form crystals of the molecular sieve.
- The present disclosure also provides SSZ-99 having a composition, as-synthesized and in the anhydrous state, in terms of mole ratios, as follows:
-
Broad Exemplary TO2/X2Ob 5 to 50 5 to 30 Q/TO2 0.02 to 0.10 0.02 to 0.10 M/TO2 0.02 to 0.15 0.02 to 0.15
wherein (1) T is selected from the group consisting of tetravalent elements from Groups 4-14 of the Periodic Table, and mixtures thereof; (2) X is selected from the group consisting of trivalent and pentavalent elements from Groups 3-13 of the Periodic Table, and mixtures thereof; (3) stoichiometric variable b equals the valence of compositional variable X (e.g., when X is trivalent, b=3; when X is pentavalent, b=5); (4) Q is a methylethyldiisopropylammonium cation; and (5) M is selected from the group consisting of elements from Groups 1 and 2 of the Periodic Table. -
FIG. 1 is a powder XRD pattern of the as-synthesized molecular sieve prepared in Example 1. -
FIG. 2 is a powder XRD pattern of the calcined molecular sieve prepared in Example 2. - Introduction
- The term “molecular sieve” includes (a) intermediate and (b) final or target molecular sieves and molecular sieves produced by (1) direct synthesis or (2) post-crystallization treatment (secondary synthesis). Secondary synthesis techniques allow for the synthesis of a target material from an intermediate material by heteroatom lattice substitution or other techniques. For example, an aluminosilicate can be synthesized from an intermediate borosilicate by post-crystallization heteroatom lattice substitution of the boron for aluminum. Such techniques are known, for example as described in U.S. Pat. No. 6,790,433.
- As used herein, the numbering scheme for the Periodic Table Groups is as disclosed in Chem. Eng. News, 63(5), 27 (1985).
- In preparing SSZ-99, a methylethyldiisopropylammonium cation is used as a structure directing agent (“SDA”), also known as a crystallization template. The SDA useful for making SSZ-99 is represented by the following structure (1):
- The SDA cation is associated with anions which can be any anion that is not detrimental to the formation of the molecular sieve. Representative anions include elements from Group 17 of the Periodic Table (e.g., fluoride, chloride, bromide and iodide), hydroxide, acetate, sulfate, tetrafluoroborate, carboxylate, and the like.
- Reaction Mixture
- In general, SSZ-99 is prepared by: (a) preparing a reaction mixture containing (1) at least one source of an oxide of at least one tetravalent element; (2) one or more sources of one or more oxides selected from the group consisting of oxides of trivalent elements, pentavalent elements, and mixtures thereof; (3) at least one source of an element selected from Groups 1 and 2 of the Periodic Table; (4) hydroxide ions; (5) a methylethyldiisopropylammonium cation; and (6) water; and (b) subjecting the reaction mixture to crystallization conditions sufficient to form crystals of the molecular sieve.
- The composition of the reaction mixture from which the molecular sieve is formed, in terms of mole ratios, is identified in Table 1 below, wherein compositional variables T, X, M and Q and stoichiometric variable b are as described herein above.
-
TABLE 1 Components Broad Exemplary TO2/X2Ob 5 to 50 5 to 50 M/TO2 0.01 to 1.0 0.30 to 0.80 Q/TO2 0.05 to 0.50 0.10 to 0.30 OH/TO2 0.10 to 1.0 0.30 to 0.80 H2O/TO2 10 to 100 20 to 50 - In one sub-embodiment, the composition of the reaction mixture from which SSZ-99 is formed, in terms of mole ratios, is identified in Table 2 below, wherein compositional variables M and Q are as described herein above.
-
TABLE 2 Components Broad Exemplary SiO2/Al2O3 5 to 50 5 to 50 M/SiO2 0.01 to 1.0 0.30 to 0.80 Q/SiO2 0.05 to 0.50 0.10 to 0.30 OH/SiO2 0.10 to 1.0 0.30 to 0.80 H2O/SiO2 10 to 100 20 to 50 - As noted above, for each embodiment described herein, T is selected from the group consisting of tetravalent elements from Groups 4-14 of the Periodic Table. In one sub-embodiment, T is selected from the group consisting of silicon (Si), germanium (Ge), titanium (Ti), and mixtures thereof. In another sub-embodiment, T is selected from the group consisting of Si, Ge, and mixtures thereof. In one sub-embodiment, T is Si. Sources of elements selected for composition variable T include oxides, hydroxides, acetates, oxalates, ammonium salts and sulfates of the element(s) selected for T. In one sub-embodiment, each source(s) of the element(s) selected for compositional variable T is an oxide. Where T is Si, sources useful for Si include fumed silica, precipitated silicates, silica hydrogel, silicic acid, colloidal silica, tetra-alkyl orthosilicates (e.g., tetraethyl orthosilicate), and silica hydroxides. Sources useful herein for Ge include germanium oxide and germanium ethoxide.
- For each embodiment described herein, X is selected from the group consisting of trivalent and pentavalent elements from Groups 3-13 of the Periodic Table. In one sub-embodiment, X is selected from the group consisting of boron (B), aluminum (Al), gallium (Ga), indium (In), iron (Fe), and mixtures thereof. In another sub-embodiment, X is selected from the group consisting of B, Al, Ga, In, and mixtures thereof. In one sub-embodiment X is Al. Sources of elements selected for compositional variable X include oxides, hydroxides, acetates, oxalates, ammonium salts and sulfates of the element(s) selected for X. Where X is Al, sources useful for Al include aluminates, alumina, and aluminum compounds such as AlCl3, Al2(SO4)3, Al(OH)3, kaolin clays, and other zeolites. An example of the source of aluminum oxide is Na-Y zeolite. Boron, gallium, indium, titanium, and iron can be added in forms corresponding to their aluminum and silicon counterparts.
- As described herein above, for each embodiment described herein, the reaction mixture can be formed using at least one source of an element selected from Groups 1 and 2 of the Periodic Table (referred to herein as M). In one sub-embodiment, the reaction mixture is formed using a source of an element from Group 1 of the Periodic Table. In another sub-embodiment, the reaction mixture is formed using a source of sodium (Na). Any M-containing compound which is not detrimental to the crystallization process is suitable. Sources for such Groups 1 and 2 elements include oxides, hydroxides, nitrates, sulfates, halides, oxalates, citrates and acetates thereof.
- For each embodiment described herein, the molecular sieve reaction mixture 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 batch wise or continuously. Crystal size, morphology and crystallization time of the molecular sieve described herein can vary with the nature of the reaction mixture and the crystallization conditions.
- Crystallization and Post-Synthesis Treatment
- In practice, the molecular sieve is prepared by: (a) preparing a reaction mixture as described herein above; and (b) subjecting the reaction mixture to crystallization conditions sufficient to form crystals of the molecular sieve.
- The reaction mixture is maintained at an elevated temperature until the crystals of the molecular sieve are formed. The hydrothermal crystallization is usually conducted under pressure, and usually in an autoclave so that the reaction mixture is subject to autogenous pressure, at a temperature between 125° C. and 200° C.
- The reaction mixture can be subjected to mild stirring or agitation during the crystallization step. It will be understood by the skilled artisan that the molecular sieves described herein can contain impurities, such as amorphous materials, unit cells having framework topologies which do not coincide with the molecular sieve, and/or other impurities (e.g., organic hydrocarbons).
- During the hydrothermal crystallization step, the molecular sieve crystals can be allowed to nucleate spontaneously from the reaction mixture. The use of crystals of the molecular sieve as seed material can be advantageous in decreasing the time necessary for complete crystallization to occur. In addition, seeding can lead to an increased purity of the product obtained by promoting the nucleation and/or formation of the molecular sieve over any undesired phases. When used as seeds, seed crystals are added in an amount between 1% and 10% of the weight of the source for compositional variable T used in the reaction mixture.
- Once the molecular sieve crystals have formed, the solid product is separated from the reaction mixture by standard mechanical separation techniques such as filtration. The crystals are water-washed and then dried to obtain the as-synthesized molecular sieve crystals. The drying step can be performed at atmospheric pressure or under vacuum.
- The molecular sieve can be used as-synthesized, but typically will be thermally treated (calcined). The term “as-synthesized” refers to the molecular sieve in its form after crystallization, prior to removal of the SDA cation. The SDA can be removed by thermal treatment (e.g., calcination), preferably in an oxidative atmosphere (e.g., air, gas with an oxygen partial pressure of greater than 0 kPa) at a temperature readily determinable by the skilled artisan sufficient to remove the SDA from the molecular sieve. The SDA can also be removed by photolysis techniques (e.g., exposing the SDA-containing molecular sieve product to light or electromagnetic radiation that has a wavelength shorter than visible light under conditions sufficient to selectively remove the organic compound from the molecular sieve) as described in U.S. Pat. No. 6,960,327.
- The molecular sieve can subsequently be calcined in steam, air or inert gas at temperatures ranging from 200° C. to 800° C. for periods of time ranging from 1 to 48 hours, or more. Usually, it is desirable to remove the extra-framework cation (e.g., Na+) by ion exchange and replace it with hydrogen, ammonium, or any desired metal-ion.
- Where the molecular sieve formed is an intermediate material, the target molecular sieve can be achieved using post-synthesis techniques such as heteroatom lattice substitution techniques. The target molecular sieve can also be achieved by removing heteroatoms from the lattice by known techniques such as acid leaching.
- The molecular sieve made from the process disclosed herein can be formed into a wide variety of physical shapes. Generally speaking, the molecular sieve can be in the form of a powder, a granule, or a molded product, such as extrudate having a particle size sufficient to pass through a 2-mesh (Tyler) screen and be retained on a 400-mesh (Tyler) screen. In cases where the catalyst is molded, such as by extrusion with an organic binder, the molecular sieve can be extruded before drying or dried (or partially dried) and then extruded.
- The molecular sieve can be composited with other materials resistant to the temperatures and other conditions employed in organic conversion processes. Such matrix materials include active and inactive materials and synthetic or naturally occurring zeolites as well as inorganic materials such as clays, silica and metal oxides. Examples of such materials and the manner in which they can be used are disclosed in U.S. Pat. Nos. 4,910,006 and 5,316,753.
- Characterization of the Molecular Sieve
- Molecular sieves made by the process disclosed herein have a composition, as-synthesized and in the anhydrous state, as described in Table 3 (in terms of mole ratios), wherein compositional variables T, X, Q and M and stoichiometric variable b are as described herein above:
-
TABLE 3 Broad Exemplary TO2/X2Ob 5 to 50 5 to 30 Q/TO2 0.02 to 0.10 0.02 to 0.10 M/TO2 0.02 to 0.15 0.02 to 0.15 - In one sub-embodiment, the molecular sieves made by the process disclosed herein have a composition, as-synthesized and in the anhydrous state, as described in Table 4 (in terms of mole ratios), wherein compositional variables Q and M are as described herein above:
-
TABLE 4 Broad Exemplary SiO2/Al2O3 5 to 50 5 to 30 Q/SiO2 0.02 to 0.10 0.02 to 0.10 M/SiO2 0.02 to 0.15 0.02 to 0.15 - Molecular sieves synthesized by the process disclosed herein are characterized by their XRD pattern. The powder XRD pattern lines of Table 5 are representative of as-synthesized SSZ-99 made in accordance with the present disclosure. 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.
-
TABLE 5 Characteristic Peaks for As-Synthesized SSZ-99 Relative Peak 2-Theta(a) d-Spacing, nm Intensity(b) Broadening(c) P/N(d) 7.54 1.172 M B L 9.71 0.910 W VB L 12.94 0.684 W Sh H 14.97 0.591 M Sh L 15.92 0.556 S Sh H 17.78 0.499 M Sh H 18.40 0.482 W Sh L 19.86 0.447 M B L 21.26 0.418 S VB L 22.51 0.395 W B L 24.40 0.365 W Sh L 26.10 0.341 VS Sh H 27.35 0.326 W B L 28.17 0.317 W B L (a)±0.20 (b)The powder XRD patterns provided are based on a relative intensity scale in which the strongest line in the X-ray pattern is assigned a value of 100: W = weak (>0 to ≦20); M = medium (>20 to ≦40); S = strong (>40 to ≦60); VS = very strong (>60 to ≦100) (c)Peak Broadening is characterized by the Full-Width at Half Maximum (FWHM) of the XRD peak. Based on the FWHM values, the peaks are classified as: Sh = sharp (≦2* smallest FWHM); B = broad (>2*smallest FWHM to ≦5* smallest FWHM); VB = very broad (>5*smallest FWHM) (d)P/N is the peak to noise ratio which is calculated as P/N = (Peak Height − Background)/√ Peak Height. L = low (≦15); H = high (>15) - The X-ray diffraction pattern lines of Table 6 are representative of calcined SSZ-99 made in accordance with the present disclosure.
-
TABLE 6 Characteristic Peaks for Calcined SSZ-99 Relative Peak 2-Theta(a) d-Spacing, nm Intensity(b) Broadening(c) P/N(d) 7.47 1.183 M B L 9.75 0.907 W VB L 12.93 0.684 M Sh H 15.06 0.588 W Sh L 15.90 0.557 VS Sh L 17.82 0.497 M Sh H 18.39 0.482 W Sh L 19.86 0.447 M B L 21.38 0.415 S VB L 24.44 0.364 W Sh L 26.12 0.341 VS Sh H 27.17 0.328 W B L 28.22 0.316 W B L (a)±0.20 (b)The powder XRD patterns provided are based on a relative intensity scale in which the strongest line in the X-ray pattern is assigned a value of 100: W = weak (>0 to ≦20); M = medium (>20 to ≦40); S = strong (>40 to ≦60); VS = very strong (>60 to ≦100) (c)Peak Broadening is characterized by the Full-Width at Half Maximum (FWHM) of the XRD peak. Based on the FWHM values, the peaks are classified as: Sh = sharp (≦2* smallest FWHM); B = broad (>2*smallest FWHM to ≦5* smallest FWHM); VB = very broad (>5*smallest FWHM) (d)P/N is the peak to noise ratio which is calculated as P/N = (Peak Height − Background)/√ Peak Height. L = low (≦15); H = high (>15) - The powder X-ray diffraction patterns presented herein were collected by standard techniques. The radiation was CuKα radiation. The peak heights and the positions, as a function of 20 where 0 is the Bragg angle, were read from the relative intensities of the peaks (adjusting for background), and d, the interplanar spacing corresponding to the recorded lines, can be calculated.
- Processes Using SSZ-99
- SSZ-99 is useful as an adsorbent for gas separations. SSZ-99 can also be used as a catalyst for converting oxygenates (e.g., methanol) to olefins and for making small amines. SSZ-99 can be used to reduce oxides of nitrogen in a gas streams, such as automobile exhaust. SSZ-99 can also be used to as a cold start hydrocarbon trap in combustion engine pollution control systems. SSZ-99 is particularly useful for trapping C3 fragments.
- The following illustrative examples are intended to be non-limiting.
- A Teflon liner was charged with sodium silicate, 1 N NaOH, a FAU zeolite (SiO2/Al2O3 mole ratio=5) and a methylethyldiisopropylammonium hydroxide solution. The composition of the reaction mixture, in terms of mole ratios, is reported in Table 7.
-
TABLE 7 SiO2/Al2O3 30 Q/SiO2 0.15 OH/SiO2 0.8 H2O/SiO2 30 - The Teflon liner was then capped and sealed within a steel Parr autoclave. The autoclave was placed on a spit within a convection oven at 135° C. The autoclave was tumbled at 43 rpm for 6 days in the heated oven. The autoclave was then removed and allowed to cool to room temperature. The solids were then recovered by filtration and washed thoroughly with deionized water. The solids were allowed to dry at room temperature.
- The powder XRD pattern of the resulting product is shown in
FIG. 1 . - Elemental analysis indicated the product contained 30.8% Si and 7.89% Al.
- The resulting product was calcined inside a muffle furnace under a flow of air heated to 595° C. at a rate of 1° C/minute and held at 595° C. for 5 hours, cooled and then analyzed by powder XRD. The powder XRD pattern of the resulting product is shown in
FIG. 2 . The powder XRD pattern indicates that the material remains stable after calcination to remove the organic SDA. - Calcined SSZ-99 was subjected to a micropore volume analysis using N2 as adsorbate and via the BET method. The zeolite exhibited a considerable void volume with a micropore volume of 0.17 cm3/g.
- Calcined SSZ-99 exhibited no uptake of n-hexane at room temperature indicating that SSZ-99 is a small pore molecular sieve (i.e., a molecular sieve having a pore size of from 3 Å to less than 5.0 Å).
- The Na+ form of calcined SSZ-99 was converted to the NH4 + form of SSZ-99 by heating the material in an aqueous solution of NH4NO3 (typically, 1 g of NH4NO3/1 g of SSZ-99 in 20 mL of H2O) at 95° C. for 2-3 hours. The mixture was then filtered and the step was repeated as many times as desired (usually 2-3 times). After filtration, the obtained NH4 +-exchanged product was washed with deionized water and air dried. The NH4 + form of SSZ-99 can be converted to the H+ form by calcination to 540° C.
- The H+ form of SSZ-99 prepared per Example 4 was pelletized at 4 kpsi, crushed and granulated to 20-40 mesh. A 0.6 g sample of the granulated material was calcined in air at 540° C. for 4 hours and cooled in a desiccator to ensure dryness. Then, 0.5 g of material was packed into a ¼ inch stainless steel tube with alundum on both sides of the molecular sieve bed. A furnace (Applied Test Systems, Inc.) was used to heat the reactor tube. Nitrogen was introduced into the reactor tube at 9.4 mL/min and at atmospheric pressure. The reactor was heated to about 600° F. (315.6° C.), and a 50/50 feed of n-hexane and 3-methylpentane was introduced into the reactor at a rate of 8 μL/min. The feed was delivered by an ISCO pump. Direct sampling into a GC began after 15 minutes of feed introduction.
- After 15 minutes on stream (600° F.), the catalyst converted about 40% of the n-hexane feed and none of the 3-methylpentane feed, indicating that SSZ-99 is a small pore shape-selective molecular sieve.
- For the purposes of this specification and appended claims, unless otherwise indicated, all numbers expressing quantities, percentages or proportions, and other numerical values used in the specification and claims, are to be understood as being modified in all instances by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that can vary depending upon the desired properties sought to be obtained. It is noted that, as used in this specification and the appended claims, the singular forms “a,” “an,” and “the,” include plural references unless expressly and unequivocally limited to one referent. As used herein, the term “include” and its grammatical variants are intended to be non-limiting, such that recitation of items in a list is not to the exclusion of other like items that can be substituted or added to the listed items. As used herein, the term “comprising” means including elements or steps that are identified following that term, but any such elements or steps are not exhaustive, and an embodiment can include other elements or steps.
- Unless otherwise specified, the recitation of a genus of elements, materials or other components, from which an individual component or mixture of components can be selected, is intended to include all possible sub-generic combinations of the listed components and mixtures thereof.
- The patentable scope is defined by the claims, and can include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims. To an extent not inconsistent herewith, all citations referred to herein are hereby incorporated by reference.
Claims (11)
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US14/296,370 US9193600B1 (en) | 2014-06-04 | 2014-06-04 | Method for making molecular sieve SSZ-99 |
EP15710623.8A EP3151959B1 (en) | 2014-06-04 | 2015-02-19 | Method for making molecular sieve ssz-99 |
CN201580029087.8A CN106457232A (en) | 2014-06-04 | 2015-02-19 | Method for making molecular sieve SSZ-99 |
SG11201609964YA SG11201609964YA (en) | 2014-06-04 | 2015-02-19 | Method for making molecular sieve ssz-99 |
JP2016570966A JP6371417B2 (en) | 2014-06-04 | 2015-02-19 | Method for producing molecular sieve SSZ-99 |
PCT/US2015/016506 WO2015187212A1 (en) | 2014-06-04 | 2015-02-19 | Method for making molecular sieve ssz-99 |
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US9908784B2 (en) | 2016-04-14 | 2018-03-06 | Chevron U.S.A. Inc. | Synthesis of molecular sieve SSZ-99 |
KR102541358B1 (en) * | 2017-04-28 | 2023-06-08 | 셰브런 유.에스.에이.인크. | Molecular Sieve SSZ-109, Synthesis and Uses thereof |
WO2019234517A1 (en) * | 2018-06-07 | 2019-12-12 | Chevron U.S.A. Inc. | Synthesis of molecular sieve ssz-109 |
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US2692285A (en) | 1951-05-07 | 1954-10-19 | Searle & Co | Di-sec-alkyl-dialkylammonium salts and processes for preparing the same |
DD232841A1 (en) * | 1984-08-30 | 1986-02-12 | Council Of Scient U Ind Resear | METHOD FOR PRODUCING CATALYST COMPOSITE MATERIAL, CALLED ENCILIT |
US4910006A (en) | 1988-03-23 | 1990-03-20 | Chevron Research Company | Zeolite SSZ-26 |
US5316753A (en) | 1992-10-09 | 1994-05-31 | Chevron Research And Technology Company | Zeolite SSZ-35 |
US6254849B1 (en) * | 1999-07-28 | 2001-07-03 | Chevron U.S.A. Inc. | Zeolite SSZ-52 |
US6468501B1 (en) | 2000-09-14 | 2002-10-22 | Chevrontexaco Corporation | Method for heteroatom lattice substitution in large and extra-large pore borosilicate zeolites |
US6960327B2 (en) | 2003-01-30 | 2005-11-01 | The Regents Of The University Of California | Methods for removing organic compounds from nano-composite materials |
DE102004017915A1 (en) * | 2004-04-13 | 2005-11-03 | Basf Ag | Microporous framework silicate and process for its preparation |
CA2592136C (en) * | 2004-12-23 | 2013-01-15 | Chevron U.S.A. Inc. | Molecular sieve ssz-70 composition of matter and synthesis thereof |
US7157075B1 (en) * | 2005-08-30 | 2007-01-02 | Chevron U.S.A. Inc. | Process for preparing MTT zeolites using nitrogen-containing organic compounds |
US7837979B2 (en) * | 2006-11-06 | 2010-11-23 | Exxonmobil Research And Engineering Company | Synthesis of ITQ-12 |
US8025864B2 (en) * | 2006-12-07 | 2011-09-27 | Exxonmobil Research And Engineering Company | ITQ-34, new crystalline microporous material |
CA2729266C (en) * | 2008-07-28 | 2013-06-25 | Exxonmobil Chemical Patents Inc. | A novel molecular sieve composition emm-13, a method of making and a process of using the same |
US8163268B2 (en) * | 2008-09-29 | 2012-04-24 | Exxonmobil Chemical Patents Inc. | EMM-11, a novel synthetic crystalline microporous material, its preparation and use |
WO2010065319A2 (en) | 2008-11-25 | 2010-06-10 | Chevron U.S.A. Inc. | Processes using molecular sieve ssz-83 |
WO2010088243A2 (en) | 2009-01-28 | 2010-08-05 | Chevron U.S.A. Inc. | Processes using molecular sieve ssz-79 |
US7981273B2 (en) * | 2009-06-22 | 2011-07-19 | Uop Llc | Process for catalytic cracking of hydrocarbons using UZM-35 |
US7982081B2 (en) * | 2009-06-29 | 2011-07-19 | Uop Llc | Process for alkylation of aromatic hydrocarbons using UZM-35 |
US8058496B2 (en) * | 2010-03-31 | 2011-11-15 | Uop Llc | Process for xylene and ethylbenzene isomerization using UZM-35 |
RU2525417C2 (en) * | 2010-06-21 | 2014-08-10 | Юоп Ллк | Uzm-35 zeolite composition, method of production and methods of use |
EP2900372B1 (en) * | 2012-09-28 | 2018-01-10 | Pacific Industrial Development Corporation | An alumina silicate zeolite-type material for use as a catalyst in selective catalytic reduction and process of making thereof |
US8999288B1 (en) * | 2013-09-16 | 2015-04-07 | Chevron U.S.A. Inc. | Method for preparing zeolite SSZ-35 |
US9108856B2 (en) * | 2013-09-18 | 2015-08-18 | Chevron U.S.A. Inc. | Method for preparing CHA-type molecular sieves using colloidal aluminosilicate and novel structure directing agents |
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JP2017516740A (en) | 2017-06-22 |
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JP6371417B2 (en) | 2018-08-08 |
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