US20210363023A1 - Molecular sieve ssz-120, its synthesis and use - Google Patents
Molecular sieve ssz-120, its synthesis and use Download PDFInfo
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- US20210363023A1 US20210363023A1 US17/323,005 US202117323005A US2021363023A1 US 20210363023 A1 US20210363023 A1 US 20210363023A1 US 202117323005 A US202117323005 A US 202117323005A US 2021363023 A1 US2021363023 A1 US 2021363023A1
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- aluminogermanosilicate
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 55
- 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 55
- 238000003786 synthesis reaction Methods 0.000 title description 10
- 230000015572 biosynthetic process Effects 0.000 title description 8
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000013078 crystal Substances 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims abstract description 13
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 68
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 55
- 239000000377 silicon dioxide Substances 0.000 claims description 34
- 229910052681 coesite Inorganic materials 0.000 claims description 29
- 229910052906 cristobalite Inorganic materials 0.000 claims description 29
- 229910052682 stishovite Inorganic materials 0.000 claims description 29
- 229910052905 tridymite Inorganic materials 0.000 claims description 29
- 239000010457 zeolite Substances 0.000 claims description 27
- 229910021536 Zeolite Inorganic materials 0.000 claims description 21
- 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
- 238000006243 chemical reaction Methods 0.000 claims description 18
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 17
- 239000011541 reaction mixture Substances 0.000 claims description 17
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 229910052593 corundum Inorganic materials 0.000 claims description 12
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- 229910001868 water Inorganic materials 0.000 claims description 9
- -1 fluoride ions Chemical class 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000004375 physisorption Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 229910052732 germanium Inorganic materials 0.000 claims description 5
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 4
- 239000012084 conversion product Substances 0.000 claims description 2
- 150000002897 organic nitrogen compounds Chemical class 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 21
- 239000000047 product Substances 0.000 description 18
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 10
- PFEOZHBOMNWTJB-UHFFFAOYSA-N 3-methylpentane Chemical compound CCC(C)CC PFEOZHBOMNWTJB-UHFFFAOYSA-N 0.000 description 8
- 238000001354 calcination Methods 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000007669 thermal treatment Methods 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 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
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 3
- PLVSAMCJZXDVSF-UHFFFAOYSA-N CC1=N(CC2=CC3=C(C=C2)C=C(CN2=C(C)N(C)C=C2)C=C3)C=CN1C Chemical compound CC1=N(CC2=CC3=C(C=C2)C=C(CN2=C(C)N(C)C=C2)C=C3)C=CN1C PLVSAMCJZXDVSF-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000001144 powder X-ray diffraction data Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical group [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 229910052909 inorganic silicate Inorganic materials 0.000 description 2
- 238000006317 isomerization reaction Methods 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
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- JRHSGFPVPTWMND-UHFFFAOYSA-N 2,6-bis(bromomethyl)naphthalene Chemical compound C1=C(CBr)C=CC2=CC(CBr)=CC=C21 JRHSGFPVPTWMND-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 229910005833 GeO4 Inorganic materials 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
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 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
- 150000003868 ammonium compounds Chemical group 0.000 description 1
- 238000005899 aromatization reaction 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
- 238000003965 capillary gas chromatography Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000006555 catalytic reaction 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
- 230000002860 competitive effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000013480 data collection Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000003795 desorption Methods 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
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 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
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 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
- 238000000643 oven drying Methods 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(II) nitrate Inorganic materials [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 239000000376 reactant Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
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- 239000011347 resin Substances 0.000 description 1
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- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
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- 238000010561 standard procedure Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- GXMNGLIMQIPFEB-UHFFFAOYSA-N tetraethoxygermane Chemical compound CCO[Ge](OCC)(OCC)OCC GXMNGLIMQIPFEB-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 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
- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/12—Noble metals
- B01J29/126—Y-type faujasite
-
- 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
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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
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
-
- 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
- C01B39/20—Faujasite type, e.g. type X or Y
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
-
- 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
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
Definitions
- This disclosure relates to a small crystal size, high surface area aluminogermanosilicate molecular sieve designated SSZ-120, its synthesis, and its use in organic compound conversion reactions 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.
- a small crystal size, high surface area aluminogermanosilicate molecular sieve designated SSZ-120 and having a unique powder X-ray diffraction pattern, has been synthesized using 3,3′-[2,6-naphthalenebis(methylene)]bis[1,2-dimethyl-1H-imidazolium] dications as a structure directing agent.
- an aluminogermanosilicate molecular sieve having, in its calcined form, a powder X-ray diffraction pattern including the peaks in the following table:
- the calcined molecular sieve can have a total surface area (as determined by the t-plot method for nitrogen physisorption) of at least 500 m 2 /g and/or an external surface area (as determined by the t-plot method for nitrogen physisorption) of at least 100 m 2 /g.
- an aluminogermanosilicate molecular sieve having, in its as-synthesized form, a powder X-ray diffraction pattern including the peaks in the following table:
- the aluminogermanosilicate molecular sieve can have a chemical composition comprising the following molar relationship:
- a method of synthesizing an aluminogermanosilicate molecular sieve comprising (1) providing a reaction mixture comprising: (a) a FAU framework type zeolite; (b) a source of germanium; (c) a structure directing agent (Q) comprising 3,3′-[2,6-naphthalenebis(methylene)]bis[1,2-dimethyl-1H-imidazolium] dications; (d) a source of fluoride ions; and (e) water; and (2) subjecting the reaction mixture to crystallization conditions sufficient to form crystals of the aluminogermanosilicate molecular sieve.
- a reaction mixture comprising: (a) a FAU framework type zeolite; (b) a source of germanium; (c) a structure directing agent (Q) comprising 3,3′-[2,6-naphthalenebis(methylene)]bis[1,2-dimethyl-1H-imidazolium] dications;
- 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 active form of the aluminogermanosilicate molecular sieve, described herein.
- an organic nitrogen compound comprising a dication having the following structure:
- FIG. 1 shows the powder X-ray diffraction (XRD) pattern of the as-synthesized product of Example 2.
- FIGS. 2(A)-2(D) show scanning electron micrograph (SEM) images of the as-synthesized product of Example 2 at different magnifications.
- FIG. 3 shows the powder XRD pattern of the calcined product of Example 3.
- FIG. 4 is a graph illustrating the relationship between conversion or yield and temperature in the hydroconversion of n-decane over a Pd/SSZ-120 catalyst.
- frame type has the meaning described in the “ Atlas of Zeolite Framework Types ”, by Ch. Baerlocher and L. B. McCusker and D. H. Olsen (Sixth Revised Edition, Elsevier, 2007).
- zeolite refers an aluminosilicate molecular sieve having a framework constructed of alumina and silica (i.e., repeating AlO4 and SiO4 tetrahedral units).
- aluminogermanosilicate refers to a molecular sieve having a framework constructed of AlO4, GeO4 and SiO4 tetrahedral units.
- the alumingermanosilicate may contain only the named oxides, in which case, it may be described as a “pure aluminogermanosilicate” or it may contain other additional oxides as well.
- as-synthesized is employed herein to refer to a molecular sieve in its form after crystallization, prior to removal of the structure directing agent.
- anhydrous is employed herein to refer 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”.
- Aluminogermanosilicate molecular sieve SSZ-120 can be synthesized by: (1) providing a reaction mixture comprising (a) a FAU framework type zeolite; (b) a source of germanium; (c) a structure directing agent (Q) comprising 3,3′-[2,6-naphthalenebis(methylene)]bis[1,2-dimethyl-1H-imidazolium] dications; (d) a source of fluoride ions; and (e) water; and (2) subjecting the reaction mixture to crystallization conditions sufficient to form crystals of the aluminogermanosilicate molecular sieve.
- a reaction mixture comprising (a) a FAU framework type zeolite; (b) a source of germanium; (c) a structure directing agent (Q) comprising 3,3′-[2,6-naphthalenebis(methylene)]bis[1,2-dimethyl-1H-imidazolium] dications; (d
- the reaction mixture can have a composition, in terms of molar ratios, within the ranges set forth in Table 1:
- the reaction mixture can have a SiO 2 /GeO 2 molar ratio in a range of from 4 to 12 (e.g., from 6 to 10).
- 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., CBV720, CBV760, CBV780, HSZ-385HUA, and HSZ-390HUA).
- the FAU framework type zeolite is zeolite Y. More preferably, zeolite Y has a SiO 2 /Al 2 O 3 molar ratio in a range of about 30 to about 500.
- the FAU framework type zeolite can comprise two or more zeolites.
- the two or more zeolites are Y zeolites having different SiO 2 /Al 2 O 3 molar ratios.
- the FAU framework type zeolite can also be the only silica and aluminum source to form the aluminogermanosilicate molecular sieve.
- Sources of germanium include germanium oxide and germanium alkoxides (e.g., germanium ethoxide).
- Sources of fluoride ions include hydrogen fluoride, ammonium fluoride, and ammonium bifluoride.
- SSZ-120 can be synthesized using a structure directing agent (Q) comprising 3,3′-[2,6-naphthalenebis(methylene)]bis[1,2-dimethyl-1H-imidazolium] dications, represented by the following structure (1):
- Suitable sources of Q are the hydroxides, chlorides, bromides, and/or other salts of the diquaternary ammonium compound.
- the reaction mixture can contain seeds of a molecular sieve material, such as SSZ-120 from a previous synthesis, in an amount of from 0.01 to 10,000 ppm by weight (e.g., 100 to 5000 ppm by weight) of the reaction mixture. Seeding can be advantageous to improve selectivity for SSZ-120 and/or to shorten the crystallization process.
- a molecular sieve material such as SSZ-120 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 placed in convection oven maintained at a temperature of from 100° C. to 200° C. for a time sufficient for crystallization to occur at the temperature used (e.g., 1 day to 14 days).
- the hydrothermal crystallization process is usually conducted under autogenous pressure.
- 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-120 crystals having at least a portion of the structure directing agent 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.
- the thermal treatment may be conducted at a temperature of from 400° C. to 600° C. in air for approximately 1 to 8 hours.
- the thermally-treated product especially in its metal, hydrogen and ammonium forms, is particularly useful in the catalysis of certain organic (e.g., hydrocarbon) conversion reactions.
- 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-120 can have a chemical composition comprising the following molar relationship set forth in Table 2:
- the molecular sieve can have a SiO 2 /GeO 2 molar ratio in a range of from 4 to 12 (e.g., 6 to 10).
- molecular sieve SSZ-120 can have a chemical composition comprising the following molar relationship:
- n is ⁇ 30 (e.g., 30 to 600, ⁇ 60, 60 to 500, or 100 to 300).
- Molecular sieve SSZ-120 has a powder X-ray diffraction pattern which, in its as-synthesized form, includes at least the peaks set forth in Table 3 below and which, in its calcined form, includes at least the peaks set forth in Table 4.
- the powder X-ray diffraction patterns presented herein were collected by standard techniques using copper K-alpha radiation.
- the determination of the parameter 2-theta is subject to both human and mechanical error, which in combination can impose an uncertainty of about ⁇ 0.3° on each reported value of 2-theta. This uncertainty is, of course, also manifested in the reported values of the d-spacings, which are calculated from the 2-theta values using Bragg's law.
- the relative intensities of the lines, I/Io represents the ratio of the peak intensity to the intensity of the strongest line, above background. The intensities are uncorrected for Lorentz and polarization effects.
- Minor variations in the powder X-ray diffraction pattern can result from variations in the atomic ratios of the framework atoms due to changes in lattice constants.
- sufficiently small crystals may affect the shape and intensity of peaks, possibly leading to peak broadening.
- Calcination can also cause minor shifts in the powder X-ray diffraction pattern compared to the pre-calcination powder X-ray diffraction pattern. Notwithstanding these minor perturbations, the crystal lattice structure may remain unchanged following calcination.
- the syntheses described herein can produce a molecular sieve having a small crystal size, such that the total surface area of the material can be at least 500 m 2 /g and the external surface area can be at least 100 m 2 /g.
- the molecular sieve described herein can comprise crystals having a total external surface area of at least 600 m 2 /g, at least 625 m 2 /g, at least or at least 650 m 2 /g, such as from 500 to 800 m 2 /g, from 600 to 800 m 2 /g, or from 650 to 800 m 2 /g.
- the molecular sieve described herein can comprise crystals having an external surface area of at least 100 m 2 /g, at least 110 m 2 /g, at least 120 m 2 /g, at least 130 m 2 /g, or at least 140 m 2 /g, such as from 100 to 300 m 2 /g, from 120 to 300 m 2 /g, or from 140 to 300 m 2 /g. All surface area values given herein are determined from nitrogen physisorption using the t-plot method. Details of this method are described by B. C. Lippens and J. H. de Boer ( J. Catal. 1965, 4, 319-323).
- Molecular sieve SSZ-120 (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-120 include aromatization, cracking, hydrocracking, disproportionation, alkylation, oligomerization, and isomerization.
- SSZ-120 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-120 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-120 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-120 also include inorganic oxides, such as silica, zirconia, titania, magnesia, beryllia, alumina, and mixtures thereof.
- SSZ-120 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-120 and inorganic oxide matrix may vary widely, with the SSZ-120 content ranging from 1 to 90 wt. % (e.g., 2 to 80 wt. %) of the composite.
- the dibromide salt was exchanged to the corresponding dihydroxide salt by stirring it with hydroxide exchange resin in deionized water overnight.
- the solution was filtered, and the filtrate was analyzed for hydroxide concentration by titration of a small sample with a standardized solution of 0.1 N HCl.
- Powder XRD of the as-synthesized product gave the pattern indicated in FIG. 1 and showed the product to be a pure form of a new phase, SSZ-120. Significantly decreased crystal size is inferred from the peak broadening in the powder XRD pattern.
- FIGS. 2(A)-2(D) show illustrative SEM images of the as-synthesized product at various magnifications.
- the product had a SiO 2 /GeO 2 molar ratio of 8, as determined by Inductively Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES).
- ICP-AES Inductively Coupled Plasma-Atomic Emission Spectroscopy
- the as-synthesized molecular sieve of Example 1 was calcined inside a muffle furnace under a flow of air heated to 550° C. at a rate of 1° C./minute and held at 550° C. for 5 hours, cooled and then analyzed by powder XRD.
- the powder XRD pattern of the calcined material is shown in FIG. 3 and indicates that the material remains stable after calcination to remove the structure directing agent.
- the product was calcined as described in Example 2.
- the surface area of the sample was then measured using nitrogen physisorption and the data were analyzed with the t-plot method.
- the determined total surface area was 693 m 2 /g and the external surface area was 144 m 2 /g.
- the micropore volume was 0.2666 cm 3 /g.
- Br ⁇ nsted acidity of the molecular sieve of Example 5 in its calcined form was determined by n-propylamine temperature-programmed desorption (TPD) adapted from the published descriptions by T. J. Gricus Kofke et al. ( J. Catal. 1988, 114, 34-45); T. J. Gricus Kofke et al. ( J. Catal. 1989, 115, 265-272); and J. G. Tittensor et al. ( J. Catal. 1992, 138, 714-720). A sample was pre-treated at 400° C.-500° C. for 1 hour in flowing dry H 2 . The dehydrated sample was then cooled down to 120° C.
- TPD n-propylamine temperature-programmed desorption
- Constraint Index is a test to determine shape-selective catalytic behavior in molecular sieves. It compares the reaction rates for the cracking of n-hexane (n-C6) and its isomer 3-methylpentane (3-MP) under competitive conditions (see V. J. Frillette et al., J. Catal. 1981, 67, 218-222).
- the hydrogen form of the molecular sieve prepared per Example 5 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, 0.47 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/minute and at atmospheric pressure. The reactor was heated to about 700° F.
- Material from Example 5 was calcined in air at 595° C. for 5 hours. After calcination, the material was loaded with palladium by mixing for three days at room temperature 4.5 g of a 0.148 N NH 4 OH solution with 5.5 g of deionized water and then a (NH 3 ) 4 Pd(NO 3 ) 2 solution (buffered at pH 9.5) such that 1 g of this solution mixed in with 1 g of molecular sieve provided a 0.5 wt. % Pd loading.
- the recovered Pd/SSZ-120 material was washed with deionized water, dried at 95° C., and then calcined to 300° C. for 3 hours. The calcined Pd/SSZ-120 catalyst was then pelletized, crushed, and sieved to 20-40 mesh.
- 0.5 g of the Pd/SSZ-120 catalyst was loaded in the center of a 23 inch-long ⁇ 1 ⁇ 4 inch outside diameter stainless steel reactor tube with alundum loaded upstream of the catalyst for preheating the feed (a total pressure of 1200 psig; a down-flow hydrogen rate of 160 mL/minute when measured at 1 atmosphere pressure and 25° C.; and a down-flow liquid feed rate of 1 mL/hour). All materials were first reduced in flowing hydrogen at about 315° C. for 1 hour. Products were analyzed by on-line capillary GC once every 60 minutes. Raw data from the GC was collected by an automated data collection/processing system and hydrocarbon conversions were calculated from the raw data.
- Conversion is defined as the amount n-decane reacted to produce other products (including iso-C10). Yields are expressed as mole percent of products other than n-decane and include iso-C10 isomers as a yield product. The results are shown in FIG. 4 and indicate that the catalyst is quite active and not particularly selective for isomerization, making considerable cracked product from n-decane.
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Abstract
A small crystal size, high surface area aluminogermanosilicate molecular sieve material, designated SSZ-120, is provided. SSZ-120 can be synthesized using 3,3′-[2,6-naphthalenebis(methylene)]bis[1,2-dimethyl-1H-imidazolium] dications as a structure directing agent. SSZ-120 may be used in organic compound conversion reactions and/or sorptive processes.
Description
- This application claims priority to and the benefit of U.S. Provisional Application Ser. No. 63/028,642, filed May 22, 2020.
- This disclosure relates to a small crystal size, high surface area aluminogermanosilicate molecular sieve designated SSZ-120, its synthesis, and its use in organic compound conversion reactions 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.
- According to the present disclosure, a small crystal size, high surface area aluminogermanosilicate molecular sieve, designated SSZ-120 and having a unique powder X-ray diffraction pattern, has been synthesized using 3,3′-[2,6-naphthalenebis(methylene)]bis[1,2-dimethyl-1H-imidazolium] dications as a structure directing agent.
- In a first aspect, there is provided an aluminogermanosilicate molecular sieve having, in its calcined form, a powder X-ray diffraction pattern including the peaks in the following table:
-
2-Theta d-Spacing Relative Intensity [°] [nm] [100 × I/Io] 6.8 1.30 W 9.5 0.93 W 15.6 0.57 M 21.0 0.42 W 22.2 0.40 VS 25.9 0.34 M 26.9 0.33 M. - The calcined molecular sieve can have a total surface area (as determined by the t-plot method for nitrogen physisorption) of at least 500 m2/g and/or an external surface area (as determined by the t-plot method for nitrogen physisorption) of at least 100 m2/g.
- In a second aspect, there is provided an aluminogermanosilicate molecular sieve having, in its as-synthesized form, a powder X-ray diffraction pattern including the peaks in the following table:
-
2-Theta d-Spacing Relative Intensity [°] [nm] [100 × I/Io] 6.8 1.31 W 9.4 0.94 W 15.7 0.57 M 21.0 0.42 M 22.0 0.40 VS 25.9 0.34 M 26.9 0.33 M - In its as-synthesized and anhydrous form, the aluminogermanosilicate molecular sieve can have a chemical composition comprising the following molar relationship:
-
Broadest Secondary (SiO2 + GeO2)/Al2O3 ≥30 ≥60 Q/(SiO2 + GeO2) >0 to 0.1 >0 to 0.1
wherein Q comprises 3,3′-[2,6-naphthalenebis(methylene)]bis[1,2-dimethyl-1H-imidazolium] dications. - In a third aspect, there is provided a method of synthesizing an aluminogermanosilicate molecular sieve, the method comprising (1) providing a reaction mixture comprising: (a) a FAU framework type zeolite; (b) a source of germanium; (c) a structure directing agent (Q) comprising 3,3′-[2,6-naphthalenebis(methylene)]bis[1,2-dimethyl-1H-imidazolium] dications; (d) a source of fluoride ions; and (e) water; and (2) subjecting the reaction mixture to crystallization conditions sufficient to form crystals of the aluminogermanosilicate 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 active form of the aluminogermanosilicate molecular sieve, described herein.
- In a fifth aspect, there is provided an organic nitrogen compound comprising a dication having the following structure:
-
FIG. 1 shows the powder X-ray diffraction (XRD) pattern of the as-synthesized product of Example 2. -
FIGS. 2(A)-2(D) show scanning electron micrograph (SEM) images of the as-synthesized product of Example 2 at different magnifications. -
FIG. 3 shows the powder XRD pattern of the calcined product of Example 3. -
FIG. 4 is a graph illustrating the relationship between conversion or yield and temperature in the hydroconversion of n-decane over a Pd/SSZ-120 catalyst. - The term “framework type” has the meaning described in the “Atlas of Zeolite Framework Types”, by Ch. Baerlocher and L. B. McCusker and D. H. Olsen (Sixth Revised Edition, Elsevier, 2007).
- The term “zeolite” refers an aluminosilicate molecular sieve having a framework constructed of alumina and silica (i.e., repeating AlO4 and SiO4 tetrahedral units).
- The term “aluminogermanosilicate” refers to a molecular sieve having a framework constructed of AlO4, GeO4 and SiO4 tetrahedral units. The alumingermanosilicate may contain only the named oxides, in which case, it may be described as a “pure aluminogermanosilicate” or it may contain other additional oxides as well.
- The term “as-synthesized” is employed herein to refer to a molecular sieve in its form after crystallization, prior to removal of the structure directing agent.
- The term “anhydrous” is employed herein to refer 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
- Aluminogermanosilicate molecular sieve SSZ-120 can be synthesized by: (1) providing a reaction mixture comprising (a) a FAU framework type zeolite; (b) a source of germanium; (c) a structure directing agent (Q) comprising 3,3′-[2,6-naphthalenebis(methylene)]bis[1,2-dimethyl-1H-imidazolium] dications; (d) a source of fluoride ions; and (e) water; and (2) subjecting the reaction mixture to crystallization conditions sufficient to form crystals of the aluminogermanosilicate 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 Secondary (SiO2 + GeO2)/Al2O3 30 to 600 60 to 500 Q/(SiO2 + GeO2) 0.10 to 1.00 0.20 to 0.70 F/(SiO2 + GeO2) 0.10 to 1.00 0.20 to 0.70 H2O/(SiO2 + GeO2) 2 to 10 4 to 8
wherein Q comprises 3,3′-[2,6-naphthalenebis(methylene)]bis[1,2-dimethyl-1H-imidazolium] dications. - In some aspects, the reaction mixture can have a SiO2/GeO2 molar ratio in a range of from 4 to 12 (e.g., from 6 to 10).
- 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., CBV720, CBV760, CBV780, HSZ-385HUA, and HSZ-390HUA). Preferably, the FAU framework type zeolite is zeolite Y. More preferably, zeolite Y has a SiO2/Al2O3 molar ratio in a range of about 30 to about 500. The FAU framework type zeolite can comprise two or more zeolites. Typically, the two or more zeolites are Y zeolites having different SiO2/Al2O3 molar ratios. The FAU framework type zeolite can also be the only silica and aluminum source to form the aluminogermanosilicate molecular sieve.
- Sources of germanium include germanium oxide and germanium alkoxides (e.g., germanium ethoxide).
- Sources of fluoride ions include hydrogen fluoride, ammonium fluoride, and ammonium bifluoride.
- SSZ-120 can be synthesized using a structure directing agent (Q) comprising 3,3′-[2,6-naphthalenebis(methylene)]bis[1,2-dimethyl-1H-imidazolium] dications, represented by the following structure (1):
- Suitable sources of Q are the hydroxides, chlorides, bromides, and/or other salts of the diquaternary ammonium compound.
- The reaction mixture can contain seeds of a molecular sieve material, such as SSZ-120 from a previous synthesis, in an amount of from 0.01 to 10,000 ppm by weight (e.g., 100 to 5000 ppm by weight) of the reaction mixture. Seeding can be advantageous to improve selectivity for SSZ-120 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 placed in convection oven maintained at a temperature of from 100° C. to 200° C. for a time sufficient for crystallization to occur at the temperature used (e.g., 1 day to 14 days). The hydrothermal crystallization process is usually conducted under 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-120 crystals having at least a portion of the structure directing agent 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 from 400° C. to 600° C. in air for approximately 1 to 8 hours. The thermally-treated product, especially in its metal, hydrogen and ammonium forms, is particularly useful in the catalysis of certain organic (e.g., hydrocarbon) conversion reactions.
- 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-120 can have a chemical composition comprising the following molar relationship set forth in Table 2:
-
TABLE 2 Broadest Secondary (SiO2 + GeO2)/Al2O3 ≥30 ≥60 Q/(SiO2 + GeO2) >0 to 0.1 >0 to 0.1
wherein Q comprises 3,3′-[2,6-naphthalenebis(methylene)]bis[1,2-dimethyl-1H-imidazolium] dications. - In some aspects, the molecular sieve can have a SiO2/GeO2 molar ratio in a range of from 4 to 12 (e.g., 6 to 10).
- In its calcined form, molecular sieve SSZ-120 can have a chemical composition comprising the following molar relationship:
-
Al2O3:(n)(SiO2+GeO2) - wherein n is ≥30 (e.g., 30 to 600, ≥60, 60 to 500, or 100 to 300).
- Molecular sieve SSZ-120 has a powder X-ray diffraction pattern which, in its as-synthesized form, includes at least the peaks set forth in Table 3 below and which, in its calcined form, includes at least the peaks set forth in Table 4.
-
TABLE 3 Characteristic Peaks for As-Synthesized SSZ-120 2-Theta d-Spacing Relative Intensity [°] [nm] [100 × I/Io] 6.8 1.31 W 9.4 0.94 W 15.7 0.57 M 21.0 0.42 M 22.0 0.40 VS 25.9 0.34 M 26.9 0.33 M -
TABLE 4 Characteristic Peaks for Calcined SSZ-120 2-Theta d-Spacing Relative Intensity [°] [nm] [100 × I/Io] 6.8 1.30 W 9.5 0.93 W 15.6 0.57 M 21.0 0.42 W 22.2 0.40 VS 25.9 0.34 M 26.9 0.33 M - The powder X-ray diffraction patterns presented herein were collected by standard techniques using copper K-alpha radiation. As will be understood by those of skill in the art, the determination of the parameter 2-theta is subject to both human and mechanical error, which in combination can impose an uncertainty of about ±0.3° on each reported value of 2-theta. This uncertainty is, of course, also manifested in the reported values of the d-spacings, which are calculated from the 2-theta values using Bragg's law. The relative intensities of the lines, I/Io, represents the ratio of the peak intensity to the intensity of the strongest line, above background. The intensities are uncorrected for Lorentz and polarization effects. The relative intensities are given in terms of the symbols VS=very strong (>60 to 100), S=strong (>40 to 60), M=medium (>20 to 60), and W=weak (>0 to 20).
- Minor variations in the powder X-ray diffraction pattern (e.g., experimental variation in peak ratios and peak positions) can result from variations in the atomic ratios of the framework atoms due to changes in lattice constants. In addition, sufficiently small crystals may affect the shape and intensity of peaks, possibly leading to peak broadening. Calcination can also cause minor shifts in the powder X-ray diffraction pattern compared to the pre-calcination powder X-ray diffraction pattern. Notwithstanding these minor perturbations, the crystal lattice structure may remain unchanged following calcination.
- The syntheses described herein can produce a molecular sieve having a small crystal size, such that the total surface area of the material can be at least 500 m2/g and the external surface area can be at least 100 m2/g. In some aspects, the molecular sieve described herein can comprise crystals having a total external surface area of at least 600 m2/g, at least 625 m2/g, at least or at least 650 m2/g, such as from 500 to 800 m2/g, from 600 to 800 m2/g, or from 650 to 800 m2/g. Additionally or alternatively, the molecular sieve described herein can comprise crystals having an external surface area of at least 100 m2/g, at least 110 m2/g, at least 120 m2/g, at least 130 m2/g, or at least 140 m2/g, such as from 100 to 300 m2/g, from 120 to 300 m2/g, or from 140 to 300 m2/g. All surface area values given herein are determined from nitrogen physisorption using the t-plot method. Details of this method are described by B. C. Lippens and J. H. de Boer (J. Catal. 1965, 4, 319-323).
- Molecular sieve SSZ-120 (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-120, 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-120 include aromatization, cracking, hydrocracking, disproportionation, alkylation, oligomerization, and isomerization.
- As in the case of many catalysts, it may be desirable to incorporate SSZ-120 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-120 (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-120 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-120 also include inorganic oxides, such as silica, zirconia, titania, magnesia, beryllia, alumina, and mixtures thereof.
- In addition to the foregoing materials, SSZ-120 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-120 and inorganic oxide matrix may vary widely, with the SSZ-120 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.
- A 250 mL round bottom flask equipped with a magnetic stir bar was charged with 5 g of 2,6-bis(bromomethyl)naphthalene, 3.83 g of 1,2-dimethylimidazole and 100 mL of methanol. A reflux condenser was then attached, and the mixture heated at 65° C. for 3 days. After cooling, methanol was removed on a rotary evaporator to provide white solids. The initially recovered solids from rotary evaporation were further purified by recrystallization from cold ethanol. The recrystallized dibromide salt was pure by 1H- and 13C-NMR spectroscopy.
- The dibromide salt was exchanged to the corresponding dihydroxide salt by stirring it with hydroxide exchange resin in deionized water overnight. The solution was filtered, and the filtrate was analyzed for hydroxide concentration by titration of a small sample with a standardized solution of 0.1 N HCl.
- Into a tared 23 mL Parr reactor was added 0.27 g of Tosoh HSZ-390HUA Y-zeolite (SAR=500), 0.05 g of GeO2 and 2.5 mmol of an aqueous 3,3′-[2,6-naphthalenebis(methylene)]bis[1,2-dimethyl-1H-imidazolium] dihydroxide solution. The reactor was then placed in a vented hood and water was allowed to evaporate to bring the H2O/(SiO2+GeO2) molar ratio to 7 (as determined by the total mass of the suspension). Then, 2.5 mmol of HF was added and the reactor was heated to 160° C. with tumbling at 43 rpm for about 7 days. The solid products were recovered by centrifugation, washed with deionized water and dried at 95° C.
- Powder XRD of the as-synthesized product gave the pattern indicated in
FIG. 1 and showed the product to be a pure form of a new phase, SSZ-120. Significantly decreased crystal size is inferred from the peak broadening in the powder XRD pattern. -
FIGS. 2(A)-2(D) show illustrative SEM images of the as-synthesized product at various magnifications. - The product had a SiO2/GeO2 molar ratio of 8, as determined by Inductively Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES).
- The as-synthesized molecular sieve of Example 1 was calcined inside a muffle furnace under a flow of air heated to 550° C. at a rate of 1° C./minute and held at 550° C. for 5 hours, cooled and then analyzed by powder XRD.
- The powder XRD pattern of the calcined material is shown in
FIG. 3 and indicates that the material remains stable after calcination to remove the structure directing agent. - Example 2 was repeated using Zeolyst CBV780 Y-zeolite (SAR=80) as the FAU source. Powder XRD showed the product to be SSZ-120.
- Example 2 was repeated using Zeolyst CBV760 Y-zeolite (SAR=60) as the FAU source. Powder XRD showed the product to be SSZ-120.
- The product was calcined as described in Example 2. The surface area of the sample was then measured using nitrogen physisorption and the data were analyzed with the t-plot method. The determined total surface area was 693 m2/g and the external surface area was 144 m2/g. The micropore volume was 0.2666 cm3/g.
- Example 2 was repeated using Zeolyst CBV720 Y-zeolite (SAR=30) as the FAU source. Powder XRD showed the product to be SSZ-120.
- Brønsted acidity of the molecular sieve of Example 5 in its calcined form was determined by n-propylamine temperature-programmed desorption (TPD) adapted from the published descriptions by T. J. Gricus Kofke et al. (J. Catal. 1988, 114, 34-45); T. J. Gricus Kofke et al. (J. Catal. 1989, 115, 265-272); and J. G. Tittensor et al. (J. Catal. 1992, 138, 714-720). A sample was pre-treated at 400° C.-500° C. for 1 hour in flowing dry H2. The dehydrated sample was then cooled down to 120° C. in flowing dry helium and held at 120° C. for 30 minutes in a flowing helium saturated with n-propylamine for adsorption. The n-propylamine-saturated sample was then heated up to 500° C. at a rate of 10° C./minute in flowing dry helium. The Brønsted acidity was calculated based on the weight loss vs. temperature by thermogravimetric analysis (TGA) and effluent NH3 and propene by mass spectrometry. The sample had a Brønsted acidity of 250 μmol/g, indicating that aluminum sites are incorporated into the framework of the molecular sieve.
- Constraint Index is a test to determine shape-selective catalytic behavior in molecular sieves. It compares the reaction rates for the cracking of n-hexane (n-C6) and its isomer 3-methylpentane (3-MP) under competitive conditions (see V. J. Frillette et al., J. Catal. 1981, 67, 218-222).
- The hydrogen form of the molecular sieve prepared per Example 5 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, 0.47 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/minute and at atmospheric pressure. The reactor was heated to about 700° F. (371° C.), and a 50/50 feed of n-hexane and 3-methylpentane was introduced into the reactor at a rate of 8 μL/minute. The feed was delivered by an ISCO pump. Direct sampling into a GC began after 15 minutes of feed introduction. Test data results after 15 minutes on stream (700° F.) are presented in Table 5.
-
TABLE 5 Constraint Index Test n-Hexane Conversion, % 64.8 3-Methylpentane Conversion, % 93.3 Feed Conversion, % 79.1 Constraint Index (excluding 2MP) 0.39 Constraint Index (including 2MP) 0.39 - Material from Example 5 was calcined in air at 595° C. for 5 hours. After calcination, the material was loaded with palladium by mixing for three days at room temperature 4.5 g of a 0.148 N NH4OH solution with 5.5 g of deionized water and then a (NH3)4Pd(NO3)2 solution (buffered at pH 9.5) such that 1 g of this solution mixed in with 1 g of molecular sieve provided a 0.5 wt. % Pd loading. The recovered Pd/SSZ-120 material was washed with deionized water, dried at 95° C., and then calcined to 300° C. for 3 hours. The calcined Pd/SSZ-120 catalyst was then pelletized, crushed, and sieved to 20-40 mesh.
- 0.5 g of the Pd/SSZ-120 catalyst was loaded in the center of a 23 inch-long×¼ inch outside diameter stainless steel reactor tube with alundum loaded upstream of the catalyst for preheating the feed (a total pressure of 1200 psig; a down-flow hydrogen rate of 160 mL/minute when measured at 1 atmosphere pressure and 25° C.; and a down-flow liquid feed rate of 1 mL/hour). All materials were first reduced in flowing hydrogen at about 315° C. for 1 hour. Products were analyzed by on-line capillary GC once every 60 minutes. Raw data from the GC was collected by an automated data collection/processing system and hydrocarbon conversions were calculated from the raw data. Conversion is defined as the amount n-decane reacted to produce other products (including iso-C10). Yields are expressed as mole percent of products other than n-decane and include iso-C10 isomers as a yield product. The results are shown in
FIG. 4 and indicate that the catalyst is quite active and not particularly selective for isomerization, making considerable cracked product from n-decane.
Claims (15)
1. An aluminogermanosilicate molecular sieve having, in its calcined form, a powder X-ray diffraction pattern including the peaks in the following table:
2. The aluminogemanosilicate molecular sieve of claim 1 , the molecular sieve comprising crystals having a total surface area of at least 500 m2/g, as determined by the t-plot method for nitrogen physisorption, and/or an external surface area in a range of at least 100 m2/g, as determined by determined from the t-plot method of nitrogen physisorption.
3. The aluminogemanosilicate molecular sieve of claim 2 , wherein the total surface area is in a range of from 500 to 800 m2/g.
4. The aluminogemanosilicate molecular sieve of claim 2 , wherein the external surface area is in a range of from 100 to 300 m2/g.
5. The aluminogermanosilicate molecular sieve of claim 1 , having a composition comprising the molar relationship:
Al2O3:(n)(SiO2+GeO2)
Al2O3:(n)(SiO2+GeO2)
wherein n is ≥30.
6. An aluminogermanosilicate molecular sieve having, in its as-synthesized form, a powder X-ray diffraction pattern including the peaks in the following table:
7. The aluminogermanosilicate molecular sieve of claim 6 , having a composition, in terms of molar ratios, as follows:
wherein Q comprises 3,3′-[2,6-naphthalenebis(methylene)]bis[1,2-dimethyl-1H-imidazolium] dications.
8. The aluminogermanosilicate molecular sieve of claim 6 , having a chemical composition comprising the following molar relationship:
wherein Q comprises 3,3′-[2,6-naphthalenebis(methylene)]bis[1,2-dimethyl-1H-imidazolium] dications.
9. A method of synthesizing an aluminogermanosilicate molecular sieve, the method comprising:
(1) providing a reaction mixture comprising:
(a) a FAU framework type zeolite;
(b) a source of germanium;
(c) a structure directing agent (Q) comprising 3,3′-[2,6-naphthalenebis(methylene)]bis[1,2-dimethyl-1H-imidazolium] dications;
(d) a source of fluoride ions; and
(e) water; and
(2) subjecting the reaction mixture to crystallization conditions sufficient to form crystals of the aluminogermanosilicate molecular sieve.
10. The method of claim 9 , wherein the reaction mixture has a composition, in terms of molar ratios, as follows:
11. The method of claim 9 , wherein the reaction mixture has a composition, in terms of molar ratios, as follows:
12. The method of claim 9 , wherein the FAU framework type zeolite is zeolite Y.
13. The method of claim 9 , wherein the crystallization conditions include heating the reaction mixture under autogenous pressure at a temperature of from 100° C. to 200° C. and for a time of from 1 day to 14 days.
14. A process for converting a feedstock comprising an organic compound to a conversion product, the process comprising contacting the feedstock at organic compound conversion conditions with a catalyst comprising the aluminogermanosilicate molecular sieve of claim 1 .
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