CN101124162A - 微孔结晶材料、沸石itq-33、及其制备方法和用途 - Google Patents
微孔结晶材料、沸石itq-33、及其制备方法和用途 Download PDFInfo
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- CN101124162A CN101124162A CNA2006800024936A CN200680002493A CN101124162A CN 101124162 A CN101124162 A CN 101124162A CN A2006800024936 A CNA2006800024936 A CN A2006800024936A CN 200680002493 A CN200680002493 A CN 200680002493A CN 101124162 A CN101124162 A CN 101124162A
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- crystalline material
- synthetic mixture
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- oxide compound
- crystal
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- 239000002178 crystalline material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims description 24
- 239000010457 zeolite Substances 0.000 title claims description 12
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims description 11
- 229910021536 Zeolite Inorganic materials 0.000 title claims description 10
- 239000000203 mixture Substances 0.000 claims abstract description 88
- 238000000034 method Methods 0.000 claims abstract description 32
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 42
- 229910005793 GeO 2 Inorganic materials 0.000 claims description 36
- 239000013078 crystal Substances 0.000 claims description 32
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 28
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 10
- 229910052732 germanium Inorganic materials 0.000 claims description 8
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- 125000002091 cationic group Chemical group 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 238000004364 calculation method Methods 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 238000004523 catalytic cracking Methods 0.000 claims description 3
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 3
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 3
- 230000032050 esterification Effects 0.000 claims description 3
- 238000005886 esterification reaction Methods 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 230000035935 pregnancy Effects 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 2
- 150000005621 tetraalkylammonium salts Chemical class 0.000 claims description 2
- 238000007669 thermal treatment Methods 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 abstract 2
- 235000013305 food Nutrition 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 10
- 230000003068 static effect Effects 0.000 description 10
- 229910000831 Steel Inorganic materials 0.000 description 9
- 239000004809 Teflon Substances 0.000 description 9
- 229920006362 Teflon® Polymers 0.000 description 9
- 230000031709 bromination Effects 0.000 description 9
- 238000005893 bromination reaction Methods 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 238000001704 evaporation Methods 0.000 description 9
- 230000008020 evaporation Effects 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 239000010959 steel Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 206010013786 Dry skin Diseases 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- -1 rare-earth cation Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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
- C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B01J23/44—Palladium
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
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- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- 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
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- 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
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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- C01B39/065—Galloaluminosilicates; Group IVB- metalloaluminosilicates; Ferroaluminosilicates
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
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- C01B39/12—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the replacing atoms being at least boron atoms
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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- C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
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Abstract
本发明涉及一种多孔结晶材料,特征在于其在煅烧态具有如下式所示的化学组成:X2O3∶nYO2∶mGeO2其中(n+m)至少为5,X为三价元素,Y表示一种或多种Ge之外的四价元素,Y/Ge之比大于1。而且,在没有煅烧的合成态,所述材料的X射线衍射图形的主线为:(右表)其中“mf”指相对强度80~100,“d”指相对强度20~40,“md”指相对强度0~20,以相对于最高强度的峰值的百分比计算。本发明还涉及制备所述材料的方法,及其在包含有机化合物的食品转化中的用途。
Description
技术领域
本发明涉及一种新型的微孔结晶材料、ITQ-33、涉及其制备方法及其在有机化合物的催化转化中的用途。
发明背景
沸石是多孔结晶铝硅酸盐,其作为催化剂、吸附剂和离子交换剂具有重要的用途。这些沸石材料很多具有明确的结构,在其中形成具有均匀尺寸和形状的通道和空穴,可以吸附特定的分子,同时防止其它过大不能通过孔扩散的分子通过,到达晶体的内部。这种特征赋予了这些材料具有分子筛的性质。这些分子筛的晶格可以包括Si和元素周期表的IIIA族的其它元素,它们都是四面体配位,具有在其顶点通过氧原子相连的四面体结构,形成三维网络。IIIA组元素在晶格点产生的负电荷由晶体内存在的阳离子补偿,例如碱金属或碱土金属的阳离子。通过离子交换技术,可以将一种类型的阳离子全部或部分被另一种类型的阳离子交换,使得通过选择所希望的阳离子可以改变给定硅酸盐的性质。
很多沸石都是在作为结构控制剂的有机分子的存在下合成的。作为结构控制剂(SCAs)的有机分子通常在其组成中包括氮,可以产生在反应混合物中稳定的有机阳离子。
在可以作为所述SCA的氢氧化物引入的OH-根和碱性介质的存在下,可以实现二氧化硅的活动化,例如在沸石ZSM-5情况下的氢氧化四丙基铵。
发明内容
本发明涉及一种新型的微孔结晶材料ITQ-33,在其煅烧态具有下式所示的化学组成:
X2O3:nYO2:mGeO2
其中(n+m)至少为5,X为三价元素,Y表示一种或多种Ge之外的四价元素,Y/Ge之比大于1,其非煅烧合成态具有的X射线衍射图形的的主线如下:
(d±0.2)(_) | 相对强度 |
16.5911.639.578.316.764.814.624.273.643.15 | vsvwvwvwvwvwvwwww |
其中“vs”指相对强度80~100,“w”指相对强度20~40,“vw”指相对强度0~20,作为相对于最高强度的峰值的百分比计算而得。
因此该新型多孔结晶材料可以在不存在锗的情况下获得。
这种称作ITQ-33的新型材料,在其煅烧态或非煅烧合成态,都具有与其它已知沸石材料不同的X射线衍射图形,表1中给出了其煅烧态最重要的衍射线:
表1
(d±0.2)(_) | 相对强度 |
16.8111.509.718.416.794.844.654.244.013.843.813.663.363.172.812.562.372.27 | vsvwvwvwvwvwvwvwvwwvwvwwvwvwvwvwvw |
晶面间距d以埃计,线的相对强度以相对于最高强度的峰值的百分比计算,(vs)=80~100为非常强,(s)=60~80为强,(m)=40~60为中等,(w)=20~40为弱,以及(vw)=0~20为非常弱。
ITQ-33的优选实施方式在其未煅烧态具有表2中所示的衍射线。
表2
(d±0.2)(_) | 相对强度 |
16.5911.639.578.316.764.814.624.274.023.863.823.643.333.152.782.752.542.382.27 | vsvwvwvwvwvwvwwvwvwvwwvwwvwvwvwvwvw |
这些衍射图形是用配置有石墨单色器和使用铜Kα放射的自动发散狭缝的Philips X’Pert衍射计得到的。用0.01°的步级2θ记录衍射数据,其中θ为布拉格角(Bragg angle),每一步级的计数时间为10秒。晶面间距d以埃计,线的相对强度以相对于最高强度的峰值的百分比计算,(vs)=80~100为非常强,(s)=60~80为强,(m)=40~60为中等,(w)=20~40为弱,以及(vw)=0~20为非常弱。
必须考虑该例子中所列的作为单线或唯一线的衍射数据可以由多个交迭或重合的反射形成,所述反射在某种情况例如在晶体变化不同时,会作为分解线或部分分解线出现。通常,晶体变化可以包括晶胞参数的小变化和/或晶体对称性的变化,不会产生结构的变化。这些改变,也包括相对强度的改变,也可能是由于补偿的阳离子的类型和数量、晶格组成、晶体大小和形态、优选定向、或者所实施的热或水热处理的类型的差异造成的。
该结晶材料优选在其无水煅烧态具有如下所示的组成:
X2O3:nYO2:mGeO2
其中(n+m)至少为5,n/m值至少为1,X表示选自Al、B、In、Ga、Fe和Cr中的一种或多种的三价元素;Y表示选自Si、Sn、Ti、V中的一种或多种四价元素。
在特别优选的实施方式中,该结晶材料在煅烧态具有如上所述的通式,其中X选自B、Al或二者的混合物;Y为Si。
从给出的数值中明显可以看到结晶材料ITQ-33可以在不添加三价元素的情况下合成。
合成的材料的有机组分可以除去,例如通过萃取或通过加热到高于250℃的温度热处理2分钟~25小时的时间段。
材料在未煅烧态或在热处理后的补偿阳离子如果存在的话,可以被其它阳离子取代,例如金属离子、H+和H+的前体,例如NH4 +。在可以通过离子交换引入的阳离子中,优选的是作为催化剂对材料的活性具有积极影响的那些,优选更特别的阳离子是例如H+、稀土阳离子、和VIII族金属、以及元素周期表的IIA、IIIA、IVA、VA、IB、IIB、IIIB、IVB、VB、VIIB族。
本发明的结晶材料也可以与加氢-脱氢组分紧密结合,例如铂、钯、镍、铼、钴、钨、钼、钒、铬、锰、铁及其组合物。引入这些元素可以发生在结晶阶段,通过交换(如果发生的话)、和/或通过浸渍或通过物理混合。这些元素可以其阳离子态和/或从盐或其它化合物引入,其一旦分解会产生其适当催化形态中的金属或氧化物组分。
本发明还涉及如上所限定的结晶材料的制备方法,至少包括:
-制备合成混合物,该合成混合物至少包含H2O、一种或多种四价元素Y的来源、以及作为结构控制剂(R)的有机化合物,
-将所述合成混合物保持在80~200℃的温度,直到形成多孔结晶材料的晶体;以及
-回收所述结晶材料。
依照优选的实施方式,如上所限定的结晶材料的制备方法至少包括:
-制备合成混合物,该合成混合物至少包含:
-H2O,
-一种或多种四价元素Y的氧化物,
-和作为结构控制剂(R)的有机化合物,氧化物的摩尔比为:
H2O/(YO2) 1-50
R/(YO2) 0.1-3.0
-将所述合成混合物保持在80~200℃的温度,直到形成多孔结晶材料的晶体;以及
-回收所述结晶材料。
在该实施方式中,特别优选氧化物的摩尔比为:
H2O/(YO2) 2-20
R/(YO2) 0.1-1.0
该方法进一步的优选实施方式包括:
-制备合成混合物,该合成混合物至少包含H2O、一种或多种四价元素Y的来源、Ge的来源和作为结构控制剂(R)的有机化合物,
-将所述合成混合物保持在80~200℃的温度,直到形成多孔结晶材料的晶体;以及
-回收所述结晶材料。
依照优选的实施方式,如上所限定的结晶材料的制备方法至少包括:
-制备合成混合物,该合成混合物至少包含:
-H2O,
-一种或多种四价元素Y的氧化物,
-Ge的氧化物
-和作为结构控制剂(R)的有机化合物,氧化物的摩尔比为:
H2O/(YO2+GeO2) 1-50
R/(YO2+GeO2) 0.1-3.0
YO2/GeO2 大于1
-将所述合成混合物保持在80~200℃的温度,直到形成多孔结晶材料的晶体;以及
-回收所述结晶材料。
在该实施方式中,特别优选氧化物的摩尔比为:
H2O/(YO2+GeO2) 2-20
R/(YO2+GeO2) 0.1-1.0
YO2/GeO2 大于1
该方法的另一种优选的实施方式至少包括:
-制备合成混合物,该合成混合物至少包含H2O、一种或多种三价元素X的来源、一种或多种四价元素Y的来源、和作为结构控制剂(R)的有机化合物,
-将所述合成混合物保持在80~200℃的温度,直到形成多孔结晶材料的晶体;以及
-回收所述结晶材料。
该方法的另一种优选的实施方式至少包括:
-制备合成混合物,该合成混合物至少包含H2O、一种或多种三价元素X的氧化物、一种或多种四价元素Y的氧化物、和作为结构控制剂(R)的有机化合物,氧化物的摩尔比为:
YO2/X2O3 至少5
H2O/YO2 1-50
R/YO2 0.1-3.0
-将所述合成混合物保持在80~200℃的温度,直到形成多孔结晶材料的晶体;以及
-回收所述结晶材料。
依照前述实施方式,优选的氧化物的摩尔比为:
YO2/X2O3 大于7
H2O/YO2 2-20
R/YO2 0.1-1.0
该方法的另一种优选的实施方式包括:
-制备合成混合物,该合成混合物至少包含H2O、一种或多种三价元素X的来源;一种或多种四价元素Y的来源、Ge的氧化物、和作为结构控制剂(R)的有机化合物,
-将所述合成混合物保持在80~200℃的温度,直到形成多孔结晶材料的晶体;以及
-回收所述结晶材料。
该方法进一步的优选实施方式包括:
-制备合成混合物,该合成混合物至少包含H2O、一种或多种三价元素X的氧化物;一种或多种四价元素Y的氧化物、Ge的氧化物和作为结构控制剂的有机化合物(R),氧化物的摩尔比为:
(YO2+GeO2)/X2O3 大于5
H2O/(YO2+GeO2) 1-50
R/(YO2+GeO2) 0.1-3.0
YO2/GeO2 大于1
-将所述合成混合物保持在80~200℃的温度,直到形成多孔结晶材料的晶体;以及
-回收所述结晶材料。
依照该实施方式,氧化物的摩尔比优选为:
(YO2+GeO2)/X2O3 大于7
H2O/(YO2+GeO2) 2-20
R/(YO2+GeO2) 0.1-1.0
YO2/GeO2 大于1
在本发明的方法的任一实施方式中,可以将作为晶种的沸石ITQ-33的晶体(多达20wt.%)加到合成混合物中。
在本发明方法的任一实施方式中,用作结构控制剂的有机化合物优选选自胺和四烷基铵盐,优选为氢氧化物。
本发明的方法当用于制备煅烧态的结晶材料时,包括去除材料内部截留的有机物质的步骤,该步骤可以通过萃取、在高于250℃的温度热处理2分钟~25小时的时间段进行。
依照本发明方法的进一步优选实施方式,其包括:
-制备合成混合物,该合成混合物至少包含H2O、一种或多种选自Al、B及二者混合物的三价元素X的氧化物、Si的氧化物、Ge的氧化物和作为R的六甲铵盐,氧化物的摩尔比为:
(SiO2+GeO2)/X2O3 至少5
H2O/(SiO2+GeO2) 1-50
R/(SiO2+GeO2) 0.1-3.0
SiO2/GeO2 大于1
-将所述合成混合物保持在80~200℃的温度,直到形成多孔结晶材料的晶体;以及
-回收所述结晶材料。
ITQ-33的结晶可以在静态条件或搅拌下,在80~200℃的高压釜中进行,反应时间足以实现结晶,例如12小时~60天。
一旦完成结晶阶段,将ITQ-33晶体从母液中分理出来并回收。必须注意合成混合物的组分可以来自不同的来源,结晶时间和条件也可以根据这些改变。为了便于合成,可以向合成混合物中添加ITQ-33的晶体作为晶种,其量相对于氧化物总量多达20wt.%。可以在ITQ-33的结晶之前或期间添加。
通过本发明方法制备的材料可以依照已知技术制成颗粒,可以其酸态和/或与适当阳离子交换,用于烃的催化裂化、烃的催化加氢裂化、芳族化合物与烯烃的烷化、以及酯化过程、丙烯酸化、苯胺和甲醛的反应。优选该材料作为其它催化剂的组分存在。
本发明进一步涉及有机化合物形成的进料的转化方法,其特征在于其包括将所述进料与活化态的本发明多孔结晶材料接触。
优选的所述方法选自烃的催化裂化、烃的催化加氢裂化、芳族化合物与烯烃的烷化、酯化、丙烯酸化、以及苯胺和甲醛的反应,并包括选自酸态、与阳离子交换或两者结合形态的该材料的粒化。甚至更优选地,所述材料作为催化剂的组分存在。
实施例
实施例1:合成ITO-33
将0.174g的GeO2溶解在0.373g的氢氧化六甲铵溶液(16.3wt.%)和0.843g的溴化六甲铵溶液(50wt.%)中。向前述溶液中添加6.8mg的Al2O3和0.533g的Ludox AS-40,在搅拌中保持该合成混合物蒸发,直至达到如下的最终组成:0.68 SiO2:0.32GeO2:0.019 Al2O3:0.10R(OH)2:0.16R(Br)2:2.63H2O其中R为六甲铵。
在Teflon衬里的钢制高压釜中,在静态条件下将凝胶在175℃加热4天。在过滤、用蒸馏水洗涤和在100℃下干燥之后得到的固体为ITQ-33。
于540℃下在空气流中将材料煅烧3小时,去除有机物质。所得到固体的X射线粉末衍射图符合表1中的数值。
实施例2:
将0.174g的GeO2溶解在0.353g的氢氧化六甲铵溶液(16.6wt.%)和0.895g的溴化六甲铵溶液(50wt.%)中。向前述溶液中添加7.3mg的Al2O3和0.542g的Ludox AS-40,搅拌该合成混合物直至通过蒸发达到如下的组成:0.68 SiO2:0.32GeO2:0.020Al2O3:0.09R(OH)2:0.17R(Br)2:2.3H2O其中R为六甲铵。
在Teflon衬里的钢制高压釜中,在静态条件下将凝胶在175℃加热14天。在过滤、用蒸馏水洗涤和在100℃干燥之后得到的固体为ITQ-33。
实施例3:
将0.174g的GeO2溶解在0.359g的氢氧化六甲铵溶液(16.3wt.%)和0.824g的溴化六甲铵溶液(50wt.%)中。向得到的溶液中添加0.151g的H3BO3溶液(5wt.%)和0.497g的LudoxAS-40,在搅拌下保持蒸发,直至合成混合物达到如下组成:0.66 SiO2:0.34GeO2:0.025B2O3:0.10R(OH)2:0.16R(Br)2:3.13H2O其中R为六甲铵。
在Teflon衬里的钢制高压釜中,在静态条件下将凝胶在175℃加热5天。在过滤、用蒸馏水洗涤和在100℃干燥之后得到的固体为沸石ITQ-33。
实施例4:
将0.174g的GeO2溶解在0.381g的氢氧化六甲铵溶液(15.4wt.%)和0.854g的溴化六甲铵溶液(50wt.%)中。在得到的溶液中添加7.0mg的Al2O3和0.516g的LudoxAS-40,在搅拌中保持蒸发,直至混合物达到如下组成:0.67 SiO2:0.33GeO2:0.020Al2O3:0.10R(OH)2:0.17R(Br)2:1.91H2O其中R为六甲铵。
在Teflon衬里的钢制高压釜中,在静态条件下将凝胶在175℃加热8天。在过滤、用蒸馏水洗涤和在100℃干燥之后得到的固体为沸石ITQ-33。
实施例5:
将0.174g的GeO2溶解在0.384g的氢氧化六甲铵溶液(15.4wt.%)和0.897g的溴化六甲铵溶液(50wt.%)中。向前述溶液中添加11.2mg的Al2O3和0.515g的LudoxAS-40,在搅拌中保持该混合物蒸发,直至达到如下的最终组成:0.67SiO2:0.33GeO2:0.032Al2O3:0.10R(OH)2:0.18R(Br)2:2.80H2O其中R为六甲铵。
在Teflon衬里的钢制高压釜中,在静态条件下将凝胶在175℃加热8天。在过滤、用蒸馏水洗涤和在100℃干燥之后得到的固体为ITQ-33。
实施例6:
将0.174g的GeO2溶解在0.317g的氢氧化六甲铵溶液(18.3wt.%)和0.830g的溴化六甲铵溶液(50wt.%)中。向得到的溶液中添加6.9mg的Al2O3和0.513g的Ludox AS-40,在搅拌中保持蒸发,直至混合物达到如下组成:0.67SiO2:0.33GeO2:0.020Al2O3:0.10R(OH)2:0.16R(Br)2:2.78H2O其中R为六甲铵。
在Teflon衬里的钢制高压釜中,在静态条件下将凝胶在150℃加热25天。在过滤、用蒸馏水洗涤和在100℃干燥之后得到的固体为沸石ITQ-33。
实施例7:
将0.176g的GeO2溶解在0.322g的氢氧化六甲铵溶液(18.3wt.%)和0.882g的溴化六甲铵溶液(50wt.%)中。添加0.122g的H3BO3溶液(5wt.%)和0.525g的Ludox AS-40。在搅拌中保持该混合物蒸发,直至该反应混合物达到如下的最终组成:0.67SiO2:0.33GeO2:0.01B2O3:0.10R(OH)2:0.16R(Br)2:4.2H2O其中R为六甲铵。
在Teflon衬里的钢制高压釜中,在静态条件下将凝胶在175℃加热14天。在过滤、用蒸馏水洗涤和在100℃干燥之后得到的固体为ITQ-33和ITQ-24相的混合物。
实施例8:
将0.174g的GeO2溶解在0.320g的氢氧化六甲铵溶液(18.3wt.%)和0.823g的溴化六甲铵溶液(50wt.%)中。向所得到的溶液中添加0.311g的H3BO3溶液(5wt.%)和0.507g的Ludox AS-40,在搅拌中保持蒸发,直至该混合物达到如下组成:0.67SiO2:0.33GeO2:0.025B2O3:0.10R(OH)2:0.15R(Br)2:4.7H2O其中R为六甲铵。
在Teflon衬里的钢制高压釜中,在静态条件下将凝胶在175℃加热14天。在过滤、用蒸馏水洗涤和在100℃干燥之后得到的固体为ITQ-33和ITQ-24相的混合物。
实施例9:
将0.105g的GeO2溶解在0.586g的氢氧化六甲铵溶液(17.6wt.%)和0.239g的溴化六甲铵溶液(50wt.%)中。添加0.010g的Al2O3和0.303g的Ludox AS-40。最后添加0.322g的氟化铵溶液(10wt.%),在搅拌中保持该混合物蒸发,直至该反应混合物达到如下的最终组成:0.67SiO2:0.33GeO2:0.025Al2O3:0.15R(OH)2:0.10R(Br)2:0.30NH4F:3H2O其中R为六甲铵。
添加0.018g的ITQ-33晶体,并使该混合物均质化。在Teflon衬里的钢制高压釜中,在静态条件下将凝胶在175℃加热20小时。在过滤、用蒸馏水洗涤和在100℃干燥之后得到的固体为ITQ-33。
Claims (27)
1.一种多孔结晶材料,特征在于其在煅烧态具有如下式所示的化学组成:
X2O3:nYO2:mGeO2
其中(n+m)至少为5,X为三价元素,Y表示一种或多种Ge之外的四价元素,Y/Ge之比大于1,其非煅烧合成态具有的X射线衍射图形的主线为:
其中“vs”指相对强度80~100,“w”指相对强度20~40,“vw”指相对强度0~20,以相对于最高强度的峰值的百分比计算。
2.如权利要求1所述的多孔结晶材料,特征在于其煅烧态的X射线衍射图形的主线为:
其中“vs”、“w”、“vw”具有如权利要求1所述的含义。
3.如权利要求1或2之一所述的结晶材料,其特征在于X表示选自Al、B、In、Ga、Fe和Cr中的一种或多种三价元素;Y表示选自Si、Sn、Ti、V中的一种或多种四价元素。
4.如权利要求3所述的结晶材料,其特征在于X选自B、Al或二者的混合物;Y为Si。
5.一种催化剂,特征在于其包含前述权利要求之一所述的材料,该材料与加氢-脱氢组分结合。
6.如权利要求5所述的催化剂,其特征在于所述加氢-脱氢组分选自铂、钯、镍、铼、钴、钨、钼、钒、铬、锰、铁及其组合物。
7.种如权利要求1~4之一所述的结晶材料的合成方法,特征在于其至少包括:
-制备合成混合物,该合成混合物至少包含H2O、一种或多种四价元素Y的来源,以及作为结构控制剂(R)的有机化合物,
-将所述合成混合物保持在80~200℃的温度,直到形成多孔结晶材料的晶体;以及
-回收所述结晶材料。
8.如权利要求7所述的方法,特征在于其至少包括:
-制备合成混合物,该合成混合物至少包含:
-H2O,
-一种或多种四价元素Y的氧化物,
-和作为结构控制剂(R)的有机化合物,
氧化物的摩尔比为:
H2O/(YO2) 1-50
R/(YO2) 0.1-3.0
-将所述合成混合物保持在80~200℃的温度,直到形成多孔结晶材料的晶体;以及
-回收所述结晶材料。
9.如权利要求8所述的方法,其特征在于氧化物的摩尔比为:
H2O/(YO2) 2-20
R/(YO2) 0.1-1.0
10.如权利要求7所述的方法,特征在于其至少包括:
-制备合成混合物,该合成混合物至少包含H2O、一种或多种四价元素Y的来源、Ge的来源和作为结构控制剂(R)的有机化合物,
-将所述合成混合物保持在80~200℃的温度,直到形成多孔结晶材料的晶体;以及
-回收所述结晶材料。
11.如权利要求10所述的方法,特征在于其至少包括:
-制备合成混合物,该合成混合物至少包含H2O、一种或多种四价元素Y的氧化物、Ge的氧化物和作为结构控制剂(R)的有机化合物,氧化物的摩尔比为:
H2O/(YO2+GeO2) 1-50
R/(YO2+GeO2) 0.1-3.0
YO2/GeO2 大于1
-将所述合成混合物保持在80~200℃的温度,直到形成多孔结晶材料的晶体;以及
-回收所述结晶材料。
12.如权利要求11所述的方法,其特征在于氧化物的摩尔比为:
H2O/(YO2+GeO2) 2-20
R/(YO2+GeO2) 0.1-1.0
YO2/GeO2 大于1
13.如权利要求7所述的方法,特征在于其至少包括:
-制备合成混合物,该合成混合物至少包含H2O、一种或多种三价元素X的来源;一种或多种四价元素Y的来源和作为结构控制剂(R)的有机化合物,
-将所述合成混合物保持在80~200℃的温度,直到形成多孔结晶材料的晶体;以及
-回收所述结晶材料。
14.如权利要求13所述的方法,特征在于其包括:
-制备合成混合物,该合成混合物至少包含H2O、一种或多种三价元素X的氧化物;一种或多种四价元素Y的氧化物和作为结构控制剂(R)的有机化合物,氧化物的摩尔比为:
YO2/X2O3 至少5
H2O/YO2 1-50
R/YO2 0.1-3.0
-将所述合成混合物保持在80~200℃的温度,直到形成多孔结晶材料的晶体;以及
-回收所述结晶材料。
15.如权利要求14所述的方法,其特征在于氧化物的摩尔比为:
YO2/X2O3 大于7
H2O/YO2 2-20
R/YO2 0.1-1.0
16.如权利要求10所述的方法,特征在于其至少包括:
-制备合成混合物,该合成混合物至少包含H2O、一种或多种三价元素X的来源;一种或多种四价元素Y的来源、Ge的氧化物和作为结构控制剂(R)的有机化合物,
-将所述合成混合物保持在80~200℃的温度,直到形成多孔结晶材料的晶体;以及
-回收所述结晶材料。
17.如权利要求16所述的方法,特征在于其包括:
-制备合成混合物,该合成混合物至少包含H2O、一种或多种三价元素X的氧化物;一种或多种四价元素Y的氧化物、Ge的氧化物和作为结构控制剂(R)的有机化合物,氧化物的摩尔比为:
(YO2+GeO2)/X2O3 至少5
H2O/(YO2+GeO2) 1-50
R/(YO2+GeO2) 0.1-3.0
YO2/GeO2 大于1
-将所述合成混合物保持在80~200℃的温度,直到形成多孔结晶材料的晶体;以及
-回收所述结晶材料。
18.如权利要求17所述的方法,其特征在于氧化物的摩尔比为:
(YO2+GeO2)/X2O3 大于7
H2O/(YO2+GeO2) 2-20
R/(YO2+GeO2) 0.1-1.0
YO2/GeO2 大于1
19.如权利要求7~18之一所述的方法,其特征在于将作为晶种的沸石ITQ-33的晶体加到合成混合物中。
20.如权利要求19所述的方法,其特征在于作为晶种的沸石ITQ-33的所述晶体以相对于氧化物总重量多达20wt.%的比例添加。
21.如权利要求7~19之一所述的方法,其特征在于用作结构控制剂的所述有机化合物选自胺和四烷基铵盐。
22.利要求7~19之一所述的方法,其特征在于用作结构控制剂的有机化合物为氢氧化六甲铵。
23.如权利要求7所述的方法,特征在于其包括:
-制备合成混合物,该合成混合物至少包含H2O、一种或多种选自Al、B及二者混合物的三价元素X的氧化物、Si的氧化物、Ge的氧化物和作为结构控制剂R的六甲铵盐,氧化物的摩尔比为:
(SiO2+GeO2)/X2O3 至少5
H2O/(SiO2+GeO2) 1-50
R/(SiO2+GeO2) 0.1-3.0
SiO2/GeO2 大于1
-将所述合成混合物保持在80~200℃的温度,直到形成多孔结晶材料的晶体;以及
-回收所述结晶材料。
24.如权利要求7~23之一所述的方法,特征在于其包括去除材料内部截留的有机物质的步骤,该步骤是通过萃取、在高于250℃的温度下热处理2分钟~25小时的时间段、或两者结合进行的。
25.权利要求1~4之一所述的多孔结晶材料的活性态作为催化剂在包含有机化合物的进料转化中的用途。
26.如权利要求25所述的用途,其特征在于所述转化选自烃的催化裂化、烃的催化加氢裂化、芳族化合物与烯烃的烷化、酯化、丙烯酸化、苯胺和甲醛的反应,其包括选自酸态、与阳离子交换或两者结合形态的所述材料的粒化。
27.如权利要求26所述的用途,其特征在于所述材料是催化剂的组分。
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ESP200500120 | 2005-01-17 | ||
ES200500120A ES2259537B1 (es) | 2005-01-17 | 2005-01-17 | Sintesis de la zeolita itq-33. |
PCT/ES2006/070002 WO2006075041A1 (es) | 2005-01-17 | 2006-01-17 | Un material cristalino microporoso, zeolita itq-33, procedimiento de preparación y uso |
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CN (1) | CN101124162B (zh) |
AU (1) | AU2006205762A1 (zh) |
CA (1) | CA2637272C (zh) |
ES (1) | ES2259537B1 (zh) |
IL (1) | IL184237A0 (zh) |
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CN104487385A (zh) * | 2012-04-18 | 2015-04-01 | 康斯乔最高科学研究公司 | Itq-49材料、其生产方法及其用途 |
CN110831897A (zh) * | 2017-07-27 | 2020-02-21 | 埃克森美孚研究工程公司 | Emm-23材料及其制备方法和用途 |
CN113955770A (zh) * | 2021-11-11 | 2022-01-21 | 南京大学 | 一种超大孔itt结构硅酸盐分子筛材料及其制备方法 |
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ES2284379B1 (es) * | 2006-02-28 | 2008-11-01 | Universidad Politecnica De Valencia | Un material cristalino microporoso, zeolita itq-37, procedimiento de preparacion y uso. |
ES2302442B1 (es) * | 2006-07-31 | 2009-06-08 | Universidad Politecnica De Valencia | Aquilacion de compuestos aromaticos utilizando la zeolita itq-33. |
ES2303448B1 (es) * | 2006-08-01 | 2009-06-22 | Universidad Politecnica De Valencia | Craqueo catalitico de compuestos organicos utilizando la zeolita itq-33. |
ES2303449B1 (es) * | 2006-08-01 | 2009-06-22 | Universidad Politecnica De Valencia | Hidrocraqueo de compuestos organicos utilizando la zeolita itq-33. |
EP2099713B1 (en) * | 2006-12-07 | 2012-09-19 | ExxonMobil Research and Engineering Company | Itq-34, crystalline microporous material |
CN103384644B (zh) | 2010-11-23 | 2016-10-26 | 信实工业公司 | 一种mww型沸石的制备方法 |
BRPI1102638B1 (pt) * | 2011-06-16 | 2020-10-20 | Universidade Federal Do Rio Grande Do Sul | zeólita e materiais mesoporosos organizados como carga para a formulação de compostos de borracha, borracha termoplástica, plástico e fabricação de produtos |
US9205416B2 (en) * | 2011-08-04 | 2015-12-08 | Exxonmobil Chemical Patents Inc. | EMM-23 molecular sieve materials, its synthesis and use |
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US4676958A (en) * | 1985-03-06 | 1987-06-30 | Chevron Research Company | Preparation of crystalline zeolites using magadiite |
US5141729A (en) * | 1988-04-08 | 1992-08-25 | Mobil Oil Corporation | Synthesis of crystalline metalloaluminophosphate composition |
GB9116668D0 (en) * | 1991-08-01 | 1991-09-18 | British Petroleum Co Plc | Novel zeolite-type material |
US6043179A (en) * | 1997-08-13 | 2000-03-28 | California Institute Of Technology | Zeolite CIT-5 and method of making |
ES2186487B1 (es) * | 2000-10-11 | 2004-01-16 | Univ Valencia Politecnica | Zeolita itq-15. |
US6471941B1 (en) * | 2001-05-29 | 2002-10-29 | Exxonmobil Research And Engineering Company | Synthetic porous crystalline material ITQ-13, its synthesis and use |
ES2196963B1 (es) * | 2001-07-03 | 2005-02-16 | Universidad Politecnica De Valencia | Sintesis de itq-17 en ausencia de iones fluoruro. |
US6887159B2 (en) * | 2001-07-13 | 2005-05-03 | Gameaccount Limited | System and method for matching users of a gaming application |
ES2204257B1 (es) * | 2001-11-30 | 2005-05-01 | Universidad Politecnica De Valencia | Sintesis de itq-21 en ausencia de iones fluoruro. |
US6787124B2 (en) * | 2002-03-15 | 2004-09-07 | Exxonmobil Research And Engineering Company | Synthetic porous crystalline material, EMM-1, its synthesis and use |
US6723300B2 (en) * | 2002-03-15 | 2004-04-20 | Exxonmobil Research And Engineering Company | Synthesis of porous crystalline materials in fluoride media |
ES2217962B1 (es) * | 2003-02-14 | 2006-02-16 | Universidad Politecnica De Valencia | Material cristalino poroso (zeolita itq-24),su procedimiento de preparacion y su uso en la conversion catalitica de componentes organicos. |
FR2852024B1 (fr) * | 2003-03-05 | 2005-04-15 | Inst Francais Du Petrole | Solide cristallise im-10 et son procede de preparation |
FR2860224B1 (fr) * | 2003-09-26 | 2006-06-02 | Inst Francais Du Petrole | Solide cristallise im-12 et son procede de preparation |
FR2908127B1 (fr) * | 2006-11-07 | 2009-02-06 | Inst Francais Du Petrole | Solide cristallise im-15 et son procede de preparation |
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CN104487385A (zh) * | 2012-04-18 | 2015-04-01 | 康斯乔最高科学研究公司 | Itq-49材料、其生产方法及其用途 |
CN110831897A (zh) * | 2017-07-27 | 2020-02-21 | 埃克森美孚研究工程公司 | Emm-23材料及其制备方法和用途 |
CN113955770A (zh) * | 2021-11-11 | 2022-01-21 | 南京大学 | 一种超大孔itt结构硅酸盐分子筛材料及其制备方法 |
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CA2637272A1 (en) | 2006-07-20 |
ES2259537A1 (es) | 2006-10-01 |
EP1847510A4 (en) | 2011-03-02 |
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CN101124162B (zh) | 2011-02-16 |
US7947252B2 (en) | 2011-05-24 |
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