CN1487904A - 结晶状分子筛组合物mcm-65、其合成和应用 - Google Patents
结晶状分子筛组合物mcm-65、其合成和应用 Download PDFInfo
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- CN1487904A CN1487904A CNA018222498A CN01822249A CN1487904A CN 1487904 A CN1487904 A CN 1487904A CN A018222498 A CNA018222498 A CN A018222498A CN 01822249 A CN01822249 A CN 01822249A CN 1487904 A CN1487904 A CN 1487904A
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- 239000000203 mixture Substances 0.000 title claims description 21
- 239000002808 molecular sieve Substances 0.000 title abstract description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title abstract description 7
- 230000015572 biosynthetic process Effects 0.000 title 1
- 238000003786 synthesis reaction Methods 0.000 title 1
- 239000000463 material Substances 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 239000011541 reaction mixture Substances 0.000 claims abstract description 7
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 239000004411 aluminium Substances 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 8
- 229910052784 alkaline earth metal Chemical group 0.000 claims description 7
- 229910052728 basic metal Inorganic materials 0.000 claims description 7
- 150000003818 basic metals Chemical group 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical group 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- 150000002894 organic compounds Chemical class 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000002178 crystalline material Substances 0.000 abstract 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 18
- 229910021536 Zeolite Inorganic materials 0.000 description 17
- 239000010457 zeolite Substances 0.000 description 17
- 150000002500 ions Chemical class 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 238000001354 calcination Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- 239000004927 clay Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 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 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- -1 alkaline earth metal cation Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- 239000005995 Aluminium silicate Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 229960001866 silicon dioxide Drugs 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 235000019580 granularity Nutrition 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000005504 petroleum refining Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005630 Diquat Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 229910001649 dickite Inorganic materials 0.000 description 1
- ZKRXZOLGLXXMEA-UHFFFAOYSA-N dioxosilane zirconium Chemical compound [Zr].[Si](=O)=O ZKRXZOLGLXXMEA-UHFFFAOYSA-N 0.000 description 1
- SYJFEGQWDCRVNX-UHFFFAOYSA-N diquat Chemical compound C1=CC=[N+]2CC[N+]3=CC=CC=C3C2=C1 SYJFEGQWDCRVNX-UHFFFAOYSA-N 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000021321 essential mineral Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 229910003452 thorium oxide Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000010555 transalkylation reaction Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
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-
- 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
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
-
- 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
-
- 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
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/02—Crystalline silica-polymorphs, e.g. silicalites dealuminated aluminosilicate zeolites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
- C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
-
- C—CHEMISTRY; METALLURGY
- 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
- C10G35/00—Reforming naphtha
- C10G35/04—Catalytic reforming
- C10G35/06—Catalytic reforming characterised by the catalyst used
- C10G35/095—Catalytic reforming characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/42—Addition of matrix or binder particles
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及新型的合成多孔结晶状分子筛材料MCM－65、其制备反应混合物和方法以及MCM－65在有机化合物的催化转化中的应用。该结晶状材料具有如表1所示的独特的X－射线衍射图。
Description
发明背景
1.发明领域
本发明涉及新型的合成结晶状分子筛材料MCM-65、其制备方法及其在烃类转化中的应用。
2.现有技术的描述
在过去已证实天然的和合成的沸石材料都具有催化各种类型的烃类转化的性能。某些沸石材料是有序的、具有明确的晶体结构(如通过X-射线衍射所确定)的多孔结晶状硅铝酸盐，其中具有大量的可通过许多更小的通道或孔互相连接的小空穴。在一种特定的沸石材料内，这些空穴或孔的大小是均匀的。由于这些孔的大小既能接收某些尺寸的分子的吸附，又能拒收更大尺寸的那些分子，所以将这些材料称作“分子筛”并以各种方式使用以利用这些性能。
沸石通常具有约3埃至约10埃的均匀孔径。沸石的化学组成可以在宽范围内变化，但是它们通常由其中的一些Si原子可以被四价原子诸如Ti或Ge、三价原子诸如Al、B、Ga、Fe或二价原子诸如Be或其组合取代的SiO2组成。当被二价或三价原子取代时，还存在阳离子诸如Na、K、Ca、NH4或H。
沸石包括各种各样的含有正离子的结晶状硅铝酸盐。这些硅铝酸盐可以被描述为SiO4和AlO4的刚性三维骨架，其中四面体通过氧原子的共享进行交联，因此铝和硅原子的总量与氧原子的比率为1∶2。含有铝的四面体的电价通过在晶体内包含阳离子诸如碱金属、碱土金属阳离子或有机类诸如季铵阳离子来平衡。这可以表达为其中铝与各种阳离子例如Ca/2、Sr/2、Na、K或Li的数目的比率等于1。利用离子交换技术按照常规方式，一种类型的阳离子可以被另一种类型的阳离子全部或者部分交换。利用这种阳离子交换，通过适当地选择阳离子可以改变给定硅铝酸盐的性能。在脱水前四面体之间的空间通常被水分子所占有。
现有技术已形成了各种各样的合成硅铝酸盐。这些硅铝酸盐已用字母或其它方便符号所表示，如A沸石(美国专利2,882,243)、X沸石(美国专利2,882,244)、Y沸石(美国专利3,130,007)、ZK-5沸石(美国专利3,247,195)、ZK-4沸石(美国专利3,314,752)、ZSM-5沸石(美国专利3,702,886)、ZSM-11沸石(美国专利3,709,979)和ZSM-12沸石(美国专利3,832,449)。
ZSM-52及其含硼类似物ZSM-55分别记载于美国专利4,985,223和5,063,037。
美国专利4,637,923描述了多孔的结晶状材料MCM-47及其从含有作为指示剂的二乙基化直链二季铵化合物的反应混合物的合成。美国专利5,068,096公开了使用二(甲基吡啶烷鎓盐)-DIQUAT-4作为指示剂制备MCM-47的方法。因此，MCM-47沸石的合成需要含有二季铵阳离子化合物的长链二聚体模板剂。
相反，本发明利用单体指示剂而不是二聚体diquat试剂，并且提供了具有良好的孔隙率、明显提高的热稳定性的新型结晶状材料。
发明概述
本发明涉及命名为MCM-65的新型的合成结晶状分子筛组合物，其包含具有骨架结构的晶体，所述的骨架结构的特征在于基本上如下面的表1所述的独特的X-射线衍射图。
另外，本发明涉及合成MCM-65的方法以及MCM-65在有机化合物例如烃类化合物的催化转化中的应用。
附图简要说明
图1显示了实施例1中制备的合成出的MCM-65的X-射线衍射图。
图2显示了实施例1中制备的煅烧的MCM-65的X-射线衍射图。
图3是实施例2中制备的合成出的MCM-65的X-射线衍射图。
图4是实施例2中制备的煅烧的MCM-65的X-射线衍射图。
本发明的详述
本发明的合成的多孔结晶状材料MCM-65是单一结晶相，它的煅烧形式所具有的X-射线衍射图样因下面表1所列出的衍射线而不同于其它已知的合成出的或热处理的结晶状材料的衍射图样。
表1
| d-间距() | 相对强度 |
| 8.98±0.25 | vs |
| 6.92±0.20 | w-m |
| 6.81±0.42 | m-s |
| 6.11±0.34 | vw |
| 3.46±0.11 | vw-w |
| 3.40±0.22 | vw-w |
| 1.84±0.14 | vw |
这些X-射线衍射数据用配备有锗固态检测器的Scintag衍射系统收集，使用铜K-α射线。衍射数据通过2θ为0.02度的步进扫描进行记录，其中θ是布拉格角，每一步的计数时间为10秒。晶面间距d以埃为单位进行计算，并且利用轮廓固定模式(或者二次导出算法)得到衍射线的相对强度I/I0(其中I0是基线上最强衍射线的强度的百分之一)。强度对于Lorentz和极化效应是未校正的。相对强度按照符号vs＝非常强(80-100)、s＝强(60-80)、m＝中(40-60)、w＝弱(20-40)、vw＝非常弱(0-20)给出。应该理解，对于该样品作为单一衍射线列出的衍射数据可以由多条重叠衍射线组成，所述的多条重叠衍射线在某些条件下，例如结晶学变化的不同，可能表现为分辨的或部分分辨的衍射线。结晶学变化通常可以包括晶胞参数的微小变化和/或晶体对称性的变化而没有结构上的变化。这些微小效应(包括相对强度的变化)也因阳离子含量、骨架组成、孔填充的性质和程度、晶体的大小和形状、优选的取向以及热和/或水热过程的不同而出现。
MCM-65的合成形式的X-射线衍射图类似于MCM-47的X-射线衍射图，但是衍射峰的强度不同。一旦煅烧，所合成的材料转化成具有包括表1的衍射线的独特X-射线衍射图的MCM-65。另外，MCM-47对热不稳定，但是本发明的MCM-65对热稳定。
多孔的结晶状材料MCM-65具有涉及如下摩尔关系式的组成：
X2O3∶y(YO2)
其中X是三价元素，如铝、硼、铁、铟和/或镓，优选铝；Y是四价元素，如硅、锡和/或锗，优选硅；y至少为约200，通常为约400至大于约3000，更通常是为约500至约3000。
MCM-65可以在相对宽的X2O3/YO2的摩尔比率范围内，在混合的奎宁环和四甲基铵有机指示剂的存在下来合成。在合成的形式中，以无水氧化物的摩尔数/100摩尔四价元素氧化物计，结晶状材料的组成如下：
(0-20)R’2O∶(0-20)R”2O∶(0-5)(0-20)M2/nO∶(0-2)X2O3∶(100)YO2其中X和Y如上所定义，M是碱金属或碱土金属，n是M的化合价，R’和R”分别是指示剂氢氧化四甲基铵(TMAOH)和奎宁环。
按照本领域已知的技术，通过与其它阳离子进行交换，可以将所合成的结晶状材料中的原有的碱金属或碱土金属阳离子用另一种阳离子至少部分地取代。优选的取代阳离子包括金属离子、氢离子、氢前体例如铵离子及其混合物。特别优选的阳离子是使得所述新型沸石特别是对于烃类转化具有催化活性的那些阳离子。这些阳离子包括氢、稀土金属和元素周期表(New Notation)的第2、3、4、6、9、11、12、13和14族的金属。常用的离子交换技术是将合成沸石与所需的一种或多种取代阳离子的盐的水溶液接触。这样的盐类的例子包括卤化物例如氯化物、硝酸盐和硫酸盐。
将本发明的结晶状材料进行处理以部分地或全部地除去有机成分。这可通过热处理方便地进行，其中将所合成的材料在至少约370℃的温度下煅烧至少1分钟且通常不超过20小时。虽然煅烧可以采用低于大气压的压力，但是因方便原因而希望采用常压。煅烧可以在最高约925℃、优选约450℃至约700℃的温度下进行。煅烧后的产物，特别是其金属型、氢型和铵型尤其可用于催化某些有机物例如烃类的转化反应。
当本发明的结晶状材料用作吸附剂或有机化合物转化过程中的催化剂时，应当将其至少部分地脱水。这可通过在200℃至约370℃的温度下，在诸如空气、氮气等的气氛中，在常压、低于大气压或高于大气压的压力下加热30分钟至48小时来实现。脱水作用还可以在室温下仅通过将MCM-65放置在真空中进行，但是得到充分的脱水作用需要更长的时间。
本发明的MCM-65可以从含有水和碱金属或碱土金属(M)的氧化物、三价元素(X)的氧化物、四价元素(Y)的氧化物以及指示剂氢氧化四甲基铵(R’)和奎宁环(R”)的源的反应混合物来制备。以氧化物的摩尔比率计，反应混合物优选具有如下组成范围：
| 反应物 | 用量 | 优选量 |
| YO2/X2O3 | 10至∞ | 300至∞ |
| H2O/YO2 | 5至1000 | 10至200 |
| OH-/YO2 | 0.1至2.0 | 0.20-1.00 |
| M2/n/YO2 | 0.05至2.0 | 0.10至0.80 |
| R’/Y | 0.05至2.0 | 0.2至1.0 |
| R”/Y | 0.05至2.0 | 0.2至1.0 |
结晶可以在静态或搅拌条件下，例如在高压釜或静态弹式反应器内，在约80至约220℃、更优选约160℃至约180℃的温度下，进行在所用温度下足以发生结晶的一段时间，例如约24小时至约30天、更优选约96小时至约120小时。然后将晶体与液体分离并回收。所述组合物可以利用能够提供适宜氧化物的材料来制备。这样的组合物包括硅酸钠、二氧化硅水溶胶、硅胶、硅酸、氢氧化钠、氯化钠、硫酸铝、铝酸钠、氧化铝或铝本身。
通过存在至少0.001％、优选0.10％、更优选1％的结晶状产物的晶种(按照总重计)可有利于新晶体的合成。
煅烧的MCM-65的表面积为约100至约250m2/g，更通常为约166至约199m2/g，这意味着其是多孔材料。在一种实施方案中，该材料的己烷裂化试验所测定的α值为6。α试验记载于例如美国专利3,354,078和Journal of Catalysis，4：527(1965)；6：728(1996)和61：395(1980)。试验条件包括538℃的恒温以及可变流速，如Journalof Catalysis，61：395中所述。
通过本发明制备的组合物可以成型为各种各样的粒度。一般而言，微粒可以是粉末、颗粒或模制品的形式，例如粒度足以通过2目(Tyler)筛并留在400目(Tyler)筛上的挤出物。在催化剂被模制例如通过挤出进行模制的情况下，可以将晶体在干燥前挤出，或者部分干燥、然后挤出。
在多数催化剂的情况下，需要将本发明的MCM-65与另一种能够承受有机物的转化过程中所用的温度和其它条件的材料相结合。这样的材料包括活性或非活性材料和合成的或天然存在的沸石，以及无机材料如粘土、二氧化硅和/或金属氧化物。后者可以是天然存在的，或者是包括二氧化硅和金属氧化物的凝胶状沉淀物或凝胶。使用与本发明的组合物相混合的材料，即与活性物质相混合的材料趋于提高催化剂在某些有机转化过程中的转化率和/或选择性。非活性物质适于用作稀释剂以控制给定过程的转化量，从而在不用采用其它控制反应速率的方法的情况下经济有序地得到产物。可以将这些物质结合到天然存在的粘土例如膨润土和高岭土中，以提高催化剂在商用操作条件下的耐压强度。这样的物质即粘土、氧化物等起到催化剂的粘结剂或基质的作用。由于在石油炼制过程中催化剂经常要经受剧烈的操作，这往往使催化剂破碎成引起加工处理问题的粉末状物质，所以需要提供具有良好的耐压强度的催化剂。通常只是为了提高催化剂的耐压强度而使用这些粘土粘结剂。由于在石油炼制过程中催化剂经常要经受剧烈的操作，这往往使催化剂破碎成引起加工处理问题的粉末状物质，所以需要提供具有良好的耐压强度的催化剂。
可以与本发明的晶体混合的天然存在的粘土包括蒙脱土和高岭土家族。这些家族包括变膨润土和通常被称作Dixie、McNamee、Georgia和Florida粘土的高岭土，或者其中的主要矿物组成是hallosite、高岭石、地开石、珍珠石或蠕陶土的其它物质。这样的粘土可以以如原始开采的原始态使用，或者事先经过煅烧、酸处理或化学改性。用于与本发明的晶体混合的粘结剂还包括无机氧化物，尤其是氧化铝。
除了前述材料以外，本发明的硅铝酸盐分子筛可以与多孔基质材料如二氧化硅-氧化铝、二氧化硅-氧化镁、二氧化硅-氧化锆、二氧化硅-氧化钍、二氧化硅-氧化铍、二氧化硅-二氧化钛以及三元组合物如二氧化硅-氧化铝-氧化钍、二氧化硅-氧化铝-氧化锆、二氧化硅-氧化铝-氧化镁和二氧化硅-氧化镁-氧化锆相混合。
含有本发明的材料的催化剂组合物通常含有约1至90重量％的MCM-65和约10％至99重量％的粘结剂或基质材料。更优选这样的催化剂组合物含有约2％至80重量％的MCM-65和约20％至约98重量％的基质。
本发明的MCM-65结晶状分子筛还可以用作与附加的加氢组分例如钨、钒、钼、铼、镍、钴、铬、锰或贵金属如铂或钯紧密混合的催化剂，在该催化剂中实现了加氢-脱氢功能。这样的组分可以交换进入组合物至进入结构中的程度，浸渍入其中或者与其物理紧密混合。例如，在铂的情况下，通过用含有含铂金属离子的溶液处理晶体可以将这样的组分浸入到晶体中或者浸渍到晶体上。因此，适当的铂化合物包括氯铂酸、二氯化铂和各种含有铂胺络合物的化合物。
使用含有加氢组分的本发明组合物的催化活性形式，在约300℃至约600℃的温度下，可以将重整原料进行重整。压力可以为约100至约1000psig，但优选约200至约700psig。液时空速通常为约0.1至约10，优选约0.5至约4，氢气与烃类的摩尔比率通常为约1至约20，优选约4至约12。
从本发明的沸石制备的催化剂还可用于降低瓦斯油的倾点。所述的降低在液时空速为约10至约30、温度为约400℃至约600℃的条件下进行。
利用从本发明的沸石制备的含有或不含有金属例如铂和钯的催化剂得以实现的其它反应包括加氢-脱氢反应和脱硫反应、烯烃聚合(低聚反应)、与C2-C12烯烃或与C1-C12醇类的芳烃烷基化、烯烃和芳香族化合物的异构化、烷基芳香族化合物的歧化反应和烷基转移反应或其它有机化合物的转化如醇类(例如甲醇)生成烃类的转化。
下面的非限制性实施例将进一步解释本发明。
实施例1
将35g胶体二氧化硅(30wt％SiO2)、Al(OH)3、NaOH(20wt％的溶液)、奎宁环(固体)、TMAOH(25wt％的溶液)和蒸馏水按照如下摩尔比率进行混合：
Si/Al2 500
H2O/Si 30
OH/Si 0.35
Na/Si 0.15
TMAOH/Si 0.2
奎宁环/Si 0.2
将所混合的混合物加入到高压搅拌釜中并在100rpm及180℃下加热96小时。然后将产物过滤并用水洗涤。将合成出的材料在540℃煅烧得到命名为MCM-65的新材料。将合成出的和煅烧后的材料的粉末衍射图分别在图1和2中给出。形成的结晶状材料的表面积为199m2/g。
实施例2
将35g胶体二氧化硅(30wt％SiO2)、Al(OH)3、NaOH(20wt％的溶液)、奎宁环、TMAOH(25wt％的溶液)和蒸馏水按照如下摩尔比率进行混合：
Si/Al2 2000
H2O/Si 30
OH/Si 0.35
Na/Si 0.15
TMAOH/Si 0.20
奎宁环/Si 0.20
将所混合的混合物加入到高压搅拌釜中并在100rpm及180℃下加热96小时。然后将产物过滤并用水洗涤。将合成出的材料在540℃煅烧得到命名为MCM-65的新材料。将合成出的和煅烧后的材料的粉末衍射图分别在图3和4中给出。形成的结晶状材料的表面积为166m2/g。
表2列出了实施例1和2的煅烧材料MCM-65的粉末衍射图的衍射峰的相对强度。
表2
| 实施例1 | 实施例2 | ||
| d-间距 | I/I0×100 | d-间距 | I/I0×100 |
| 8.98 | 100 | 9.13** | 100 |
| 6.92 | 31 | 6.94 | 30 |
| 6.81 | 61 | 6.82 | 67 |
| 6.11 | 9 | 6.13 | 10 |
| 5.48 | 4 | 5.51 | 3 |
| 4.85 | 2 | 4.87 | 3 |
| 4.48 | 1 | ---- | ---- |
| 4.40 | 4 | 4.43 | 2 |
| 4.10 | 4 | 4.11 | 2 |
| 3.86 | 5 | 3.88 | 4 |
| 3.82 | 4 | 3.83 | 4 |
| 3.68 | 7 | 3.68 | 8 |
| 3.46 | 12 | 3.48 | 9 |
| 3.40 | 16 | 3.41 | 19 |
| 3.34* | 1 | 3.34 | 7 |
| 3.30 | 6 | 3.31 | 8 |
| 3.22 | 1 | 3.25 | 2 |
| 1.84 | 2 | 1.84 | 1 |
| *衍射峰可能是石英或石英增强的 | **料衍射峰可能是部分分解的双重峰 | ||
Claims (8)
1、一种合成的多孔结晶状材料，其具有说明书的表1中列出的包括数值在内的X-射线衍射图。
2、根据权利要求1所述的结晶状材料，其具有包含如下摩尔关系式的组成：
X2O3∶(y)YO2
其中y为至少约200，X是三价元素，Y是四价元素。
3、根据权利要求2所述的结晶状材料，在无水基础上以氧化物的摩尔数/100摩尔四价元素氧化物计，该结晶状材料的组成如下：
(0-20)R’2O∶(0-20)R”2O∶(0-5)(0-20)M2/nO∶(0-2)X2O3∶(100)YO2M是碱金属或碱土金属，n是M的化合价，R’和R”分别是氢氧化四甲基铵(TMAOH)和奎宁环。
4、根据权利要求2所述的结晶状材料，其中X是选自铝、硼、铁、铟、镓及其组合的三价元素；Y是选自硅、锡、钛、锗及其组合的四价元素。
5、根据权利要求2所述的结晶状材料，其中X包含铝且Y包含硅。
6、一种制备权利要求1所述的结晶状材料的方法，该方法包括：
(a)制备能形成所述材料的反应混合物，所述的混合物含有四价元素(Y)的氧化物、三价元素(X)的氧化物、碱金属或碱土金属(M)、有机指示剂R’和R”的源和水，以氧化物的摩尔比率计，所述的反应混合物具有如下组成：
YO2/X2O3 10至∞
H2O/YO2 5至1000
OH-/YO2 0.1至2
M2/n/YO2 0.05至2
R’/Y 0.05至2，和
R”/Y 0.05至2
其中n是碱金属或碱土金属M的化合价，R’和R”分别是奎宁环和四甲基铵；和
(b)将所述的混合物保持在结晶条件下，直至形成所述的结晶状材料的晶体。
7、根据权利要求6所述的方法，其中所述的反应混合物包含如下组成范围：
YO2/X2O3 300至∞
H2O/YO2 10至200
OH-/YO2 0.2至1
M2/n/YO2 0.1至0.8
R’/Y 0.2至1，和
R”/Y 0.2至1。
8、一种含烃原料的催化转化方法，该方法包括在催化转化条件下将所述的原料与含有权利要求1的结晶状材料的活性形式的催化剂接触。
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| US25324500P | 2000-11-27 | 2000-11-27 | |
| US60/253,245 | 2000-11-27 |
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| EP (1) | EP1351884A1 (zh) |
| CN (1) | CN1487904A (zh) |
| AR (1) | AR031496A1 (zh) |
| AU (1) | AU2002219833A1 (zh) |
| CA (1) | CA2439439A1 (zh) |
| RU (1) | RU2282588C2 (zh) |
| TW (1) | TW574142B (zh) |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103180042A (zh) * | 2010-10-15 | 2013-06-26 | 埃克森美孚化学专利公司 | 选择改进的催化剂组合物和使用所述催化剂组合物的烃转化方法 |
| CN104903235A (zh) * | 2012-11-05 | 2015-09-09 | 巴斯夫欧洲公司 | 具有mww型骨架结构的含锡沸石材料 |
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| FR2852024B1 (fr) | 2003-03-05 | 2005-04-15 | Inst Francais Du Petrole | Solide cristallise im-10 et son procede de preparation |
| US7867474B2 (en) | 2004-09-20 | 2011-01-11 | Uop Llc | Crystalline aluminosilicates: UZM-13, UZM-17, UZM-19 and UZM-25 |
| US8500991B2 (en) * | 2008-12-16 | 2013-08-06 | Exxonmobil Research And Engineering Company | High activity MTT framework type molecular sieves |
| RU2467793C2 (ru) * | 2011-02-03 | 2012-11-27 | Открытое акционерное общество "Научно-исследовательский институт конструкционных материалов на основе графита "НИИграфит" | Углеродное молекулярное сито |
| WO2019038571A1 (en) * | 2017-08-23 | 2019-02-28 | Khalifa University of Science and Technology | HIGH YIELD YIELD LOW TEMPERATURE CONTROLLABLE PARTICLE SIZE Y NANOZEOLITE Y CRYSTAL |
| CN113050745B (zh) * | 2020-12-22 | 2022-05-06 | 三峡大学 | 选秀竞争算法dca及基于该算法的光伏系统最大功率点跟踪方法 |
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| US4376757A (en) * | 1979-11-07 | 1983-03-15 | National Distillers & Chemical Corp. | Synthetic crystalline silicate compositions and preparation thereof |
| DE3274844D1 (en) * | 1981-04-14 | 1987-02-05 | Ici Plc | Zeolites |
| JPS6183621A (ja) * | 1984-09-05 | 1986-04-28 | モ−ビル オイル コ−ポレ−シヨン | 結晶性メタロシリケ−ト、その合成法及び有機転化反応に於けるその利用 |
| US4985223A (en) * | 1984-09-17 | 1991-01-15 | Mobil Oil Corporation | Crystalline aluminosilicate |
| US4721607A (en) * | 1986-01-31 | 1988-01-26 | Amoco Corporation | Process for the production of boronaaronate molecular sieve using ethylenediamine and quinoline or isoquinoline |
| US4954325A (en) * | 1986-07-29 | 1990-09-04 | Mobil Oil Corp. | Composition of synthetic porous crystalline material, its synthesis and use |
| US5013536A (en) * | 1988-08-22 | 1991-05-07 | Exxon Research And Engineering Company | ECR-18, method of its preparation, and uses for sorption and separation |
| GB8818452D0 (en) * | 1988-08-03 | 1988-09-07 | British Petroleum Co Plc | Process for preparation of crystalline(metallo)silicates & germanates |
| US5068096A (en) * | 1991-04-08 | 1991-11-26 | Mobil Oil Corporation | Synthesis of crystalline silicate MCM-47 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103180042A (zh) * | 2010-10-15 | 2013-06-26 | 埃克森美孚化学专利公司 | 选择改进的催化剂组合物和使用所述催化剂组合物的烃转化方法 |
| CN103180042B (zh) * | 2010-10-15 | 2015-07-22 | 埃克森美孚化学专利公司 | 选择改进的催化剂组合物和使用所述催化剂组合物的烃转化方法 |
| CN104903235A (zh) * | 2012-11-05 | 2015-09-09 | 巴斯夫欧洲公司 | 具有mww型骨架结构的含锡沸石材料 |
| CN104903235B (zh) * | 2012-11-05 | 2017-07-14 | 巴斯夫欧洲公司 | 具有mww型骨架结构的含锡沸石材料 |
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| WO2002042208A1 (en) | 2002-05-30 |
| RU2003119450A (ru) | 2005-02-10 |
| RU2282588C2 (ru) | 2006-08-27 |
| ZA200304934B (en) | 2004-05-06 |
| US20040047802A1 (en) | 2004-03-11 |
| AU2002219833A1 (en) | 2002-06-03 |
| TW574142B (en) | 2004-02-01 |
| AR031496A1 (es) | 2003-09-24 |
| CA2439439A1 (en) | 2002-05-30 |
| US6869587B2 (en) | 2005-03-22 |
| EP1351884A1 (en) | 2003-10-15 |
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