JP5990594B2 - 高活性大結晶zsm−5の合成 - Google Patents
高活性大結晶zsm−5の合成 Download PDFInfo
- Publication number
- JP5990594B2 JP5990594B2 JP2014544807A JP2014544807A JP5990594B2 JP 5990594 B2 JP5990594 B2 JP 5990594B2 JP 2014544807 A JP2014544807 A JP 2014544807A JP 2014544807 A JP2014544807 A JP 2014544807A JP 5990594 B2 JP5990594 B2 JP 5990594B2
- Authority
- JP
- Japan
- Prior art keywords
- zsm
- sio
- reaction mixture
- crystals
- less
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000013078 crystal Substances 0.000 title claims description 47
- 238000003786 synthesis reaction Methods 0.000 title description 14
- 230000015572 biosynthetic process Effects 0.000 title description 13
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 60
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 48
- 239000000203 mixture Substances 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 40
- 239000011541 reaction mixture Substances 0.000 claims description 33
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000000377 silicon dioxide Substances 0.000 claims description 19
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 15
- 239000010457 zeolite Substances 0.000 claims description 14
- 229910021536 Zeolite Inorganic materials 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 7
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 5
- 239000000174 gluconic acid Substances 0.000 claims description 5
- 235000012208 gluconic acid Nutrition 0.000 claims description 5
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000000463 material Substances 0.000 description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 239000003054 catalyst Substances 0.000 description 25
- -1 alkali metal cation Chemical class 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000000047 product Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 12
- 229920001296 polysiloxane Polymers 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000007323 disproportionation reaction Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 229910001388 sodium aluminate Inorganic materials 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 235000001014 amino acid Nutrition 0.000 description 4
- 150000001413 amino acids Chemical class 0.000 description 4
- NOWPEMKUZKNSGG-UHFFFAOYSA-N azane;platinum(2+) Chemical compound N.N.N.N.[Pt+2] NOWPEMKUZKNSGG-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 229950006191 gluconic acid Drugs 0.000 description 4
- 239000003112 inhibitor 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
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 4
- 230000006911 nucleation Effects 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 3
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 150000001924 cycloalkanes Chemical class 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 229960001484 edetic acid Drugs 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- KDXKERNSBIXSRK-UHFFFAOYSA-N lysine Chemical compound NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 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
- 238000002156 mixing Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- UPMFZISCCZSDND-JJKGCWMISA-M sodium gluconate Chemical compound [Na+].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O UPMFZISCCZSDND-JJKGCWMISA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- VSIKJPJINIDELZ-UHFFFAOYSA-N 2,2,4,4,6,6,8,8-octakis-phenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound O1[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si]1(C=1C=CC=CC=1)C1=CC=CC=C1 VSIKJPJINIDELZ-UHFFFAOYSA-N 0.000 description 1
- VCYDUTCMKSROID-UHFFFAOYSA-N 2,2,4,4,6,6-hexakis-phenyl-1,3,5,2,4,6-trioxatrisilinane Chemical compound O1[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si]1(C=1C=CC=CC=1)C1=CC=CC=C1 VCYDUTCMKSROID-UHFFFAOYSA-N 0.000 description 1
- PFZMRLJAZFISGP-UHFFFAOYSA-N 2-(2-adamantylazaniumyl)acetate Chemical compound C1C(C2)CC3CC1C([NH2+]CC(=O)[O-])C2C3 PFZMRLJAZFISGP-UHFFFAOYSA-N 0.000 description 1
- OQMYZVWIXPPDDE-UHFFFAOYSA-N 2-(cyclohexylazaniumyl)acetate Chemical compound OC(=O)CNC1CCCCC1 OQMYZVWIXPPDDE-UHFFFAOYSA-N 0.000 description 1
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 1
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- 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
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 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
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 229960002684 aminocaproic acid Drugs 0.000 description 1
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 239000011324 bead Substances 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
- CCDWGDHTPAJHOA-UHFFFAOYSA-N benzylsilicon Chemical compound [Si]CC1=CC=CC=C1 CCDWGDHTPAJHOA-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000002288 cocrystallisation Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 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
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000011738 major mineral Substances 0.000 description 1
- 235000011963 major mineral Nutrition 0.000 description 1
- 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 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910052605 nesosilicate Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 150000004762 orthosilicates Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000012254 powdered material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 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
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
- C07C6/08—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond
- C07C6/12—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring
- C07C6/123—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring of only one hydrocarbon
-
- 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
- B01J2229/12—After treatment, characterised by the effect to be obtained to alter the outside of the crystallites, e.g. selectivation
- B01J2229/123—After treatment, characterised by the effect to be obtained to alter the outside of the crystallites, e.g. selectivation in order to deactivate outer surface
-
- 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
- B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
を特徴とすることができるシロキサンを挙げることができるが、これらに限定されるものではない。R1基およびR2基中の炭化水素置換基は、一般にそれぞれ1〜10個の炭素原子を含有することができる(たとえば、ある実施形態においてはメチル、エチル、および/またはフェニルを含有する基が好ましくなりうる)。使用されるシロキサンの(数平均)分子量は、一般に約80g/mol〜約20,000g/mol(たとえば約150g/mol〜約10,000g/mol)であり得る。代表的なシロキサンとしては、ジメチルシリコーン、ジエチルシリコーン、フェニルメチルシリコーン、メチル水素シリコーン、エチル水素シリコーン、フェニル水素シリコーン、メチルエチルシリコーン、フェニルエチルシリコーン、ジフェニルシリコーン、メチルトリフルオロプロピルシリコーン、エチルトリフルオロプロピルシリコーン、ポリジメチルシリコーン、テトラクロロフェニルメチルシリコーン、テトラクロロフェニルエチルシリコーン、テトラクロロフェニル水素シリコーン、テトラクロロフェニルフェニルシリコーン、メチルビニルシリコーン、エチルビニルシリコーンなど、ならびにそれらの組み合わせおよび/またはコポリマーを挙げることができるが、これらに限定されるものではない。シロキサン化合物は、直鎖である必要はなく、分岐および/または環状(たとえば、ヘキサメチルシクロトリシロキサン、オクタメチルシクロテトラシロキサン、ヘキサフェニルシクロトリシロキサン、オクタフェニルシクロテトラシロキサンなど、およびそれらの組み合わせ)であってよい。これに加えて、またはこれと交代にこれらの化合物の混合物を使用することができ、他の官能基を有するシロキサン/シリコーンを使用することもできる。
本明細書に記載された主な形態を以下に示す。
1.テンプレートの非存在下での高活性大結晶ZSM−5型ゼオライトの製造方法であって:
(a)水、150m 2 /g未満の表面積を有するシリカ源、アルミナ源、シード、アルカリ金属酸化物の供給源M及び、グルコン酸またはその塩の供給源Qを含む反応混合物を調製するステップであって、前記混合物が、40以下のSiO 2 /Al 2 O 3 モル比を有するステップ;
(b)前記反応混合物を約100℃〜200℃の結晶化温度で、ZSM−5の結晶を形成するために十分な時間加熱するステップ;
(c)前記反応混合物から、40以下のSiO 2 /Al 2 O 3 モル比を有するZSM−5の結晶を回収するステップであって、前記結晶の大部分は、少なくとも約2μmの少なくとも1つの結晶寸法を有するステップを含む、製造方法。
2.前記シリカ源が、125m 2 /g未満の比表面積を有する、上記1に記載の方法。
3.前記反応混合物が:
SiO 2 /Al 2 O 3 :最大約40/1;
H 2 O/SiO 2 :約5〜約50;
OH − /SiO 2 :約0.05〜約0.5
M/SiO 2 ;約0.05〜約0.5;および
Q/SiO 2 :約0.05〜約1.0
の量のモル組成を有する、上記1または2に記載の方法。
4.前記反応混合物が、約15/1〜約40/1のSiO 2 /Al 2 O 3 モル比を有する、上記1〜3のいずれかに記載の方法。
5.加熱ステップ(b)が、約2時間〜約100時間の時間で行われる、上記1〜4のいずれかに記載の方法。
6.前記反応混合物が、前の合成で得たZSM−5シードを含有する、上記1〜5のいずれかに記載の方法。
7.前記反応混合物が、25℃において1000cP未満の粘度を有する、上記1〜6のいずれかに記載の方法。
8.ステップ(c)で回収される前記ZSM−5が、35以下のSiO 2 /Al 2 O 3 モル比を有する、上記1〜7のいずれかに記載の方法。
9.上記1〜8のいずれかに記載の製造方法によって製造されたZSM−5。
10.転化条件下、トルエン供給材料を、上記1〜8のいずれかに記載の製造方法によって製造された活性およびケイ素選択化型のZSM−5と接触させるステップを含む、トルエンからパラキシレンへの選択的不均化方法。
以下のモル組成を得るのに十分な量のSipernat(登録商標)−320シリカ、硫酸アルミニウム、NaOH、および脱イオン水を含む反応混合物からZSM−5結晶を合成した:
SiO2/Al2O3:約40
H2O/SiO2:約13.9
OH−/SiO2:約0.27
約950グラムの水、それぞれ約270グラムのSipernat(登録商標)−120または−350、約40グラムのアルミン酸ナトリウム溶液(水中45%)、および69グラムの50%水酸化ナトリウム水溶液から混合物を調製した。次に約9グラムのZSM−5シードを混合物に加えた。得られた混合物は以下のモル組成を示した:
SiO2/Al2O3:約40
H2O/SiO2:約13.9
OH−/SiO2:約0.27
約950グラムの水、約273グラムのSipernat(登録商標)−120、約45グラムのアルミン酸ナトリウム溶液(水中45%)、約89グラムのトリエタノールアミン(TEA)溶液(98%)、および約69グラムの50%水酸化ナトリウム水溶液混合物を調製した。次に約9グラムのZSM−5シードを混合物に加えた。得られた混合物は以下のモル組成を示した:
SiO2/Al2O3:約36
H2O/SiO2:約13.9
OH−/SiO2:約0.29
Na+/SiO2:約0.29
約950グラムの水、約270グラムのSipernat(登録商標)−120、約40グラムのアルミン酸ナトリウム溶液(水中45%)、約43グラムのd−グルコン酸一ナトリウム塩、および約69グラムの50%水酸化ナトリウム水溶液から混合物を調製した。次に約9グラムのZSM−5シードを混合物に加えた。得られた混合物は以下のモル組成を示した:
SiO2/Al2O3:約40
H2O/SiO2:約13.9
OH−/SiO2:約0.27
約9.5kgの水、約2.7kgのSipernat(登録商標)−120、約400グラムのアルミン酸ナトリウム溶液(水中45%)、約430グラムのd−グルコン酸一ナトリウム塩、および約690グラムの50%水酸化ナトリウム水溶液から混合物を調製した。次に約20グラムのZSM−5シードを混合物に加えた。得られた混合物は以下のモル組成を示した:
SiO2/Al2O3:約40
H2O/SiO2:約13.9
OH−/SiO2:約0.27
約955グラムの水、約273グラムのSipernat(登録商標)−120、約40グラムのアルミン酸ナトリウム溶液(水中45%)、約89グラムのトリエタノールアミン(TEA)溶液(98%)、および約75グラムの50%水酸化ナトリウム水溶液から混合物を調製した。次に約9グラムのZSM−5シードを混合物に加えた。得られた混合物は以下のモル組成を示した:
SiO2/Al2O3:約40
H2O/SiO2:約13.9
OH−/SiO2:約0.2
Na+/SiO2:約0.27
約65部(約538℃で焼成したものに基づく)の実施例5のZSM−5結晶を約35部の通常のUltrasil(商標)コロイダルシリカ混合物とLancasterミキサー中で混合した。十分な水を加えて、約2インチのBonnot押出機上で押出可能なペーストを形成した。実施例5のZSM−5、シリカ、および水を含有するペーストの混合物を押し出し、ホットパックオーブン中約121℃で終夜(約8〜16時間)乾燥させた。得られた押出物の圧壊強度を観測すると約125ポンド/インチであった。乾燥させた押出物を窒素中約538℃で焼成して、生成物を焼成Na型に変換した。N2焼成押出物を飽和空気で加湿し、約1N硝酸アンモニウム水溶液で交換して、ナトリウムを約500ppm未満のレベルまで除去した。硝酸アンモニウム交換の後、乾燥する前に、押出物を脱イオン水で洗浄して残留硝酸イオンを除去した。アンモニウム交換した押出物を約121℃で終夜(約8〜16時間)乾燥させ、空気中約538℃で焼成した。空気焼成後、得られたH型押出物は、約620のアルファ値を示した。
Claims (8)
- テンプレートの非存在下での高活性大結晶ZSM−5型ゼオライトの製造方法であって:
(a)水、150m2/g未満の表面積を有するシリカ源、アルミナ源、シード、アルカリ金属酸化物の供給源M及び、グルコン酸またはその塩の供給源Qを含む反応混合物を調製するステップであって、前記混合物が、40以下のSiO2/Al2O3モル比を有するステップ;
(b)前記反応混合物を100℃〜200℃の結晶化温度で、ZSM−5の結晶を形成するために十分な時間加熱するステップ;
(c)前記反応混合物から、40以下のSiO2/Al2O3モル比を有するZSM−5の結晶を回収するステップであって、前記結晶の過半数は、少なくとも2μmの少なくとも1つの結晶寸法を有するステップを含む、製造方法。 - 前記シリカ源が、125m2/g未満の比表面積を有する、請求項1に記載の方法。
- 前記反応混合物が:
SiO2/Al2O3:最大40/1;
H2O/SiO2:5〜50;
OH−/SiO2:0.05〜0.5
M/SiO2;0.05〜0.5;および
Q/SiO2:0.05〜1.0
の量のモル組成を有する、請求項1または2に記載の方法。 - 前記反応混合物が、15/1〜40/1のSiO2/Al2O3モル比を有する、請求項1〜3のいずれかに記載の方法。
- 加熱ステップ(b)が、2時間〜100時間の時間で行われる、請求項1〜4のいずれかに記載の方法。
- 前記反応混合物が、ZSM−5シードを含有する、請求項1〜5のいずれかに記載の方法。
- 前記反応混合物が、25℃において1000cP未満の粘度を有する、請求項1〜6のいずれかに記載の方法。
- ステップ(c)で回収される前記ZSM−5が、35以下のSiO2/Al2O3モル比を有する、請求項1〜7のいずれかに記載の方法。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201161565635P | 2011-12-01 | 2011-12-01 | |
US61/565,635 | 2011-12-01 | ||
PCT/US2012/066588 WO2013081994A1 (en) | 2011-12-01 | 2012-11-27 | Synthesis of high activity large crystal zsm-5 |
Publications (3)
Publication Number | Publication Date |
---|---|
JP2015507591A JP2015507591A (ja) | 2015-03-12 |
JP2015507591A5 JP2015507591A5 (ja) | 2016-08-25 |
JP5990594B2 true JP5990594B2 (ja) | 2016-09-14 |
Family
ID=47279156
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2014544807A Expired - Fee Related JP5990594B2 (ja) | 2011-12-01 | 2012-11-27 | 高活性大結晶zsm−5の合成 |
Country Status (9)
Country | Link |
---|---|
US (1) | US8900547B2 (ja) |
EP (1) | EP2785645B1 (ja) |
JP (1) | JP5990594B2 (ja) |
KR (1) | KR101858310B1 (ja) |
CN (1) | CN103958411B (ja) |
BR (1) | BR112014012577A2 (ja) |
CA (1) | CA2855875C (ja) |
SG (1) | SG11201402190SA (ja) |
WO (1) | WO2013081994A1 (ja) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102220082B1 (ko) * | 2019-07-23 | 2021-02-25 | 노경태 | 신규 구조 및 타래형 모폴로지를 갖는 알루미노실리케이트 구조체, 이의 제조방법 및 이를 고정상으로 충진한 hplc 컬럼 |
CN114426455B (zh) * | 2020-09-28 | 2024-07-23 | 中国石油化工股份有限公司 | 一种苯和乙烯烷基化反应 |
CN114478274B (zh) * | 2020-10-27 | 2024-06-28 | 中国石油化工股份有限公司 | 一种制备一乙醇胺并联产二甘醇的方法 |
CN114620743A (zh) * | 2020-12-11 | 2022-06-14 | 中国科学院大连化学物理研究所 | 一种大晶粒rho-sapo分子筛、其制备方法及其应用 |
FR3141080A1 (fr) | 2022-10-19 | 2024-04-26 | Arkema France | Procédé de synthèse de zéolithe zsm-5 en continu |
Family Cites Families (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3354078A (en) | 1965-02-04 | 1967-11-21 | Mobil Oil Corp | Catalytic conversion with a crystalline aluminosilicate activated with a metallic halide |
US3702886A (en) | 1969-10-10 | 1972-11-14 | Mobil Oil Corp | Crystalline zeolite zsm-5 and method of preparing the same |
US3676063A (en) * | 1971-03-11 | 1972-07-11 | Nalco Chemical Co | Process for preparing synthetic crystalline zeolitic sodium aluminosilicate |
US3941871A (en) | 1973-11-02 | 1976-03-02 | Mobil Oil Corporation | Crystalline silicates and method of preparing the same |
US4088605A (en) * | 1976-09-24 | 1978-05-09 | Mobil Oil Corporation | ZSM-5 containing aluminum-free shells on its surface |
NZ193928A (en) | 1979-06-11 | 1982-09-07 | Mobil Oil Corp | Preparation of large crystal zeolite zsm-5 |
AU559968B2 (en) * | 1982-04-29 | 1987-03-26 | Mobil Oil Corp. | Controlled morphology high silica zeolites |
JPH0227283B2 (ja) * | 1982-10-01 | 1990-06-15 | Toray Industries | Ketsushoseiaruminoshirikeetozeoraitonoseizoho |
US4797267A (en) * | 1987-12-23 | 1989-01-10 | Mobil Oil Corporation | Method of producing rod-shaped ZSM-5 zeolite |
JP2618021B2 (ja) * | 1988-10-03 | 1997-06-11 | 工業技術院長 | 真球状ペンタシル型ゼオライト粉体の合成方法 |
JP2844098B2 (ja) * | 1989-12-20 | 1999-01-06 | 旭化成工業株式会社 | Zsm―5微粒子体の製造法 |
US5164169A (en) * | 1991-06-14 | 1992-11-17 | Mobil Oil Corporation | Zeolite Beta |
KR100385653B1 (ko) | 1995-06-06 | 2003-10-10 | 엑손모빌 오일 코포레이션 | 대결정zsm-5,그의합성법및용도 |
US20020011429A1 (en) * | 1997-09-30 | 2002-01-31 | Akira Iino | Iron-containing crystalline aluminosilicate |
CA2446970C (en) * | 2001-05-10 | 2012-09-25 | Akzo Nobel Nv | Continuous process and apparatus for the efficient conversion of inorganic solid particles |
KR100528672B1 (ko) * | 2002-12-30 | 2005-11-15 | 학교법인 건국대학교 | 유기 템플레이트 배제 하에서 가변 온도를 이용하여zsm-5를 제조하는 방법 |
US7361328B2 (en) * | 2002-12-30 | 2008-04-22 | Sk Corporation | Method of preparing ZSM-5 using variable temperature without organic template |
JP5717447B2 (ja) * | 2008-02-22 | 2015-05-13 | エクソンモービル・ケミカル・パテンツ・インク | 大きな結晶の分子篩およびその製造 |
CN101722033A (zh) * | 2008-10-28 | 2010-06-09 | 中国石油化工股份有限公司 | 核壳型芳烃转化催化剂及其制备方法和用途 |
-
2012
- 2012-11-27 CA CA2855875A patent/CA2855875C/en not_active Expired - Fee Related
- 2012-11-27 CN CN201280059159.XA patent/CN103958411B/zh active Active
- 2012-11-27 WO PCT/US2012/066588 patent/WO2013081994A1/en active Application Filing
- 2012-11-27 US US13/685,794 patent/US8900547B2/en active Active
- 2012-11-27 EP EP12795305.7A patent/EP2785645B1/en not_active Not-in-force
- 2012-11-27 BR BR112014012577A patent/BR112014012577A2/pt active Search and Examination
- 2012-11-27 KR KR1020147018034A patent/KR101858310B1/ko active IP Right Grant
- 2012-11-27 SG SG11201402190SA patent/SG11201402190SA/en unknown
- 2012-11-27 JP JP2014544807A patent/JP5990594B2/ja not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
WO2013081994A1 (en) | 2013-06-06 |
US20130144100A1 (en) | 2013-06-06 |
SG11201402190SA (en) | 2014-09-26 |
KR20140108665A (ko) | 2014-09-12 |
BR112014012577A2 (pt) | 2017-06-06 |
KR101858310B1 (ko) | 2018-05-15 |
EP2785645B1 (en) | 2017-06-14 |
CA2855875C (en) | 2018-08-14 |
EP2785645A1 (en) | 2014-10-08 |
JP2015507591A (ja) | 2015-03-12 |
CA2855875A1 (en) | 2013-06-06 |
US8900547B2 (en) | 2014-12-02 |
CN103958411B (zh) | 2016-08-24 |
CN103958411A (zh) | 2014-07-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI360435B (en) | Process for manufacturing molecular sieve of mfs f | |
EP3253713B1 (en) | Molecular sieves and processes for preparing these molecular sieves | |
JP6386562B2 (ja) | Zsm−48結晶の合成 | |
JP6106759B2 (ja) | Mseフレームワーク型モレキュラーシーブの合成 | |
US20110117007A1 (en) | Method for making mfi-type molecular sieves | |
JP5990594B2 (ja) | 高活性大結晶zsm−5の合成 | |
KR20080091810A (ko) | 분자체의 고 처리량 제조 방법 | |
KR20150082443A (ko) | 소결정 페리에라이트 및 이를 제조하는 방법 | |
JPS62501275A (ja) | 結晶性マグネシア―シリカ触媒及びその製法 | |
JP5668422B2 (ja) | アルミノシリケートの製造方法 | |
JP2021500286A (ja) | モレキュラーシーブssz−112、その合成及び使用 | |
WO2018080640A1 (en) | Synthesis of mtw framework type molecular sieves | |
CN110248894B (zh) | 分子筛ssz-109、其合成和用途 | |
CN110300729B (zh) | 分子筛ssz-111、其合成和用途 | |
JP2021513959A (ja) | Emm−37材料並びにその方法及び使用 | |
CN1166751C (zh) | 形状选择性沸石催化剂及其在芳族化合物转化中的应用 | |
CA2436605C (en) | Crystalline molecular sieves | |
JP4345910B2 (ja) | 人工多孔性結晶質mcm−71,その合成及び用途 | |
CA2872869C (en) | Zeolite zsm-18, its synthesis and its use | |
JP2014518831A (ja) | M41s族モレキュラーシーブの合成およびその使用 | |
CN114258386B (zh) | 分子筛ssz-118、其合成及用途 | |
TWI529132B (zh) | 分子篩材料,其合成及用途 | |
JP2022519152A (ja) | モレキュラーシーブssz-63を調製する方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20151007 |
|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20151007 |
|
A871 | Explanation of circumstances concerning accelerated examination |
Free format text: JAPANESE INTERMEDIATE CODE: A871 Effective date: 20151007 |
|
RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20160217 |
|
A975 | Report on accelerated examination |
Free format text: JAPANESE INTERMEDIATE CODE: A971005 Effective date: 20160310 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20160314 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20160322 |
|
A524 | Written submission of copy of amendment under article 19 pct |
Free format text: JAPANESE INTERMEDIATE CODE: A524 Effective date: 20160622 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20160802 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20160815 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 5990594 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
LAPS | Cancellation because of no payment of annual fees |