JP2006347862A - Novel structure containing aluminosilicate, its manufacturing method, and its use - Google Patents
Novel structure containing aluminosilicate, its manufacturing method, and its use Download PDFInfo
- Publication number
- JP2006347862A JP2006347862A JP2005238648A JP2005238648A JP2006347862A JP 2006347862 A JP2006347862 A JP 2006347862A JP 2005238648 A JP2005238648 A JP 2005238648A JP 2005238648 A JP2005238648 A JP 2005238648A JP 2006347862 A JP2006347862 A JP 2006347862A
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- JP
- Japan
- Prior art keywords
- aluminum
- surface layer
- present
- silica
- crystalline porous
- 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.)
- Granted
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910000323 aluminium silicate Inorganic materials 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 95
- 239000002344 surface layer Substances 0.000 claims abstract description 50
- -1 nitrogen-containing compound Chemical class 0.000 claims abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- 238000005899 aromatization reaction Methods 0.000 claims abstract description 28
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 19
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 19
- 239000010410 layer Substances 0.000 claims abstract description 15
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 12
- 238000002425 crystallisation Methods 0.000 claims abstract description 9
- 230000008025 crystallization Effects 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 92
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 90
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 36
- 229910052710 silicon Inorganic materials 0.000 claims description 36
- 239000010703 silicon Substances 0.000 claims description 36
- 229910052725 zinc Inorganic materials 0.000 claims description 22
- 239000011701 zinc Substances 0.000 claims description 22
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 21
- 150000001336 alkenes Chemical class 0.000 claims description 21
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 16
- 229910052733 gallium Inorganic materials 0.000 claims description 16
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 14
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 abstract description 9
- 239000011973 solid acid Substances 0.000 abstract description 9
- 238000000034 method Methods 0.000 description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- 230000000737 periodic effect Effects 0.000 description 31
- 239000000377 silicon dioxide Substances 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 24
- 239000011324 bead Substances 0.000 description 22
- 238000004458 analytical method Methods 0.000 description 21
- 239000003795 chemical substances by application Substances 0.000 description 19
- 229910021536 Zeolite Inorganic materials 0.000 description 17
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 17
- 239000010457 zeolite Substances 0.000 description 17
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 16
- 238000005259 measurement Methods 0.000 description 15
- 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 14
- 150000001875 compounds Chemical class 0.000 description 14
- 239000011148 porous material Substances 0.000 description 14
- 229910052708 sodium Inorganic materials 0.000 description 14
- 239000011734 sodium Substances 0.000 description 14
- 239000002245 particle Substances 0.000 description 13
- 239000002994 raw material Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 229910052698 phosphorus Inorganic materials 0.000 description 12
- 239000011574 phosphorus Substances 0.000 description 12
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- 239000007809 chemical reaction catalyst Substances 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 9
- 238000000634 powder X-ray diffraction Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 8
- 239000004809 Teflon Substances 0.000 description 8
- 229920006362 Teflon® Polymers 0.000 description 8
- 235000019270 ammonium chloride Nutrition 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 150000001768 cations Chemical class 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 7
- 238000010304 firing Methods 0.000 description 7
- 238000011068 loading method Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000000571 coke Substances 0.000 description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 6
- 238000005342 ion exchange Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 238000006317 isomerization reaction Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000012188 paraffin wax Substances 0.000 description 5
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- 238000005211 surface analysis Methods 0.000 description 5
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 4
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 4
- KXIXHISTUVHOCY-UHFFFAOYSA-N 1-propan-2-ylpiperidine Chemical compound CC(C)N1CCCCC1 KXIXHISTUVHOCY-UHFFFAOYSA-N 0.000 description 4
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 4
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 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
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- 235000010724 Wisteria floribunda Nutrition 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000004939 coking Methods 0.000 description 4
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 4
- 238000004453 electron probe microanalysis Methods 0.000 description 4
- YOMFVLRTMZWACQ-UHFFFAOYSA-N ethyltrimethylammonium Chemical compound CC[N+](C)(C)C YOMFVLRTMZWACQ-UHFFFAOYSA-N 0.000 description 4
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 4
- VMOWKUTXPNPTEN-UHFFFAOYSA-N n,n-dimethylpropan-2-amine Chemical compound CC(C)N(C)C VMOWKUTXPNPTEN-UHFFFAOYSA-N 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- 238000000371 solid-state nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001242 acetic acid derivatives Chemical class 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000004517 catalytic hydrocracking Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 229910052701 rubidium Inorganic materials 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- CSKWZSUBRGLJBC-UHFFFAOYSA-O (3-hydroxyphenyl)-trimethylazanium Chemical compound C[N+](C)(C)C1=CC=CC(O)=C1 CSKWZSUBRGLJBC-UHFFFAOYSA-O 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 2
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- DAEPJLBNLHPAHA-UHFFFAOYSA-N 1-(2-methylpropyl)-2H-pyridine Chemical compound C(C(C)C)N1CC=CC=C1 DAEPJLBNLHPAHA-UHFFFAOYSA-N 0.000 description 2
- BNBLWPUWMNURAX-UHFFFAOYSA-N 1-(2-methylpropyl)piperidine Chemical compound CC(C)CN1CCCCC1 BNBLWPUWMNURAX-UHFFFAOYSA-N 0.000 description 2
- CDSYXCIQYSQOKF-UHFFFAOYSA-N 1-(2-methylpropyl)pyrrole Chemical compound CC(C)CN1C=CC=C1 CDSYXCIQYSQOKF-UHFFFAOYSA-N 0.000 description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 2
- AXWLKJWVMMAXBD-UHFFFAOYSA-N 1-butylpiperidine Chemical compound CCCCN1CCCCC1 AXWLKJWVMMAXBD-UHFFFAOYSA-N 0.000 description 2
- IIYSNNBEZBAQCQ-UHFFFAOYSA-N 1-butylpyrrole Chemical compound CCCCN1C=CC=C1 IIYSNNBEZBAQCQ-UHFFFAOYSA-N 0.000 description 2
- JSHASCFKOSDFHY-UHFFFAOYSA-N 1-butylpyrrolidine Chemical compound CCCCN1CCCC1 JSHASCFKOSDFHY-UHFFFAOYSA-N 0.000 description 2
- UCRIXEWTILHNCG-UHFFFAOYSA-N 1-ethyl-2h-pyridine Chemical compound CCN1CC=CC=C1 UCRIXEWTILHNCG-UHFFFAOYSA-N 0.000 description 2
- VPUAYOJTHRDUTK-UHFFFAOYSA-N 1-ethylpyrrole Chemical compound CCN1C=CC=C1 VPUAYOJTHRDUTK-UHFFFAOYSA-N 0.000 description 2
- ONQBOTKLCMXPOF-UHFFFAOYSA-N 1-ethylpyrrolidine Chemical compound CCN1CCCC1 ONQBOTKLCMXPOF-UHFFFAOYSA-N 0.000 description 2
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 2
- BBYSGWAYRRMWOW-UHFFFAOYSA-N 1-hexylpiperidine Chemical compound CCCCCCN1CCCCC1 BBYSGWAYRRMWOW-UHFFFAOYSA-N 0.000 description 2
- OUKZCQQNMWXMNE-UHFFFAOYSA-N 1-hexylpyrrolidine Chemical compound CCCCCCN1CCCC1 OUKZCQQNMWXMNE-UHFFFAOYSA-N 0.000 description 2
- LTKMTXLIAZLQHS-UHFFFAOYSA-N 1-methylpyridine Chemical compound CN1C=CC=C=C1 LTKMTXLIAZLQHS-UHFFFAOYSA-N 0.000 description 2
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 2
- VIHZQSOIAPTCGJ-UHFFFAOYSA-N 1-pentyl-2h-pyridine Chemical compound CCCCCN1CC=CC=C1 VIHZQSOIAPTCGJ-UHFFFAOYSA-N 0.000 description 2
- LQWJONARYDIOSE-UHFFFAOYSA-N 1-pentylpiperidine Chemical compound CCCCCN1CCCCC1 LQWJONARYDIOSE-UHFFFAOYSA-N 0.000 description 2
- NWRUFJHICAREBX-UHFFFAOYSA-N 1-pentylpyrrolidine Chemical compound CCCCCN1CCCC1 NWRUFJHICAREBX-UHFFFAOYSA-N 0.000 description 2
- MOKUQYSJYISPJS-UHFFFAOYSA-N 1-phenyl-2h-pyridine Chemical compound C1C=CC=CN1C1=CC=CC=C1 MOKUQYSJYISPJS-UHFFFAOYSA-N 0.000 description 2
- LLSKXGRDUPMXLC-UHFFFAOYSA-N 1-phenylpiperidine Chemical compound C1CCCCN1C1=CC=CC=C1 LLSKXGRDUPMXLC-UHFFFAOYSA-N 0.000 description 2
- GEZGAZKEOUKLBR-UHFFFAOYSA-N 1-phenylpyrrole Chemical compound C1=CC=CN1C1=CC=CC=C1 GEZGAZKEOUKLBR-UHFFFAOYSA-N 0.000 description 2
- VDQQJMHXZCMNMU-UHFFFAOYSA-N 1-phenylpyrrolidine Chemical compound C1CCCN1C1=CC=CC=C1 VDQQJMHXZCMNMU-UHFFFAOYSA-N 0.000 description 2
- DPHWUQCXOBNREF-UHFFFAOYSA-N 1-propan-2-yl-2h-pyridine Chemical compound CC(C)N1CC=CC=C1 DPHWUQCXOBNREF-UHFFFAOYSA-N 0.000 description 2
- KNDUGOWIKQAXHL-UHFFFAOYSA-N 1-propan-2-ylpyrrole Chemical compound CC(C)N1C=CC=C1 KNDUGOWIKQAXHL-UHFFFAOYSA-N 0.000 description 2
- YQOPNAOQGQSUHF-UHFFFAOYSA-N 1-propan-2-ylpyrrolidine Chemical compound CC(C)N1CCCC1 YQOPNAOQGQSUHF-UHFFFAOYSA-N 0.000 description 2
- BFEHJRCAUOMQSD-UHFFFAOYSA-N 1-propyl-2h-pyridine Chemical compound CCCN1CC=CC=C1 BFEHJRCAUOMQSD-UHFFFAOYSA-N 0.000 description 2
- VTDIWMPYBAVEDY-UHFFFAOYSA-N 1-propylpiperidine Chemical compound CCCN1CCCCC1 VTDIWMPYBAVEDY-UHFFFAOYSA-N 0.000 description 2
- MFGOZCIHXVFZBC-UHFFFAOYSA-N 1-propylpyrrole Chemical compound CCCN1C=CC=C1 MFGOZCIHXVFZBC-UHFFFAOYSA-N 0.000 description 2
- HLNRRPIYRBBHSQ-UHFFFAOYSA-N 1-propylpyrrolidine Chemical compound CCCN1CCCC1 HLNRRPIYRBBHSQ-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- NJBCRXCAPCODGX-UHFFFAOYSA-N 2-methyl-n-(2-methylpropyl)propan-1-amine Chemical compound CC(C)CNCC(C)C NJBCRXCAPCODGX-UHFFFAOYSA-N 0.000 description 2
- AACHVWXCVWWMSI-UHFFFAOYSA-N 3-hydroxypropyl(trimethyl)azanium Chemical compound C[N+](C)(C)CCCO AACHVWXCVWWMSI-UHFFFAOYSA-N 0.000 description 2
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- MXTMXRYBYWOAGX-UHFFFAOYSA-N dimethyl(diphenyl)azanium Chemical compound C=1C=CC=CC=1[N+](C)(C)C1=CC=CC=C1 MXTMXRYBYWOAGX-UHFFFAOYSA-N 0.000 description 2
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- GJZAMOYERKVOGF-UHFFFAOYSA-N dimethyl-di(propan-2-yl)azanium Chemical compound CC(C)[N+](C)(C)C(C)C GJZAMOYERKVOGF-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
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- 238000009616 inductively coupled plasma Methods 0.000 description 2
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- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
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- 239000011777 magnesium Substances 0.000 description 2
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- 239000011572 manganese Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
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- NDNHNDHVEAHYRC-UHFFFAOYSA-N methyl(tripentyl)azanium Chemical compound CCCCC[N+](C)(CCCCC)CCCCC NDNHNDHVEAHYRC-UHFFFAOYSA-N 0.000 description 2
- VFOJFWOVDZGATC-UHFFFAOYSA-N methyl(tripropyl)azanium Chemical compound CCC[N+](C)(CCC)CCC VFOJFWOVDZGATC-UHFFFAOYSA-N 0.000 description 2
- NAYLGVYVQMVNFY-UHFFFAOYSA-N methyl-tri(propan-2-yl)azanium Chemical compound CC(C)[N+](C)(C(C)C)C(C)C NAYLGVYVQMVNFY-UHFFFAOYSA-N 0.000 description 2
- MCQGLAHNZMFHKS-UHFFFAOYSA-N methyl-tris(2-methylpropyl)azanium Chemical compound CC(C)C[N+](C)(CC(C)C)CC(C)C MCQGLAHNZMFHKS-UHFFFAOYSA-N 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
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- 239000011733 molybdenum Substances 0.000 description 2
- DIAIBWNEUYXDNL-UHFFFAOYSA-N n,n-dihexylhexan-1-amine Chemical compound CCCCCCN(CCCCCC)CCCCCC DIAIBWNEUYXDNL-UHFFFAOYSA-N 0.000 description 2
- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 description 2
- QMHNQZGXPNCMCO-UHFFFAOYSA-N n,n-dimethylhexan-1-amine Chemical compound CCCCCCN(C)C QMHNQZGXPNCMCO-UHFFFAOYSA-N 0.000 description 2
- IDFANOPDMXWIOP-UHFFFAOYSA-N n,n-dimethylpentan-1-amine Chemical compound CCCCCN(C)C IDFANOPDMXWIOP-UHFFFAOYSA-N 0.000 description 2
- ZUHZZVMEUAUWHY-UHFFFAOYSA-N n,n-dimethylpropan-1-amine Chemical compound CCCN(C)C ZUHZZVMEUAUWHY-UHFFFAOYSA-N 0.000 description 2
- MTHFROHDIWGWFD-UHFFFAOYSA-N n-butyl-n-methylbutan-1-amine Chemical compound CCCCN(C)CCCC MTHFROHDIWGWFD-UHFFFAOYSA-N 0.000 description 2
- GNVRJGIVDSQCOP-UHFFFAOYSA-N n-ethyl-n-methylethanamine Chemical compound CCN(C)CC GNVRJGIVDSQCOP-UHFFFAOYSA-N 0.000 description 2
- POMGZMHIXYRARC-UHFFFAOYSA-N n-hexyl-n-methylhexan-1-amine Chemical compound CCCCCCN(C)CCCCCC POMGZMHIXYRARC-UHFFFAOYSA-N 0.000 description 2
- PXSXRABJBXYMFT-UHFFFAOYSA-N n-hexylhexan-1-amine Chemical compound CCCCCCNCCCCCC PXSXRABJBXYMFT-UHFFFAOYSA-N 0.000 description 2
- JJRDPNRWFSHHKJ-UHFFFAOYSA-N n-methyl-n-pentylpentan-1-amine Chemical compound CCCCCN(C)CCCCC JJRDPNRWFSHHKJ-UHFFFAOYSA-N 0.000 description 2
- UVBMZKBIZUWTLV-UHFFFAOYSA-N n-methyl-n-propylpropan-1-amine Chemical compound CCCN(C)CCC UVBMZKBIZUWTLV-UHFFFAOYSA-N 0.000 description 2
- JACMPVXHEARCBO-UHFFFAOYSA-N n-pentylpentan-1-amine Chemical compound CCCCCNCCCCC JACMPVXHEARCBO-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- ZNZJJSYHZBXQSM-UHFFFAOYSA-N propane-2,2-diamine Chemical compound CC(C)(N)N ZNZJJSYHZBXQSM-UHFFFAOYSA-N 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 2
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 description 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
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- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
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- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 1
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 1
- 229940102127 rubidium chloride Drugs 0.000 description 1
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 description 1
- FOGKDYADEBOSPL-UHFFFAOYSA-M rubidium(1+);acetate Chemical compound [Rb+].CC([O-])=O FOGKDYADEBOSPL-UHFFFAOYSA-M 0.000 description 1
- JIYNFFGKZCOPKN-UHFFFAOYSA-N sbb061129 Chemical compound O=C1OC(=O)C2C1C1C=C(C)C2C1 JIYNFFGKZCOPKN-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- ZAOMFOUCOHZIKK-UHFFFAOYSA-N tetra(propan-2-yl)phosphanium Chemical compound CC(C)[P+](C(C)C)(C(C)C)C(C)C ZAOMFOUCOHZIKK-UHFFFAOYSA-N 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 1
- SZWHXXNVLACKBV-UHFFFAOYSA-N tetraethylphosphanium Chemical compound CC[P+](CC)(CC)CC SZWHXXNVLACKBV-UHFFFAOYSA-N 0.000 description 1
- SMYCBOLFQFMGRH-UHFFFAOYSA-N tetrakis(2-methylpropyl)phosphanium Chemical compound CC(C)C[P+](CC(C)C)(CC(C)C)CC(C)C SMYCBOLFQFMGRH-UHFFFAOYSA-N 0.000 description 1
- BXYHVFRRNNWPMB-UHFFFAOYSA-N tetramethylphosphanium Chemical compound C[P+](C)(C)C BXYHVFRRNNWPMB-UHFFFAOYSA-N 0.000 description 1
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 1
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000010555 transalkylation reaction Methods 0.000 description 1
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 description 1
- XKFPGUWSSPXXMF-UHFFFAOYSA-N tributyl(methyl)phosphanium Chemical compound CCCC[P+](C)(CCCC)CCCC XKFPGUWSSPXXMF-UHFFFAOYSA-N 0.000 description 1
- USLHPQORLCHMOC-UHFFFAOYSA-N triethoxygallane Chemical compound CCO[Ga](OCC)OCC USLHPQORLCHMOC-UHFFFAOYSA-N 0.000 description 1
- KAJSSFQQUMPTOD-UHFFFAOYSA-N trihexyl(methyl)phosphanium Chemical compound CCCCCC[P+](C)(CCCCCC)CCCCCC KAJSSFQQUMPTOD-UHFFFAOYSA-N 0.000 description 1
- UAEJRRZPRZCUBE-UHFFFAOYSA-N trimethoxyalumane Chemical compound [Al+3].[O-]C.[O-]C.[O-]C UAEJRRZPRZCUBE-UHFFFAOYSA-N 0.000 description 1
- FUTFRQAXSYLPPW-UHFFFAOYSA-N trimethyl(2-methylpropyl)phosphanium Chemical compound CC(C)C[P+](C)(C)C FUTFRQAXSYLPPW-UHFFFAOYSA-N 0.000 description 1
- MYKCGIGJOAYNOG-UHFFFAOYSA-N trimethyl(pentyl)phosphanium Chemical compound CCCCC[P+](C)(C)C MYKCGIGJOAYNOG-UHFFFAOYSA-N 0.000 description 1
- QMKRJORUUNAPBZ-UHFFFAOYSA-N trimethyl(propan-2-yl)phosphanium Chemical compound CC(C)[P+](C)(C)C QMKRJORUUNAPBZ-UHFFFAOYSA-N 0.000 description 1
- YGDBTMJEJNVHPZ-UHFFFAOYSA-N trimethyl(propyl)phosphanium Chemical compound CCC[P+](C)(C)C YGDBTMJEJNVHPZ-UHFFFAOYSA-N 0.000 description 1
- OBROYCQXICMORW-UHFFFAOYSA-N tripropoxyalumane Chemical compound [Al+3].CCC[O-].CCC[O-].CCC[O-] OBROYCQXICMORW-UHFFFAOYSA-N 0.000 description 1
- KHAUBYTYGDOYRU-IRXASZMISA-N trospectomycin Chemical compound CN[C@H]([C@H]1O2)[C@@H](O)[C@@H](NC)[C@H](O)[C@H]1O[C@H]1[C@]2(O)C(=O)C[C@@H](CCCC)O1 KHAUBYTYGDOYRU-IRXASZMISA-N 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
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Abstract
Description
本発明は、アルミノシリケートを含む新規な構造体、その製造方法およびその用途に関する。さらに詳しくは、構造体表層部に結晶性多孔質アルミノシリケートが、構造体表層部を除く内部の層に無機支持体が存在するアルミノシリケートを含む構造体、その製造方法およびその用途に関するものである。 The present invention relates to a novel structure containing aluminosilicate, a method for producing the structure, and a use thereof. More specifically, the present invention relates to a structure containing an aluminosilicate in which a crystalline porous aluminosilicate is present in a structure surface layer portion and an inorganic support is present in an inner layer excluding the structure surface layer portion, a method for producing the structure, and a use thereof. .
結晶性多孔質アルミノシリケートはゼオライトの一種であり、その組成は一般に下記式(1)で表される。 Crystalline porous aluminosilicate is a kind of zeolite, and its composition is generally represented by the following formula (1).
xM2/nO・Al2O3・ySiO2・zH2O (1)
(ここで、nは陽イオンMの原子価、xは0.8〜2の範囲の数、yは2以上の数、zは0以上の数である。)
その基本構造は、珪素を中心として4つの酸素がその頂点に配置したSiO4で示される四面体構造と、この珪素の代わりにアルミニウムがその中心にあるAlO4で示される四面体とが、酸素/(珪素+アルミニウム)の原子比が2となるようにお互いに酸素を共有して、規則性のある三次元的に結合したものである。
xM 2 / n O · Al 2 O 3 · ySiO 2 · zH 2 O (1)
(Here, n is the valence of the cation M, x is a number in the range of 0.8 to 2, y is a number of 2 or more, and z is a number of 0 or more.)
The basic structure consists of a tetrahedral structure represented by SiO 4 in which four oxygens are arranged at the apex centered on silicon, and a tetrahedron represented by AlO 4 having aluminum in the center instead of silicon. / (Silicon + aluminum) is a three-dimensionally bonded structure that shares oxygen with each other such that the atomic ratio is 2.
その結果、この四面体の結合方式の違いによって大きさ、形の異なる細孔を有する三次元的骨格構造が形成される。 As a result, a three-dimensional skeleton structure having pores of different sizes and shapes is formed by the difference in the bonding method of the tetrahedron.
また、結晶性多孔質アルミノシリケートは固体酸性を持つことが知られている。アルミニウムが中心にある四面体の電子価は負に帯電しており、プロトン、アルカリ金属、アルカリ土類金属等の陽イオンと結合することで電気的に中和されている。特にプロトンと結合した場合では、ブレンステッド酸性を示すことから、結晶性多孔質アルミノシリケートは固体酸触媒として使用されている。即ち、接触分解、水素化分解、脂肪族や芳香族の異性化反応、オレフィンやパラフィンの芳香族化および不均化反応等の触媒として用いられる。 Crystalline porous aluminosilicate is known to have solid acidity. The tetrahedron centered on aluminum is negatively charged, and is electrically neutralized by binding to cations such as protons, alkali metals, and alkaline earth metals. In particular, when it is combined with protons, it exhibits Bronsted acidity, and thus crystalline porous aluminosilicate is used as a solid acid catalyst. That is, it is used as a catalyst for catalytic cracking, hydrocracking, aliphatic and aromatic isomerization reactions, olefin and paraffin aromatization and disproportionation reactions, and the like.
結晶性多孔質アルミノシリケートは、珪素源、アルミニウム源、アルカリ金属成分、および含窒素または含リン化合物等の構造規定剤を用いて調製した水性スラリーを水熱合成して得られる。従来の製造方法では、得られる結晶性多孔質アルミノシリケートは粉体であり、アルミノシリケートを含む構造体を製造する場合には、結晶性多孔質アルミノシリケート単独では成型性が悪いために、得られた粉体に無機バインダー添加し、アルミノシリケートを含む構造体を製造する必要がある。 The crystalline porous aluminosilicate is obtained by hydrothermal synthesis of an aqueous slurry prepared using a silicon source, an aluminum source, an alkali metal component, and a structure-directing agent such as nitrogen-containing or phosphorus-containing compound. In the conventional production method, the obtained crystalline porous aluminosilicate is a powder, and when a structure containing aluminosilicate is produced, the crystalline porous aluminosilicate alone cannot be obtained because the moldability is poor. It is necessary to add an inorganic binder to the obtained powder to produce a structure containing aluminosilicate.
ゼオライトをバインダーとしたアルミノシリケートを含む構造体の製造方法として、例えば、最初にゼオライトの第一結晶を製造し、この結晶体粉体をシリカゲルまたはゾルと混合・成型した後、添加したシリカゲルまたはゾルをゼオライト化する方法が挙げられる(例えば、特許文献1参照)。 As a method for producing a structure containing an aluminosilicate using a zeolite as a binder, for example, firstly, a first crystal of zeolite is produced, and this crystalline powder is mixed and molded with silica gel or sol, and then added silica gel or sol. (For example, refer to Patent Document 1).
バインダーを含まない結晶性多孔質アルミノシリケート構造体の製造方法として、例えば、珪素源としてシリカ構造体を用い、アルミン酸塩、アルカリ金属成分、テトラアルキルアンモニウム成分をシリカ構造体に担持させ、飽和水蒸気と接触させることで、ZSM−5型構造を有する結晶性アルミノシリケートの製造方法が挙げられる(例えば、特許文献2参照)。 As a method for producing a crystalline porous aluminosilicate structure not containing a binder, for example, a silica structure is used as a silicon source, and an aluminate, an alkali metal component, and a tetraalkylammonium component are supported on the silica structure, And a method for producing a crystalline aluminosilicate having a ZSM-5 type structure (for example, see Patent Document 2).
これらの方法では、アルミニウム原子は構造体全体に存在しており、その結果、酸点も構造体全体に存在する。 In these methods, aluminum atoms are present throughout the structure, and as a result, acid sites are also present throughout the structure.
ゼオライトを触媒構造体表層部に存在させる方法としては、例えば金属触媒、合金触媒、無機酸化物触媒等の粒状固体触媒の表層部に分子篩作用があり、実質的に不活性なゼオライト膜で表面全体がコーティングされている触媒が挙げられる(例えば、特許文献3参照)。この場合、構造体表面のゼオライト層は酸点を持たない不活性なシリカライトである。 As a method for allowing zeolite to be present in the surface layer of the catalyst structure, for example, the surface layer of a granular solid catalyst such as a metal catalyst, an alloy catalyst, or an inorganic oxide catalyst has a molecular sieving action, and the entire surface is made of a substantially inert zeolite membrane. (For example, refer patent document 3). In this case, the zeolite layer on the surface of the structure is an inert silicalite having no acid sites.
しかしながら、特許文献1および特許文献2の結晶性多孔質アルミノシリケートは、構造体全体または構造体内部に酸点等の活性点が存在するため、固体酸触媒反応における反応原料および反応生成物が、細孔を通り構造体内部まで進入する。したがって、反応原料および反応生成物の構造体内部の滞留時間が長くなり、活性点等で過剰反応が進行し、目的物の選択性が低下、コーク等の高沸物が触媒の活性点および細孔部に析出し、活性点の被毒や細孔の閉塞を生じ、結果的に触媒活性を低下させ、さらに触媒寿命の低下を招く等の問題が発生する。
However, since the crystalline porous aluminosilicates of
また、特許文献3の方法では、触媒の活性点の上に分子篩作用があり実質的に不活性なゼオライト膜で表面全体がコーティングされているため、反応における反応原料および反応生成物がゼオライト細孔を通り構造体内部に進入する必要がある。この場合も、反応原料および反応生成物の構造体内部の滞留時間が長くなり、目的物の選択性が低下、コーク等の高沸物が析出し、活性点の被毒や細孔の閉塞を生じ、結果的に触媒活性を低下させ、さらに触媒寿命の低下を招く等の問題が発生する。 Further, in the method of Patent Document 3, since the entire surface is coated with a zeolite membrane that has a molecular sieving action on the active point of the catalyst and is substantially inactive, the reaction raw materials and reaction products in the reaction can be converted into zeolite pores. It is necessary to enter the structure through. Also in this case, the residence time inside the structure of the reaction raw materials and reaction products is prolonged, the selectivity of the target product is lowered, high boiling substances such as coke are deposited, poisoning of active sites and pore clogging. As a result, problems such as a decrease in catalyst activity and a decrease in catalyst life occur.
これらの問題点を解決するためには、反応生成物が酸点、すなわち、活性点のある場所から即座に離脱する構造体が必要となる。 In order to solve these problems, a structure in which the reaction product immediately leaves from the acid site, that is, the site having the active site, is required.
本発明は、上記の課題に鑑みてなされたものであり、その目的は固体酸触媒として有効な構造体表層部に結晶性多孔質アルミノシリケートが、構造体内部に無機支持体が存在する構造体、その製造方法およびその用途を提供することにある。 The present invention has been made in view of the above problems, and its purpose is a structure in which a crystalline porous aluminosilicate is present in the surface layer of a structure effective as a solid acid catalyst, and an inorganic support is present inside the structure. It is in providing the manufacturing method and its use.
本発明者らは、上記課題を解決するため鋭意検討した結果、アルミノシリケートを含有する新規な構造体を見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have found a novel structure containing aluminosilicate and have completed the present invention.
すなわち、本発明は構造体表層部に結晶性多孔質アルミノシリケートが存在し、構造体表層部を除く内部の層に無機支持体が存在する構造体、その製造方法およびその用途に関するものである。 That is, the present invention relates to a structure in which a crystalline porous aluminosilicate is present in the structure surface layer portion and an inorganic support is present in an inner layer excluding the structure surface layer portion, a method for producing the structure, and a use thereof.
本発明のアルミノシリケートを含有する新規な構造体は、構造体表層部に結晶性多孔質アルミノシリケートが存在し、構造体表層部を除く内部の層に無機支持体が存在する構造を有することを特徴とする。 The novel structure containing the aluminosilicate of the present invention has a structure in which a crystalline porous aluminosilicate is present in the surface layer portion of the structure and an inorganic support is present in an inner layer excluding the structure surface layer portion. Features.
ここで、本発明における構造体とは、自重や外力などの荷重に抵抗できるように成形した物体のことをいう。 Here, the structure in the present invention refers to an object molded so as to resist a load such as its own weight or external force.
本発明の結晶性多孔質アルミノシリケートは、ゼオライトおよびゼオライト類似物質の一種であり、特に限定するものではなく、その構造は国際ゼオライト学会が規定する構造コードでは、例えば、ABW、AFG、ANA、*BEA、BIK、BOG、BRE、CAN、CAS、CFI、CHA、DAC、DDR、EAB、EDI、EMT、EPI、ERI、ESV、EUO、FAU、FER、FRA、GIS、GME、GOO、HEU、IFR、ITE、JBW、KFI、LAU、LEV、LIO、LOS、LTA、LTL、LTN、MAZ、MEI、MEL、MER、MFI、MFS、MON、MOR、MSO、MTF、MTN、MTT、MTW、MWW、NAT、NES、NON、OFF、−PAR、PAU、PHI、RHO、RTS、SFE、SFF、SFG、SOD、SST、STF、STI、STT、TER、THO、TON、TSC、UFI、VET、VFI、−WEN、YUG等が挙げられる。固体酸触媒として有効なゼオライトおよびゼオライト類似物質であり、さらに後記のオレフィンの芳香族化における芳香族炭化水素の収率が高いことから、好ましくはANA、*BEA、CAS、CFI、DDR、EMT、EUO、FAU、FER、ITE、LEV、LTA、MAZ、MEI、MEL、MFI、MFS、MOR、MOS、MTF、MTN、MTT、MTW、MWW、NES、NON、OFF、SFEl、SFF、SFG、SSY、STF、STT、TON、VFI等が挙げられ、さらに好ましくはMFIが挙げられる。 The crystalline porous aluminosilicate of the present invention is a kind of zeolite and zeolite-like substance, and is not particularly limited. The structure is a structure code defined by the International Zeolite Society, for example, ABW, AFG, ANA, * BEA, BIK, BOG, BRE, CAN, CAS, CFI, CHA, DAC, DDR, EAB, EDI, EMT, EPI, ERI, ESV, EUO, FAU, FER, FRA, GIS, GME, GOO, HEU, IFR, ITE, JBW, KFI, LAU, LEV, LIO, LOS, LTA, LTL, LTN, MAZ, MEI, MEL, MER, MFI, MFS, MON, MOR, MSO, MTF, MTN, MTT, MTW, MWW, NAT, NES, NON, OFF, -PAR, PAU, PHI, RHO, RT , SFE, SFF, SFG, SOD, SST, STF, STI, STT, TER, THO, TON, TSC, UFI, VET, VFI, -WEN, YUG, and the like. Zeolite and zeolite-like substances effective as a solid acid catalyst, and also because of the high yield of aromatic hydrocarbons in the olefin aromatization described below, preferably ANA, * BEA, CAS, CFI, DDR, EMT, EUO, FAU, FER, ITE, LEV, LTA, MAZ, MEI, MEL, MFI, MFS, MOR, MOS, MTF, MTN, MTT, MTW, MWW, NES, NON, OFF, SFEL, SFF, SFG, SSY, STF, STT, TON, VFI, etc. are mentioned, More preferably, MFI is mentioned.
本発明の無機支持体は、特に限定されるものではなく、例えば、結晶性多孔質シリケート、シリカ、ジルコニア、チタニア、マグネシア、窒化珪素、活性炭、粘土鉱物等が挙げられる。これらのうち、構造体の安定性の面から結晶性多孔質シリケートが好ましく用いられる。 The inorganic support of the present invention is not particularly limited, and examples thereof include crystalline porous silicate, silica, zirconia, titania, magnesia, silicon nitride, activated carbon, and clay mineral. Of these, crystalline porous silicate is preferably used from the viewpoint of the stability of the structure.
ここで、無機支持体に好ましく用いられる結晶性多孔質シリケートとはゼオライトおよびゼオライト類似物質の一種であり、その基本構造は、珪素を中心として4つの酸素がその頂点に配置したSiO4で示される四面体構造からなる規則性のある三次元的に結合したものである。その結果、この四面体の結合方式の違いによって大きさ、形の異なる細孔を有する三次元的骨格構造が形成される。また、結晶性多孔質シリケートは固体酸性を持たないことが知られている。 Here, the crystalline porous silicate preferably used for the inorganic support is a kind of zeolite and zeolite-like substance, and its basic structure is represented by SiO 4 in which four oxygens are arranged at the apex centering on silicon. A regular three-dimensional combination of tetrahedral structures. As a result, a three-dimensional skeleton structure having pores of different sizes and shapes is formed by the difference in the bonding method of the tetrahedron. Further, it is known that crystalline porous silicate does not have solid acidity.
本発明の無機支持体に好ましく用いられる結晶性多孔質シリケートは、特に限定するものではなく、その構造は国際ゼオライト学会が規定する構造コードでは、例えば、AST、*BEA、CAS、CFI、CON、DDR、DOH、EUO、FAU、FER、GON、IFR、ISV、ITE、ITH、ITW、FER、GON、IFR、ISV、ITE、ITH、ITW、LEV、MAZ、MEI、MEL、MEP、MFI、MFS、MOS、MTF、MTN、MTT、MTW、MWW、NES、NON、OFF、RTE、RTH、RUT、SFE、SFF、SFG、SGT、SSY、STF、STT、TON、VET、VFI、YUG等が挙げられる。本発明の構造体の合成が容易で、しかも構造体の安定性がさらに高いことから、好ましくは*BEA、CAS、CFI、DDR、EUO、FAU、FER、ITE、LEV、MAZ、MEI、MEL、MFI、MFS、MOS、MTF、MTN、MTT、MTW、MWW、NES、NON、OFF、SFEl、SFF、SFG、SSY、STF、STT、TON、VFI等が挙げられ、より好ましくはMFIが挙げられる。 The crystalline porous silicate preferably used for the inorganic support of the present invention is not particularly limited, and the structure is a structure code defined by the International Zeolite Society, for example, AST, * BEA, CAS, CFI, CON, DDR, DOH, EUO, FAU, FER, GON, IFR, ISV, ITE, ITH, ITW, FER, GON, IFR, ISV, ITE, ITH, ITW, LEV, MAZ, MEI, MEL, MEP, MFI, MFS, MOS, MTF, MTN, MTT, MTW, MWW, NES, NON, OFF, RTE, RTH, RUT, SFE, SFF, SFG, SGT, SSY, STF, STT, TON, VET, VFI, YUG and the like. Since the synthesis of the structure of the present invention is easy and the stability of the structure is further high, preferably * BEA, CAS, CFI, DDR, EUO, FAU, FER, ITE, LEV, MAZ, MEI, MEL, MFI, MFS, MOS, MTF, MTN, MTT, MTW, MWW, NES, NON, OFF, SFE1, SFF, SFG, SSY, STF, STT, TON, VFI and the like are preferable, and MFI is more preferable.
本発明の構造体では、構造体表層部の結晶性多孔質アルミノシリケートが存在する層の厚さは、好ましくは構造体外表面から1〜1000μm、さらに好ましくは1〜500μmである。 In the structure of the present invention, the thickness of the layer where the crystalline porous aluminosilicate is present in the surface layer of the structure is preferably 1 to 1000 μm, more preferably 1 to 500 μm from the outer surface of the structure.
本発明の構造体では、構造体表層部の結晶性多孔質アルミノシリケートのアルミニウム/珪素比(原子比)は、結晶化度の高い構造体を得ることができることから、好ましくは0.0001〜1、さらに好ましくは0.0005〜0.5である。 In the structure of the present invention, the aluminum / silicon ratio (atomic ratio) of the crystalline porous aluminosilicate in the surface layer portion of the structure is preferably 0.0001 to 1 because a structure with a high degree of crystallinity can be obtained. More preferably, it is 0.0005 to 0.5.
本発明の構造体では、構造体表層部を除く内部の層の無機支持体は、実質的にアルミニウムを含まない。 In the structure of the present invention, the inorganic support of the inner layer excluding the structure surface layer part substantially does not contain aluminum.
本発明の構造体の形状は、特に限定されるものではなく、例えば、図1〜4で示されるような球状、楕円状、円柱状、中空円柱状、板状、シート状、ハニカム状等が挙げられる。これらのうち、十分な反応活性があり、副反応、および、コーキングを抑制することができることから、好ましくは球状、楕円状、円柱状、中空円柱状、さらに好ましくは球状が挙げられる。 The shape of the structure of the present invention is not particularly limited, and examples thereof include a spherical shape, an elliptical shape, a cylindrical shape, a hollow cylindrical shape, a plate shape, a sheet shape, and a honeycomb shape as shown in FIGS. Can be mentioned. Among these, since there is sufficient reaction activity and side reactions and coking can be suppressed, preferably spherical, elliptical, cylindrical, hollow cylindrical, and more preferably spherical.
また、本発明の構造体の大きさには、特に制限されるものではなく、例えば、十分な反応活性があり、副反応およびコーキングを抑制することができることから、好ましくは0.1〜100mmの範囲、さらに好ましくは0.9〜10mmの範囲の構造体が挙げられる。 The size of the structure of the present invention is not particularly limited. For example, the structure has sufficient reaction activity, and side reactions and coking can be suppressed. Structures in the range, more preferably in the range of 0.9 to 10 mm.
本発明の構造体において、バインダーの有無に特に制限はないが、後記のオレフィンの芳香族化反応活性が維持できること、さらに副反応およびコーキングを抑制することができることから、バインダーを含まないことが好ましい。 In the structure of the present invention, there is no particular limitation on the presence or absence of a binder, but it is preferable not to include a binder because it can maintain the aromatization reaction activity of olefins described below and can further suppress side reactions and coking. .
本発明の構造体はいかなる方法により製造されても差し支えはなく、例えば、(1)アルカリ金属および/または塩基性の含窒素化合物、必要に応じ含窒素または含リン化合物等の構造規定剤をシリカ構造体に含浸または担持させた後、アルミニウム源をシリカ構造体の表層部に担持させ、必要に応じ再度含窒素または含リン化合物等の構造規定剤をシリカ構造体に含浸または担持させた後、水蒸気、または必要に応じ含窒素若しくは含リン化合物等の構造規定剤を含んだ水蒸気に接触させ結晶化処理を行う方法、(2)無機支持体を、アルカリ金属、必要に応じ含窒素または含リン化合物等の構造規定剤を含んだシリカ−アルミナゾルの中に添加し、水熱処理により結晶化する方法、(3)無機支持体表層部にアルカリ金属、必要に応じ含窒素または含リン化合物等の構造規定剤を含んだシリカ−アルミナゾルを塗布し、水蒸気、または必要に応じ含窒素若しくは含リン化合物等の構造規定剤を含んだ水蒸気に接触させ結晶化処理を行う方法等の製造方法により製造することができる。構造体の表層部に担持されるアルミニウム源が内部に拡散しにくいことから、(1)の方法が好ましく用いられる。 The structure of the present invention may be produced by any method. For example, (1) a structure-directing agent such as an alkali metal and / or basic nitrogen-containing compound, and if necessary, nitrogen-containing or phosphorus-containing compound is added to silica. After impregnating or supporting the structure, an aluminum source is supported on the surface layer of the silica structure, and if necessary, impregnating or supporting a structure-directing agent such as nitrogen-containing or phosphorus-containing compound again on the silica structure, A method of performing a crystallization treatment by contact with water vapor or water vapor containing a structure-directing agent such as nitrogen-containing or phosphorus-containing compound as necessary, (2) an inorganic support, alkali metal, nitrogen-containing or phosphorus-containing as needed A method of adding to a silica-alumina sol containing a structure-directing agent such as a compound and crystallizing by hydrothermal treatment. (3) Alkali metal in the surface of the inorganic support, optionally containing A method of performing a crystallization treatment by applying a silica-alumina sol containing a structure-directing agent such as elemental or phosphorus-containing compound, and contacting with water vapor or steam containing a structure-directing agent such as nitrogen-containing or phosphorus-containing compound as necessary. It can be manufactured by a manufacturing method such as The method (1) is preferably used because the aluminum source supported on the surface layer of the structure is difficult to diffuse inside.
本発明において、(1)の方法をさらに詳しく説明すると、シリカ構造体にアルカリ金属および/または塩基性の含窒素化合物、必要に応じ含窒素または含リン化合物等の構造規定剤を含浸または担持させた後、アルミニウム源をシリカ構造体の表層部に担持させ、乾燥の後、必要に応じ含窒素または含リン化合物等の構造規定剤をシリカ構造体に含浸または担持させ、乾燥した後、水蒸気、または必要に応じ含窒素若しくは含リン化合物等の構造規定剤を含んだ水蒸気に接触させ結晶化処理を行い、構造体表層部に結晶性多孔質アルミノシリケートが存在し、構造体表層部を除く内部の層に無機支持体が存在することからなる構造体を得る。さらに、必要に応じ、焼成、イオン交換を行っても良い。 In the present invention, the method (1) will be described in more detail. The silica structure is impregnated or supported with a structure-directing agent such as an alkali metal and / or a basic nitrogen-containing compound, and if necessary, a nitrogen-containing or phosphorus-containing compound. After that, the aluminum source is supported on the surface layer portion of the silica structure, and after drying, a structure-directing agent such as nitrogen-containing or phosphorus-containing compound is impregnated or supported on the silica structure as necessary. Or, if necessary, contact with water vapor containing a structure-directing agent such as nitrogen-containing or phosphorus-containing compound for crystallization treatment, and there is crystalline porous aluminosilicate on the surface of the structure. A structure comprising an inorganic support in the layer is obtained. Furthermore, you may perform baking and ion exchange as needed.
本発明の方法で使用される珪素源は、特に限定されるものではないが、例えば、シリカ構造体を使用することができ、市販のシリカビーズを用いることができる。シリカ構造体としては、結晶化度の高い構造体を得ることができることから、好ましくは表面積が5〜1000m2/g、さらに好ましくは10〜500m2/gのものが使用される。 The silicon source used in the method of the present invention is not particularly limited. For example, a silica structure can be used, and commercially available silica beads can be used. As the silica structure, since a structure having a high degree of crystallinity can be obtained, those having a surface area of preferably 5 to 1000 m 2 / g, more preferably 10 to 500 m 2 / g are used.
また、シリカ構造体の形状は、特に限定されるものではないが、例えば、球状、楕円状、円柱状、中空円柱状、板状、シート状、ハニカム状等が使用される。十分な反応活性があり、副反応、および、コーキングを抑制することができることから、好ましくは球状、楕円状、円柱状、中空円柱状、さらに好ましくは球状が使用される。 The shape of the silica structure is not particularly limited, and for example, a spherical shape, an elliptical shape, a cylindrical shape, a hollow cylindrical shape, a plate shape, a sheet shape, a honeycomb shape, or the like is used. Since there is sufficient reaction activity and side reactions and coking can be suppressed, spherical, elliptical, cylindrical, hollow cylindrical, and more preferably spherical are used.
また、シリカ構造体の粒子径の大きさは、特に制限されるものではなく、例えば、好ましくは0.1〜100mmの範囲、さらに好ましくは0.9〜10mmの範囲のものが使用される。 Further, the size of the particle diameter of the silica structure is not particularly limited, and for example, a silica structure having a size of preferably 0.1 to 100 mm, more preferably 0.9 to 10 mm is used.
本発明の方法で使用されるアルミニウム源は、特に限定されるものではないが、例えば、塩化アルミニウム、硝酸アルミニウム、硫酸アルミニウム、炭酸アルミニウム等のアルミニウム塩類;アルミン酸リチウム、アルミン酸ナトリウム、アルミン酸カリウム、アルミン酸ルビジウム、アルミン酸セシウム等のアルミン酸塩類;アルミニウムメトキシド、アルミニウムエトキシド、アルミニウムプロポキシド、アルミニウムブトキシド等のアルミニウムアルコキシド類等が使用される。構造体の表層部に担持されるアルミニウム源が内部に拡散しにくいことから、好ましくは、アルミニウム塩類が、さらに好ましくは、硝酸アルミニウムが使用される。 The aluminum source used in the method of the present invention is not particularly limited. For example, aluminum salts such as aluminum chloride, aluminum nitrate, aluminum sulfate, and aluminum carbonate; lithium aluminate, sodium aluminate, potassium aluminate Aluminum aluminates such as rubidium aluminate and cesium aluminate; aluminum alkoxides such as aluminum methoxide, aluminum ethoxide, aluminum propoxide and aluminum butoxide are used. Aluminum salts are preferably used, and aluminum nitrate is more preferably used because the aluminum source supported on the surface layer portion of the structure is difficult to diffuse inside.
本発明の方法で使用されるアルカリ金属は、特に限定されるものではないが、例えば、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化ルビジウム、水酸化セシウム等の水酸化物類;炭酸リチウム、炭酸ナトリウム、炭酸カリウム、炭酸ルビジウム、炭酸セシウム等の炭酸塩類;酢酸リチウム、酢酸ナトリウム、酢酸カリウム、酢酸ルビジウム、酢酸セシウム等類の酢酸塩類;塩化リチウム、塩化ナトリウム、塩化カリウム、塩化ルビジウム、塩化セシウム等の塩化物類;硝酸リチウム、硝酸ナトリウム、硝酸カリウム、硝酸ルビジウム、硝酸セシウム等の硝酸塩類が使用される。水酸化物以外のアルカリ金属成分を使用する場合には、アルミニウム源をシリカ構造体に担持させる前に焼成を行い、酸化物にすることが好ましい。 The alkali metal used in the method of the present invention is not particularly limited. For example, hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide; Carbonates such as lithium, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate; acetates such as lithium acetate, sodium acetate, potassium acetate, rubidium acetate, cesium acetate; lithium chloride, sodium chloride, potassium chloride, rubidium chloride, Chlorides such as cesium chloride; nitrates such as lithium nitrate, sodium nitrate, potassium nitrate, rubidium nitrate, and cesium nitrate are used. In the case of using an alkali metal component other than hydroxide, it is preferable to calcinate before supporting the aluminum source on the silica structure to form an oxide.
本発明で使用される塩基性の含窒素化合物は、特に限定されるものではないが、例えば、アンモニア、メチルアミン、エチルアミン、n−プロピルアミン、イソプロピルアミン、n−ブチルアミン、イソブチルアミン、n−ペンチルアミン、n−ヘキシルアミン、ピリジン、ジアミノエタン、ジアミノプロパン、ジアミノブタン、ジアミノペプタン、ジアミンヘキサン、ジメチルアミン、ジエチルアミン、ジ−n−プロピルアミン、ジ−n−ブチルアミン、ジ−n−ペンチルアミン、ジ−n−ヘキシシルアミン、ジフェニルアミン、トリメチルアミン、トリエチルアミン、トリ−n−プロピルアミン、トリイソプロピルアミン、トリ−n−ブチルアミン、トリ−n−ペンチルアミン、トリ−n−ヘキシルアミン、トリフェニルアミン、ジメチルエチルアミン、ジメチル−n−プロピルアミン、ジメチルイソプロピルアミン、ジメチル−n−ブチルアミン、ジメチルイソプロピルアミン、ジメチル−n−ペンチルアミン、ジメチル−n−ヘキシルアミン、ジメチルフェニルアミン、ジエチルメチルアミン、ジ−n−プロピルメチルアミン、ジイソプロピルアミン、ジ−n−ブチルメチルアミン、ジイソブチルアミン、ジ−n−ペンチルメチルアミン、ジ−n−ヘキシルメチルアミン、ジフェニルメチルアミン、アジリジン、アゼチジン、ピロリジン、1−メチルピロリジン、1−エチルピロリジン、1−n−プロピルピロリジン、1−イソプロピルピロリジン、1−n−ブチルピロリジン、1−イソブチルピロリジン、1−n−ペンチルピロリジン、1−n−ヘキシルピロリジン、1−フェニルピロリジン、ピペリジン、1−メチルピペリジン、1−エチルピペリジン、1−n−プロピルピペリジン、1−イソプロピルピペリジン、1−n−ブチルピペリジン、1−イソブチルピペリジン、1−n−ペンチルピペリジン、1−n−ヘキシルピペリジン、1−フェニルピペリジン、ピロール、1−メチルピロール、1−エチルピロール、1−n−プロピルピロール、1−イソプロピルピロール、1−n−ブチルピロール、1−イソブチルピロール、1−n−ペンチルピロール、1−n−ヘキシルピロール、1−フェニルピロール、ピリジン、1−メチルピリジン、1−エチルピリジン、1−n−プロピルピリジン、1−イソプロピルピリジン、1−n−ブチルピリジン、1−イソブチルピリジン、1−n−ペンチルピリジン、1−n−ヘキシルピリジン、1−フェニルピリジン等の有機アミン化合物類;テトラメチルアンモニウム、テトラエチルアンモニウム、テトラ−n−プロピルアンモニウム、テトライソプロピルアンモニウム、テトラ−n−ブチルアンモニウム、テトライソブチルアンモニウム、テトラ−n−ペンチルアンモニウム、テトラ−n−ヘキシルアンモニウム、テトラフェニルアンモニウム、トリメチルエチルアンモニウム、トリメチルエチルアンモニウム、トリメチル−n−プロピルアンモニウム、トリメチルイソプロピルアンモニウム、トリメチル−n−ブチルアンモニウム、トリメチルイソブチルアンモニウム、トリメチル−n−ペンチルアンモニウム、トリメチル−n−ヘキシルアンモニウム、トリメチルフェニルアンモニウム、ジメチルジエチルアンモニウム、ジメチルジアンモニウム、ジメチルジ−n−プロピルアンモニウム、ジメチルジイソプロピルアンモニウム、ジメチルジ−n−ブチルアンモニウム、ジメチルジイソブチルアンモニウム、ジメチルジ−n−ペンチルアンモニウム、ジメチルジ−n−ヘキシルアンモニウム、ジメチルジフェニルアンモニウム、メチルトリエチルアンモニウム、メチルトリアンモニウム、メチルトリ−n−プロピルアンモニウム、メチルトリイソプロピルアンモニウム、メチルトリ−n−ブチルアンモニウム、メチルトリイソブチルアンモニウム、メチルトリ−n−ペンチルアンモニウム、メチルトリ−n−ヘキシルアンモニウム、メチルトリフェニルアンモニウム、ヒドロキシメチルトリメチルアンモニウム、2−ヒドロキシエチルトリメチルアンモニウム、3−ヒドロキシ−n−プロピルトリメチルアンモニウム、4−ヒドロキシ−n−ブチルトリメチルアンモニウム、5−ヒドロキシ−n−ペンチルトリメチルアンモニウム、6−ヒドロキシ−n−ヘキシルトリメチルアンモニウム、3−ヒドロキシフェニルトリメチルアンモニウム等のアンモニウム塩の硝酸塩、硫酸塩、酢酸塩、水酸化物、ハロゲン化物等の塩類が使用される。構造体の表層部に担持されるアルミニウム源が内部に拡散しにくいことから、好ましくは、アンモニウム塩類の水酸化物が使用される。 The basic nitrogen-containing compound used in the present invention is not particularly limited, and examples thereof include ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, and n-pentyl. Amine, n-hexylamine, pyridine, diaminoethane, diaminopropane, diaminobutane, diaminopeptane, diamine hexane, dimethylamine, diethylamine, di-n-propylamine, di-n-butylamine, di-n-pentylamine, Di-n-hexylamine, diphenylamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, triphenylamine, dimethyl Ethylamine, dimethyl-n-propylamine, dimethylisopropylamine, dimethyl-n-butylamine, dimethylisopropylamine, dimethyl-n-pentylamine, dimethyl-n-hexylamine, dimethylphenylamine, diethylmethylamine, di-n-propyl Methylamine, diisopropylamine, di-n-butylmethylamine, diisobutylamine, di-n-pentylmethylamine, di-n-hexylmethylamine, diphenylmethylamine, aziridine, azetidine, pyrrolidine, 1-methylpyrrolidine, 1- Ethylpyrrolidine, 1-n-propylpyrrolidine, 1-isopropylpyrrolidine, 1-n-butylpyrrolidine, 1-isobutylpyrrolidine, 1-n-pentylpyrrolidine, 1-n-hexylpyrrolidine, 1 Phenylpyrrolidine, piperidine, 1-methylpiperidine, 1-ethylpiperidine, 1-n-propylpiperidine, 1-isopropylpiperidine, 1-n-butylpiperidine, 1-isobutylpiperidine, 1-n-pentylpiperidine, 1-n- Hexylpiperidine, 1-phenylpiperidine, pyrrole, 1-methylpyrrole, 1-ethylpyrrole, 1-n-propylpyrrole, 1-isopropylpyrrole, 1-n-butylpyrrole, 1-isobutylpyrrole, 1-n-pentylpyrrole 1-n-hexylpyrrole, 1-phenylpyrrole, pyridine, 1-methylpyridine, 1-ethylpyridine, 1-n-propylpyridine, 1-isopropylpyridine, 1-n-butylpyridine, 1-isobutylpyridine, 1 -N-pentylpyridine, 1 Organic amine compounds such as n-hexylpyridine and 1-phenylpyridine; tetramethylammonium, tetraethylammonium, tetra-n-propylammonium, tetraisopropylammonium, tetra-n-butylammonium, tetraisobutylammonium, tetra-n- Pentylammonium, tetra-n-hexylammonium, tetraphenylammonium, trimethylethylammonium, trimethylethylammonium, trimethyl-n-propylammonium, trimethylisopropylammonium, trimethyl-n-butylammonium, trimethylisobutylammonium, trimethyl-n-pentylammonium , Trimethyl-n-hexylammonium, trimethylphenylammonium, dimethyldi Tylammonium, dimethyldiammonium, dimethyldi-n-propylammonium, dimethyldiisopropylammonium, dimethyldi-n-butylammonium, dimethyldiisobutylammonium, dimethyldi-n-pentylammonium, dimethyldi-n-hexylammonium, dimethyldiphenylammonium, methyltriethylammonium , Methyltriammonium, methyltri-n-propylammonium, methyltriisopropylammonium, methyltri-n-butylammonium, methyltriisobutylammonium, methyltri-n-pentylammonium, methyltri-n-hexylammonium, methyltriphenylammonium, hydroxymethyl Trimethylammonium, 2-hydroxyethyltri Tillammonium, 3-hydroxy-n-propyltrimethylammonium, 4-hydroxy-n-butyltrimethylammonium, 5-hydroxy-n-pentyltrimethylammonium, 6-hydroxy-n-hexyltrimethylammonium, 3-hydroxyphenyltrimethylammonium, etc. Ammonium salt nitrates, sulfates, acetates, hydroxides, halides and the like are used. Preferably, an aluminum salt hydroxide is used because the aluminum source supported on the surface layer of the structure is difficult to diffuse inside.
本発明で使用される構造規定剤は、特に限定されるものではないが、例えば、含窒素または含リン化合物が挙げられ、より具体的な含窒素または含リン化合物としては、例えば、メチルアミン、エチルアミン、n−プロピルアミン、イソプロピルアミン、n−ブチルアミン、イソブチルアミン、n−ペンチルアミン、n−ヘキシルアミン、ピリジン、ジアミノエタン、ジアミノプロパン、ジアミノブタン、ジアミノペプタン、ジアミンヘキサン、ジメチルアミン、ジエチルアミン、ジ−n−プロピルアミン、ジ−n−ブチルアミン、ジ−n−ペンチルアミン、ジ−n−ヘキシシルアミン、ジフェニルアミン、トリメチルアミン、トリエチルアミン、トリ−n−プロピルアミン、トリイソプロピルアミン、トリ−n−ブチルアミン、トリ−n−ペンチルアミン、トリ−n−ヘキシルアミン、トリフェニルアミン、ジメチルエチルアミン、ジメチル−n−プロピルアミン、ジメチルイソプロピルアミン、ジメチル−n−ブチルアミン、ジメチルイソプロピルアミン、ジメチル−n−ペンチルアミン、ジメチル−n−ヘキシルアミン、ジメチルフェニルアミン、ジエチルメチルアミン、ジ−n−プロピルメチルアミン、ジイソプロピルアミン、ジ−n−ブチルメチルアミン、ジイソブチルアミン、ジ−n−ペンチルメチルアミン、ジ−n−ヘキシルメチルアミン、ジフェニルメチルアミン、アジリジン、アゼチジン、ピロリジン、1−メチルピロリジン、1−エチルピロリジン、1−n−プロピルピロリジン、1−イソプロピルピロリジン、1−n−ブチルピロリジン、1−イソブチルピロリジン、1−n−ペンチルピロリジン、1−n−ヘキシルピロリジン、1−フェニルピロリジン、ピペリジン、1−メチルピペリジン、1−エチルピペリジン、1−n−プロピルピペリジン、1−イソプロピルピペリジン、1−n−ブチルピペリジン、1−イソブチルピペリジン、1−n−ペンチルピペリジン、1−n−ヘキシルピペリジン、1−フェニルピペリジン、ピロール、1−メチルピロール、1−エチルピロール、1−n−プロピルピロール、1−イソプロピルピロール、1−n−ブチルピロール、1−イソブチルピロール、1−n−ペンチルピロール、1−n−ヘキシルピロール、1−フェニルピロール、ピリジン、1−メチルピリジン、1−エチルピリジン、1−n−プロピルピリジン、1−イソプロピルピリジン、1−n−ブチルピリジン、1−イソブチルピリジン、1−n−ペンチルピリジン、1−n−ヘキシルピリジン、1−フェニルピリジン等の有機アミン化合物類;テトラメチルアンモニウム、テトラエチルアンモニウム、テトラ−n−プロピルアンモニウム、テトライソプロピルアンモニウム、テトラ−n−ブチルアンモニウム、テトライソブチルアンモニウム、テトラ−n−ペンチルアンモニウム、テトラ−n−ヘキシルアンモニウム、テトラフェニルアンモニウム、トリメチルエチルアンモニウム、トリメチルエチルアンモニウム、トリメチル−n−プロピルアンモニウム、トリメチルイソプロピルアンモニウム、トリメチル−n−ブチルアンモニウム、トリメチルイソブチルアンモニウム、トリメチル−n−ペンチルアンモニウム、トリメチル−n−ヘキシルアンモニウム、トリメチルフェニルアンモニウム、ジメチルジエチルアンモニウム、ジメチルジアンモニウム、ジメチルジ−n−プロピルアンモニウム、ジメチルジイソプロピルアンモニウム、ジメチルジ−n−ブチルアンモニウム、ジメチルジイソブチルアンモニウム、ジメチルジ−n−ペンチルアンモニウム、ジメチルジ−n−ヘキシルアンモニウム、ジメチルジフェニルアンモニウム、メチルトリエチルアンモニウム、メチルトリアンモニウム、メチルトリ−n−プロピルアンモニウム、メチルトリイソプロピルアンモニウム、メチルトリ−n−ブチルアンモニウム、メチルトリイソブチルアンモニウム、メチルトリ−n−ペンチルアンモニウム、メチルトリ−n−ヘキシルアンモニウム、メチルトリフェニルアンモニウム、ヒドロキシメチルトリメチルアンモニウム、2−ヒドロキシエチルトリメチルアンモニウム、3−ヒドロキシ−n−プロピルトリメチルアンモニウム、4−ヒドロキシ−n−ブチルトリメチルアンモニウム、5−ヒドロキシ−n−ペンチルトリメチルアンモニウム、6−ヒドロキシ−n−ヘキシルトリメチルアンモニウム、3−ヒドロキシフェニルトリメチルアンモニウム等のアンモニウム塩の硝酸塩、硫酸塩、酢酸塩、水酸化物、ハロゲン化物等の塩類;テトラメチルホスホニウム、テトラエチルホスホニウム、テトラ−n−プロピルホスホニウム、テトライソプロピルホスホニウム、テトラ−n−ブチルホスホニウム、テトライソブチルホスホニウム、テトラ−n−ペンチルホスホニウム、テトラ−n−ヘキシルホスホニウム、テトラフェニルホスホニウム、トリメチルエチルホスホニウム、トリメチルエチルホスホニウム、トリメチル−n−プロピルホスホニウム、トリメチルイソプロピルホスホニウム、トリメチル−n−ブチルホスホニウム、トリメチルイソブチルホスホニウム、トリメチル−n−ペンチルホスホニウム、トリメチル−n−ヘキシルホスホニウム、トリメチルフェニルホスホニウム、ジメチルジエチルホスホニウム、ジメチルジホスホニウム、ジメチルジ−n−プロピルホスホニウム、ジメチルジイソプロピルホスホニウム、ジメチルジ−n−ブチルホスホニウム、ジメチルジイソブチルホスホニウム、ジメチルジ−n−ペンチルホスホニウム、ジメチルジ−n−ヘキシルホスホニウム、ジメチルジフェニルホスホニウム、メチルトリエチルホスホニウム、メチルトリホスホニウム、メチルトリ−n−プロピルホスホニウム、メチルトリイソプロピルホスホニウム、メチルトリ−n−ブチルホスホニウム、メチルトリイソブチルホスホニウム、メチルトリ−n−ペンチルホスホニウム、メチルトリ−n−ヘキシルホスホニウム、メチルトリフェニルホスホニウム、ヒドロキシメチルトリメチルホスホニウム、2−ヒドロキシエチルトリメチルホスホニウム、3−ヒドロキシ−n−プロピルトリメチルホスホニウム、4−ヒドロキシ−n−ブチルトリメチルホスホニウム、5−ヒドロキシ−n−ペンチルトリメチルホスホニウム、6−ヒドロキシ−n−ヘキシルトリメチルホスホニウム、3−ヒドロキシフェニルトリメチルホスホニウム等のホスホニウム塩の硝酸塩、硫酸塩、酢酸塩、水酸化物、ハロゲン化物等の塩類が使用される。これらの構造規定剤の中でも結晶化度の高い構造体を得ることができることから、好ましくは、有機アミン化合物類、アンモニウム塩類が使用される。 The structure directing agent used in the present invention is not particularly limited, and examples thereof include nitrogen-containing or phosphorus-containing compounds. More specific nitrogen-containing or phosphorus-containing compounds include, for example, methylamine, Ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, n-pentylamine, n-hexylamine, pyridine, diaminoethane, diaminopropane, diaminobutane, diaminopeptane, diamine hexane, dimethylamine, diethylamine, Di-n-propylamine, di-n-butylamine, di-n-pentylamine, di-n-hexylamine, diphenylamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, tri -N- Nthylamine, tri-n-hexylamine, triphenylamine, dimethylethylamine, dimethyl-n-propylamine, dimethylisopropylamine, dimethyl-n-butylamine, dimethylisopropylamine, dimethyl-n-pentylamine, dimethyl-n-hexylamine , Dimethylphenylamine, diethylmethylamine, di-n-propylmethylamine, diisopropylamine, di-n-butylmethylamine, diisobutylamine, di-n-pentylmethylamine, di-n-hexylmethylamine, diphenylmethylamine Aziridine, azetidine, pyrrolidine, 1-methylpyrrolidine, 1-ethylpyrrolidine, 1-n-propylpyrrolidine, 1-isopropylpyrrolidine, 1-n-butylpyrrolidine, 1-isobutylpi Lysine, 1-n-pentylpyrrolidine, 1-n-hexylpyrrolidine, 1-phenylpyrrolidine, piperidine, 1-methylpiperidine, 1-ethylpiperidine, 1-n-propylpiperidine, 1-isopropylpiperidine, 1-n-butyl Piperidine, 1-isobutylpiperidine, 1-n-pentylpiperidine, 1-n-hexylpiperidine, 1-phenylpiperidine, pyrrole, 1-methylpyrrole, 1-ethylpyrrole, 1-n-propylpyrrole, 1-isopropylpyrrole, 1-n-butylpyrrole, 1-isobutylpyrrole, 1-n-pentylpyrrole, 1-n-hexylpyrrole, 1-phenylpyrrole, pyridine, 1-methylpyridine, 1-ethylpyridine, 1-n-propylpyridine, 1-isopropylpyridine, 1-n- Organic amine compounds such as butylpyridine, 1-isobutylpyridine, 1-n-pentylpyridine, 1-n-hexylpyridine, 1-phenylpyridine; tetramethylammonium, tetraethylammonium, tetra-n-propylammonium, tetraisopropylammonium , Tetra-n-butylammonium, tetraisobutylammonium, tetra-n-pentylammonium, tetra-n-hexylammonium, tetraphenylammonium, trimethylethylammonium, trimethylethylammonium, trimethyl-n-propylammonium, trimethylisopropylammonium, trimethyl -N-butylammonium, trimethylisobutylammonium, trimethyl-n-pentylammonium, trimethyl- -Hexylammonium, trimethylphenylammonium, dimethyldiethylammonium, dimethyldiammonium, dimethyldi-n-propylammonium, dimethyldiisopropylammonium, dimethyldi-n-butylammonium, dimethyldiisobutylammonium, dimethyldi-n-pentylammonium, dimethyldi-n-hexyl Ammonium, dimethyldiphenylammonium, methyltriethylammonium, methyltriammonium, methyltri-n-propylammonium, methyltriisopropylammonium, methyltri-n-butylammonium, methyltriisobutylammonium, methyltri-n-pentylammonium, methyltri-n-hexyl Ammonium, methyltriphenylammonium Hydroxymethyltrimethylammonium, 2-hydroxyethyltrimethylammonium, 3-hydroxy-n-propyltrimethylammonium, 4-hydroxy-n-butyltrimethylammonium, 5-hydroxy-n-pentyltrimethylammonium, 6-hydroxy-n-hexyl Nitrates, sulfates, acetates, hydroxides, halides and the like of ammonium salts such as trimethylammonium and 3-hydroxyphenyltrimethylammonium; tetramethylphosphonium, tetraethylphosphonium, tetra-n-propylphosphonium, tetraisopropylphosphonium, Tetra-n-butylphosphonium, tetraisobutylphosphonium, tetra-n-pentylphosphonium, tetra-n-hexylphosphonium, tetra Phenylphosphonium, trimethylethylphosphonium, trimethylethylphosphonium, trimethyl-n-propylphosphonium, trimethylisopropylphosphonium, trimethyl-n-butylphosphonium, trimethylisobutylphosphonium, trimethyl-n-pentylphosphonium, trimethyl-n-hexylphosphonium, trimethylphenylphosphonium Dimethyldiethylphosphonium, dimethyldiphosphonium, dimethyldi-n-propylphosphonium, dimethyldiisopropylphosphonium, dimethyldi-n-butylphosphonium, dimethyldiisobutylphosphonium, dimethyldi-n-pentylphosphonium, dimethyldi-n-hexylphosphonium, dimethyldiphenylphosphonium, methyl Triethylphosphoniu , Methyltriphosphonium, methyltri-n-propylphosphonium, methyltriisopropylphosphonium, methyltri-n-butylphosphonium, methyltriisobutylphosphonium, methyltri-n-pentylphosphonium, methyltri-n-hexylphosphonium, methyltriphenylphosphonium, hydroxymethyl Trimethylphosphonium, 2-hydroxyethyltrimethylphosphonium, 3-hydroxy-n-propyltrimethylphosphonium, 4-hydroxy-n-butyltrimethylphosphonium, 5-hydroxy-n-pentyltrimethylphosphonium, 6-hydroxy-n-hexyltrimethylphosphonium, Nitrate, sulfate, acetate, hydroxide of phosphonium salts such as 3-hydroxyphenyltrimethylphosphonium Salts such as halides are used. Among these structure directing agents, organic amine compounds and ammonium salts are preferably used because a structure having a high degree of crystallinity can be obtained.
本発明において、珪素源であるシリカ構造体へのアルミニウム源、アルカリ成分、塩基性の含窒素化合物、構造規定剤の含浸または担持の順序は、特に限定されない。構造体の表層部に担持されるアルミニウム源が内部に拡散しにくいことから、アルカリ金属および/または塩基性の含窒素化合物、構造規定剤、アルミニウム源の順もしくはアルカリ金属および/または塩基性の含窒素化合物、アルミニウム源、構造規定剤の順が好ましい。アルカリ金属の担持は、アルミニウム源担持後に行っても良い。 In the present invention, the order of impregnation or loading of the aluminum source, the alkali component, the basic nitrogen-containing compound, and the structure-directing agent on the silica structure as the silicon source is not particularly limited. Since the aluminum source supported on the surface layer of the structure is difficult to diffuse inside, the alkali metal and / or basic nitrogen-containing compound, the structure directing agent, the order of the aluminum source, or the alkali metal and / or basic content. The order of nitrogen compound, aluminum source, and structure directing agent is preferred. The alkali metal may be supported after the aluminum source is supported.
本発明において、珪素源であるシリカ構造体へのアルカリ金属および/または塩基性の含窒素化合物の担持方法は、特に限定されるものではないが、シリカ担体等に物質を担持させる従来公知の方法、例えば、含浸法、沈着法、イオン交換法等が用いられる。必要であれば、乾燥、焼成を行っても良い。珪素源であるシリカ構造体へのアルカリ金属および/または塩基性の含窒素化合物の担持量は、制限されるものではないが、結晶化度の高い構造体を得ることができることから、例えば、アルカリ金属および/または塩基性の含窒素化合物/珪素比(原子比)で0.00015〜1.5が好ましく、前記効果に加えてさらに構造体の表層部に担持されるアルミニウム源が内部に拡散しにくいことから、より好ましくは0.00075〜0.75の範囲である。 In the present invention, the method for supporting an alkali metal and / or basic nitrogen-containing compound on the silica structure as a silicon source is not particularly limited, but a conventionally known method for supporting a substance on a silica support or the like. For example, an impregnation method, a deposition method, an ion exchange method, or the like is used. If necessary, drying and baking may be performed. The amount of alkali metal and / or basic nitrogen-containing compound supported on the silica structure, which is a silicon source, is not limited, but a structure with a high degree of crystallinity can be obtained. The metal and / or basic nitrogen-containing compound / silicon ratio (atomic ratio) is preferably 0.00015 to 1.5, and in addition to the above effects, the aluminum source supported on the surface layer portion of the structure diffuses inside. Since it is difficult, it is more preferably in the range of 0.00075 to 0.75.
本発明において、珪素源であるシリカ構造体への構造規定剤の担持方法は、特に限定されるものではないが、シリカ担体等に物質を担持させる従来公知の方法、例えば、含浸法、沈着法、イオン交換法等が用いられる。構造規定剤の含浸量、または、担持量は、構造規定剤/珪素比(モル比)で0〜1.0の範囲であることが好ましい。 In the present invention, the method for supporting the structure directing agent on the silica structure as a silicon source is not particularly limited, but a conventionally known method for supporting a substance on a silica support or the like, for example, an impregnation method or a deposition method. An ion exchange method or the like is used. The amount of impregnation or loading of the structure-directing agent is preferably in the range of 0 to 1.0 as a structure-directing agent / silicon ratio (molar ratio).
本発明において、珪素源であるシリカ構造体へのアルミニウム源の担持方法は、特に限定されるものではないが、例えば、アルミニウム源を溶媒に溶解させ、加温し、先に示したアルカリ金属および/または塩基性の含窒素化合物を含浸または担持したシリカ担体を瞬時に添加し、加熱攪拌する方法が挙げられる。該溶媒は、アルミニウム源が溶解すれば如何なる溶媒でもよく、例えば水、メタノール、エタノール等のアルコール類を用いることができる。該溶媒の量は、特に制限されるものではないが、例えば、構造体の表層部に担持されるアルミニウム源が内部に拡散しにくいことから、好ましくは、珪素源であるシリカ構造体の細孔容積以上であり、さらに好ましくは、珪素源であるシリカ構造体の細孔容積の1〜5倍量である。アルミニウム源を溶解した溶液の加熱温度は、特に制限されるものではないが、例えば、構造体の表層部に担持されるアルミニウム源が内部に拡散しにくいことから、好ましくは30〜100℃、さらに好ましくは60〜95℃である。加熱撹拌温度は、特に制限されるものではないが、例えば、構造体の表層部に担持されるアルミニウム源が内部に拡散しにくいことから、好ましくは30〜100℃、さらに好ましくは60〜95℃である。加熱撹拌時間は、特に制限されるものではないが、例えば、構造体の表層部に担持するアルミニウム源が内部に拡散しにくいことから、好ましくは1分から10時間、さらに好ましくは5分から5時間である。珪素源であるシリカ構造体に担持されたアルカリ金属および/または塩基性の含窒素化合物とアルミニウム源の比は、特に制限されるものではないが、例えば、構造体の表層部に担持されるアルミニウム源が内部に拡散しにくく、結晶化度の高い構造体を得ることができることから、好ましくは、アルカリ金属および/または塩基性の含窒素化合物/アルミニウム源比(元素比)で、1〜100、さらに好ましくは3〜50である。担持後は、デカンテーション、濾過、加熱または減圧加熱等の操作で溶媒を除去する。その後、乾燥、焼成を行っても良い。さらに、必要であれば、再度、構造規定剤を構造体に含浸、乾燥させても良い。 In the present invention, the method for supporting the aluminum source on the silica structure, which is the silicon source, is not particularly limited. For example, the aluminum source is dissolved in a solvent and heated, Examples thereof include a method in which a silica carrier impregnated or supported with a basic nitrogen-containing compound is instantaneously added and heated and stirred. The solvent may be any solvent as long as the aluminum source is dissolved, and for example, alcohols such as water, methanol and ethanol can be used. The amount of the solvent is not particularly limited. For example, since the aluminum source supported on the surface layer portion of the structure is difficult to diffuse inside, the pores of the silica structure which is a silicon source are preferable. More than the volume, more preferably 1 to 5 times the pore volume of the silica structure as a silicon source. The heating temperature of the solution in which the aluminum source is dissolved is not particularly limited, but is preferably 30 to 100 ° C., for example, because the aluminum source supported on the surface layer portion of the structure is difficult to diffuse inside. Preferably it is 60-95 degreeC. The heating and stirring temperature is not particularly limited, but is preferably 30 to 100 ° C., more preferably 60 to 95 ° C., because, for example, the aluminum source supported on the surface layer portion of the structure is difficult to diffuse inside. It is. Although the heating and stirring time is not particularly limited, for example, since the aluminum source supported on the surface layer portion of the structure is difficult to diffuse inside, it is preferably 1 minute to 10 hours, more preferably 5 minutes to 5 hours. is there. The ratio of the alkali metal and / or basic nitrogen-containing compound supported on the silica structure, which is a silicon source, and the aluminum source is not particularly limited. For example, aluminum supported on the surface layer of the structure Since the source is difficult to diffuse inside and a structure having a high degree of crystallinity can be obtained, the alkali metal and / or basic nitrogen-containing compound / aluminum source ratio (element ratio) is preferably 1 to 100, More preferably, it is 3-50. After loading, the solvent is removed by operations such as decantation, filtration, heating or heating under reduced pressure. Thereafter, drying and baking may be performed. Furthermore, if necessary, the structure-directing agent may be impregnated into the structure again and dried.
本発明の方法では、珪素源であるシリカ構造体へのアルミニウム源の担持は、シリカ構造体外表面から1〜1000μmの位置に担持されることが好ましく、さらに1〜500μmの位置に担持されることが好ましい。 In the method of the present invention, the loading of the aluminum source on the silica structure as the silicon source is preferably carried at a position of 1 to 1000 μm from the outer surface of the silica structure, and further carried at a position of 1 to 500 μm. Is preferred.
本発明の方法では、構造体表層部の結晶性多孔質アルミノシリケートのアルミニウム/珪素比(原子比)は、結晶化度の高い構造体を得ることができることから、好ましくは0.0001〜1、さらに好ましくは0.0005〜0.5である。 In the method of the present invention, the aluminum / silicon ratio (atomic ratio) of the crystalline porous aluminosilicate in the surface layer portion of the structure is preferably 0.0001 to 1, because a structure with a high degree of crystallinity can be obtained. More preferably, it is 0.0005-0.5.
本発明において、構造体を結晶化させる方法は、特に限定されるものではないが、例えば、水蒸気と接触させ、結晶化させることが好ましい。水蒸気の温度は特に制限されるものではないが、結晶性多孔質アルミノシリケートが製造されればよく、結晶化度の高い構造体を得ることができることから、好ましくは80〜260℃、さらに好ましくは100〜230℃の範囲である。水蒸気との接触時間は、特に制限されるものではないが、結晶化度の高い構造体を得ることができることから、好ましくは2時間以上、さらに好ましくは2時間〜80日の範囲である。 In the present invention, the method for crystallizing the structure is not particularly limited. For example, it is preferable to crystallize the structure by bringing it into contact with water vapor. The temperature of the water vapor is not particularly limited, but it is sufficient that a crystalline porous aluminosilicate is produced, and a structure having a high degree of crystallinity can be obtained. Therefore, the temperature is preferably 80 to 260 ° C., more preferably It is the range of 100-230 degreeC. Although the contact time with water vapor | steam is not restrict | limited in particular, Since a structure with a high crystallinity degree can be obtained, Preferably it is 2 hours or more, More preferably, it is the range of 2 hours-80 days.
飽和水蒸気と接触させる方法およびその装置は、構造体が製造されれば良く、特に限定されるものではないが、例えば、耐圧容器の空中にアルミニウム源、アルカリ金属を担持させたシリカ構造体を設置し、容器下部に水を添加し、密封した後、恒温槽内で加熱することで製造することができる。添加する水の量は、特に制限されるものではないが、結晶化度の高い構造体を得ることができることから、珪素源であるシリカ構造体の重さに対し0.1wt%以上が好ましい。 The method of contacting with saturated water vapor and the apparatus thereof are not particularly limited as long as the structure is produced. For example, a silica structure carrying an aluminum source and an alkali metal is installed in the air of a pressure vessel. And after adding water to a container lower part and sealing, it can manufacture by heating in a thermostat. The amount of water to be added is not particularly limited, but is preferably 0.1 wt% or more with respect to the weight of the silica structure as a silicon source because a structure with high crystallinity can be obtained.
本発明で得られた構造体は、水洗した後、乾燥し、必要により焼成、イオン交換を行っても良い。 The structure obtained in the present invention may be washed with water, dried, and fired and ion exchanged as necessary.
本発明の構造体の用途としては、特に制限はなく、その中でも触媒の担体あるいは固体酸触媒で反応する系の触媒として用いることが好ましい。 The use of the structure of the present invention is not particularly limited, and among them, it is preferably used as a catalyst for a system that reacts with a catalyst carrier or a solid acid catalyst.
本発明の構造体を触媒の担体としても使用する際の担持する元素としては、例えば、リチウム、ナトリウム、カリウム、ルビジウム、セシウムなどの周期表1族元素;ベリリウム、マグネシウム、カルシウム、ストロンチウム、バリウムなどの周期表2族元素;スカンジウム、イットリウム、ランタノイド、アクチノイドなどの周期表3族元素;チタニウム、ジルコニウム等の周期表4族元素;バナジウム、ニオブ、タンタル等の周期表5族元素;クロム、モリブデン、タングステン等の周期表6族元素;マンガン、レニウム等の周期表7族元素;鉄、ルテニウム、オスニウム等の周期表8族元素;コバルト、ロジウム、イリジウム等の周期表9族元素;ニッケル、パラジウム、白金などの周期表10族元素;銅、銀、金等の周期表11族元素;亜鉛、カドミウムなどの周期表12族元素;ホウ素、アルミニウム、ガリウム、インジウム、タリウム等の周期表13族元素;ゲルマニウム、スズ、鉛等の周期表14族元素;アンチモン、ビスマス等の周期表15族元素;硫黄、テルル等の周期表16族元素等の一種類以上の元素が挙げられる。
Examples of supported elements when the structure of the present invention is used as a catalyst carrier include, for example, elements of
また、本発明の構造体を固体酸触媒で反応する系の触媒として使用する反応系としては、例えば、軽油および重質油などの接触分解反応;重質油の水素化分解反応;シクロヘキサンの脱水素、シクロペンテンの異性化脱水素、パラフィンの環化脱水素、パラフィンの異性化、パラフィンの水素化分解などの石油ナフサの重質留分の接触改質反応;ブタン、ペンタン、ヘキサン、ブテン、ペンテン、ヘキセン、キシレンなどのアルカン、アルケンの異性化反応;メタン、エタン、プロパン、ブタン、ペンタン、ヘキサン、エチレン、プロピレン、ブテン、ペンテン、ヘキセン等の芳香族化反応;ベンゼン、アルキルベンゼン、ナフタレン、フェノール、チオフェン、ピリジン等とエチレン、プロピレン、ブテン、ペンテン、ヘキセン、メタノール、エタノール、プロパノール、ブタノール、エチルクロリド、プロピルプロリド、ブチルクロリド等のオレフィン、アルコールハロゲン化アルキル等の芳香族のアルキル化反応;トルエン、エチルベンゼン、プロピルベンゼン、ブチルベンゼン、キシレン、ジエチルベンゼン、ジプロピルベンゼン、ジブチルベンゼン、トリメチルベンゼン、トリエチルベンゼン、トリプロピルベンゼン、トリブチルベンゼン等のアルキル芳香族の異性化、不均化、トランスアルキル化、脱アルキル化反応;エチレン、プロピレン、ブテン、ペンテン、ヘキセン等のオレフィン重合反応等が挙げられる。これらの系のなかでも、芳香族化反応用触媒に用いることが好ましい。 Examples of a reaction system that uses the structure of the present invention as a catalyst for reacting with a solid acid catalyst include catalytic cracking reaction of light oil and heavy oil; hydrocracking reaction of heavy oil; cyclohexane dehydration. Catalytic reforming of heavy fractions of petroleum naphtha such as isomerization dehydrogenation of benzene, cyclopentene, cyclization dehydrogenation of paraffin, isomerization of paraffin, hydrocracking of paraffin; butane, pentane, hexane, butene, pentene Isomerization reaction of alkanes, alkenes such as hexene, xylene; methane, ethane, propane, butane, pentane, hexane, ethylene, propylene, butene, pentene, hexene, etc .; benzene, alkylbenzene, naphthalene, phenol, Thiophene, pyridine, etc. and ethylene, propylene, butene, pentene, hexene, methanol , Ethanol, propanol, butanol, ethyl chloride, propyl prolide, butyl chloride and other olefins, alcohol alkyl halides and other aromatic alkylation reactions; toluene, ethylbenzene, propylbenzene, butylbenzene, xylene, diethylbenzene, dipropylbenzene Isomerization, disproportionation, transalkylation, dealkylation reactions of alkylaromatics such as benzene, dibutylbenzene, trimethylbenzene, triethylbenzene, tripropylbenzene, tributylbenzene; olefins such as ethylene, propylene, butene, pentene, hexene Polymerization reaction etc. are mentioned. Among these systems, it is preferable to use the catalyst for aromatization reaction.
本発明の構造体を芳香族化反応用触媒に用いる際には、亜鉛および/またはガリウムを担持することを特徴とする。 When the structure of the present invention is used as a catalyst for aromatization reaction, it is characterized by supporting zinc and / or gallium.
その際に、構造体上に担持される亜鉛および/またはガリウムの量は特に制限されないが、好ましくは構造体の全重量に対して、0.01〜30重量%、さらに好ましくは1〜25重量%である。構造体に担持されている亜鉛またはガリウムの担持状態については、特に限定されず、例えば、酸化物、硝酸塩、塩化物等の状態で担持されている。本発明の芳香族反応用触媒に用いられる亜鉛またはガリウムは、それぞれ単独、または混合して用いても差し支えなく、特に原料の入手が容易であり、しかも構造体の調製が容易であることから、亜鉛が好ましく用いられる。 At that time, the amount of zinc and / or gallium supported on the structure is not particularly limited, but is preferably 0.01 to 30% by weight, more preferably 1 to 25% by weight based on the total weight of the structure. %. The state of supporting zinc or gallium supported on the structure is not particularly limited, and for example, it is supported in the state of oxide, nitrate, chloride or the like. Zinc or gallium used in the aromatic reaction catalyst of the present invention may be used alone or in combination, and since the raw materials are particularly easily obtained and the structure can be easily prepared, Zinc is preferably used.
本発明の芳香族化反応用触媒の調製法は特に制限はなく、本発明の芳香族化反応用触媒の調製が可能である限り、如何なる方法を用いても差し支えない。以下に、本発明の芳香族化反応用触媒の調製方法として、好ましい態様を示すが、本発明はこれに限定されるものではない。 The method for preparing the aromatization reaction catalyst of the present invention is not particularly limited, and any method may be used as long as the aromatization reaction catalyst of the present invention can be prepared. Hereinafter, preferred embodiments of the method for preparing the aromatization reaction catalyst of the present invention will be described, but the present invention is not limited thereto.
本発明の芳香族化反応用触媒の調製方法は、例えば、あらかじめ構造体表層部に結晶性多孔質アルミノシリケートが存在し、構造体表層部を除く内部の層に無機支持体が存在する前記の構造体を調製し、この構造体に亜鉛および/またはガリウムを担持して調製する方法が挙げられる。 The method for preparing the catalyst for aromatization reaction of the present invention is, for example, the above-mentioned method wherein the crystalline porous aluminosilicate is present in the structure surface layer portion in advance and the inorganic support is present in the inner layer excluding the structure surface layer portion. Examples thereof include a method of preparing a structure and preparing the structure by supporting zinc and / or gallium.
結晶性多孔質アルミノシリケートの組成は一般に下記式(1)で表される。 The composition of the crystalline porous aluminosilicate is generally represented by the following formula (1).
xM2/nO・Al2O3・ySiO2・zH2O (1)
(ここで、nは陽イオンMの原子価、xは0.8〜2の範囲の数、yは2以上の数、zは0以上の数である。)
一方、上記の方法で調製される構造体は、構造体表層部に結晶性多孔質アルミノシリケートが存在する。該結晶性多孔質アルミノシリケートの組成は下記式(2)で表され、陽イオンはナトリウムイオンである(以下、陽イオンがナトリウムイオンとなる組成を持つ構造体をナトリウム型と呼ぶ)。
xM 2 / n O · Al 2 O 3 ·
(Here, n is the valence of the cation M, x is a number in the range of 0.8 to 2, y is a number of 2 or more, and z is a number of 0 or more.)
On the other hand, the structure prepared by the above method has crystalline porous aluminosilicate in the surface layer portion of the structure. The composition of the crystalline porous aluminosilicate is represented by the following formula (2), and the cation is a sodium ion (hereinafter, a structure having a composition in which the cation becomes a sodium ion is referred to as a sodium type).
aNa2O・Al2O3・bSiO2・cH2O (2)
(ここで、aは0.8〜2の範囲の数、bは2以上の数、cは0以上の数である。)
本発明で用いる芳香族反応用触媒では触媒活性が高いことから、(1)式の陽イオンが水素イオン、すなわちプロトン(以下、陽イオンが水素イオンとなる組成を持つ構造体をプロトン型と呼ぶ)であることが好ましい。ナトリウム型をプロトン型に転換する方法は、特に限定されるものではないが、例えば、ナトリウム型の構造体を塩化アンモニウムでイオン交換し、次いで空気中で焼成処理する方法が挙げられる。ここで、塩化アンモニウムでのイオン交換は常法に従って行えばよく、また焼成を行う場合には、酸素、または、窒素、ヘリウム、アルゴン等の不活性ガスで希釈した酸素、あるいは、空気の雰囲気下100〜1,000℃で行うと良い。
aNa 2 O · Al 2 O 3 ·
(Here, a is a number in the range of 0.8 to 2, b is a number of 2 or more, and c is a number of 0 or more.)
Since the aromatic reaction catalyst used in the present invention has high catalytic activity, a structure having a composition in which the cation of formula (1) is a hydrogen ion, that is, a proton (hereinafter, the cation becomes a hydrogen ion) is called a proton type. ) Is preferable. The method for converting the sodium type to the proton type is not particularly limited, and examples thereof include a method in which a sodium type structure is ion-exchanged with ammonium chloride and then calcined in air. Here, ion exchange with ammonium chloride may be carried out in accordance with a conventional method. In the case of firing, oxygen, oxygen diluted with an inert gas such as nitrogen, helium, or argon, or an air atmosphere. It is good to carry out at 100-1,000 degreeC.
上記の方法により、本発明で用いられる芳香族化反応用触媒の構造体が得られる。本発明の芳香族化反応用触媒は、前記の構造体に亜鉛および/またはガリウムを担持して調製される。ここで、亜鉛としては、特に限定されないが、例えば、亜鉛金属、酸化亜鉛、水酸化亜鉛、硝酸亜鉛、炭酸亜鉛、硫酸亜鉛、塩化亜鉛、酢酸亜鉛、シュウ酸亜鉛などの塩類;あるいはアルキル亜鉛などの有機亜鉛化合物類等が挙げられる。これらのうち、担持が容易であり、しかもオレフィンの芳香族化において芳香族炭化水素の収率が高いことから、塩類が好ましく用いられ、さらに好ましくは硝酸亜鉛が用いられる。また、ガリウムとしては、特に限定されないが、例えば、塩化ガリウム、臭化ガリウム、硝酸ガリウム、酸化ガリウムなどの塩類;あるいはアセチルアセトナトガリウム、ガリウムエトキシドなどの有機ガリウム化合物類等が挙げられる。これらのうち、担持が容易であり、しかもオレフィンの芳香族化において芳香族炭化水素の収率が高いことから、塩類が好ましく用いられ、さらに好ましくは硝酸ガリウムが用いられる。 By the above method, the structure of the aromatization reaction catalyst used in the present invention is obtained. The catalyst for aromatization reaction of the present invention is prepared by supporting zinc and / or gallium on the above structure. Here, although it does not specifically limit as zinc, For example, salts, such as zinc metal, zinc oxide, zinc hydroxide, zinc nitrate, zinc carbonate, zinc sulfate, zinc chloride, zinc acetate, zinc oxalate; Or alkyl zinc etc. Organic zinc compounds and the like. Among these, salts are preferably used, and zinc nitrate is more preferably used since it is easily supported and has a high yield of aromatic hydrocarbons in the olefin aromatization. Examples of gallium include, but are not limited to, salts such as gallium chloride, gallium bromide, gallium nitrate, and gallium oxide; or organic gallium compounds such as acetylacetonatogallium and gallium ethoxide. Of these, salts are preferably used, and gallium nitrate is more preferably used because of its easy loading and high yield of aromatic hydrocarbons in the olefin aromatization.
亜鉛および/またはガリウムを構造体に担持させる方法に特に制約はなく、通常の担持方法、例えば、含浸担持法、イオン交換法および共沈法を用いることができ、好ましくは含浸担持法がよい。含浸担持法で芳香族化反応用触媒を調製する場合、例えば、上記の亜鉛やガリウムを含む溶液を、構造体に含浸させ、乾燥、さらに焼成処理を行い、芳香族化反応用触媒を調製する方法が挙げられる。 There is no particular limitation on the method for supporting zinc and / or gallium on the structure, and usual supporting methods such as an impregnation supporting method, an ion exchange method and a coprecipitation method can be used, and an impregnation supporting method is preferable. When preparing an aromatization reaction catalyst by the impregnation support method, for example, impregnating the above-described solution containing zinc or gallium into a structure, drying, and further firing treatment to prepare an aromatization reaction catalyst A method is mentioned.
担持後は含浸法またはイオン交換法における常法に従って、デカンテーション、濾過、加熱または減圧加熱等の操作で溶媒を除去する。溶媒を除去後の乾燥は、加熱乾燥、減圧乾燥等を用いることができる。焼成を行う場合には、酸素、または、窒素、ヘリウム、アルゴン等の不活性ガスで希釈した酸素、あるいは、空気の雰囲気下100〜1,000℃で行うと良い。ここで、亜鉛および/またはガリウムを構造体に担持させる順序は、特に制限されず、前記のプロトン型の構造体に担持してもよいし、アンモニウム型の構造体に担持して、続いて焼成処理を行って調製しても良い。 After the loading, the solvent is removed by operations such as decantation, filtration, heating or heating under reduced pressure according to a conventional method in the impregnation method or ion exchange method. Drying after removing the solvent can be performed by heat drying, drying under reduced pressure, or the like. In the case of performing the firing, the firing is preferably performed at 100 to 1,000 ° C. in an atmosphere of oxygen, oxygen diluted with an inert gas such as nitrogen, helium, or argon, or air. Here, the order in which zinc and / or gallium are supported on the structure is not particularly limited, and may be supported on the proton-type structure or may be supported on the ammonium-type structure and then fired. You may prepare by processing.
本発明においては、上記の芳香族化用反応触媒に、オレフィンの芳香族化に差し支えない範囲で、亜鉛およびガリウム以外の金属がさらに担持されていてもよく、例えば、リチウム、ナトリウム、カリウム、ルビジウム、セシウムなどの周期表1族元素;ベリリウム、マグネシウム、カルシウム、ストロンチウム、バリウムなどの周期表2族元素;スカンジウム、イットリウム、ランタノイド、アクチノイドなどの周期表3族元素;チタニウム、ジルコニウム等の周期表4族元素;バナジウム、ニオブ、タンタル等の周期表5族元素;クロム、モリブデン、タングステン等の周期表6族元素;マンガン、レニウム等の周期表7族元素;鉄、ルテニウム、オスニウム等の周期表8族元素;コバルト、ロジウム、イリジウム等の周期表9族元素;ニッケル、パラジウム、白金などの周期表10族元素;銅、銀、金等の周期表11族元素;亜鉛、カドミウムなどの周期表12族元素;ホウ素、アルミニウム、ガリウム、インジウム、タリウム等の周期表13族元素;ゲルマニウム、スズ、鉛等の周期表14族元素;アンチモン、ビスマス等の周期表15族元素;硫黄、テルル等の周期表16族元素などの金属が挙げられる。
In the present invention, the aromatization reaction catalyst may further carry a metal other than zinc and gallium within a range that does not interfere with the olefin aromatization. For example, lithium, sodium, potassium, rubidium
本発明の構造体表層部に結晶性多孔質アルミノシリケートが存在し、構造体表層部を除く内部の層に無機支持体が存在する構造体に亜鉛および/またはガリウムが担持した芳香族化反応用触媒は、オレフィンの芳香族化による芳香族炭化水素の製造方法にも用いられる。 For the aromatization reaction in which zinc and / or gallium is supported on a structure in which a crystalline porous aluminosilicate is present in the surface layer of the structure of the present invention and an inorganic support is present in an inner layer excluding the surface layer of the structure The catalyst is also used in a method for producing an aromatic hydrocarbon by aromatizing an olefin.
前記オレフィンは、該化合物中に二重結合が含まれれば特に限定されるものではないが、例えば、エチレン、プロピレン、ブテン、ペンテン、ヘキセン、ヘプテン、オクテン、ノネン、デセン等が挙げられる。 The olefin is not particularly limited as long as the compound contains a double bond, and examples thereof include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, and decene.
本発明においては、上記オレフィンにさらにエタン、プロパン、ブタン、ペンタン、ヘキサン、ヘプタン、オクタン、ノナン等のパラフィン類;および/またシクロペンタン、シクロペンテン、メチルシクロペンタン、シクロヘキサン、メチルシクロペンテン、シクロヘキセン、シクロヘプテン、シクロオクテン、シクロヘキサジエン等のナフテン類が混合していても差し支えない。これらパラフィン類とナフテン類は芳香族化の原料に成り得るが、オレフィンに比べ芳香族化の速度が遅いため、パラフィン類とナフテン類を混合する量は、好ましくは全重量に対して50重量%未満、さらに好ましくは30重量%未満にコントロールされる。これらのオレフィンは単独で使用し得るのみならず、二種以上を混合して用いることも可能である。混合物としては、上記のそれぞれの混合物、あるいはナフサなどの熱分解生成物のC4留分、前記C4留分よりブタジエンを除いた留分(S(以下、スペントと略称する)−C4またはラフィネート1と呼ばれる)、前記C4留分よりブタジエンとi−ブテンを除いた留分(SS−C4またはラフィネート2と呼ばれる)、ナフサなどの熱分解生成物のC5留分、前記C5留分からジエン類を除いた留分(S−C5と呼ばれる)、熱分解ガソリン、熱分解ガソリンよりBTX抽出を行ったラフィネート、FCC分解ガス、FCC分解ガソリン、リフォメートよりBTXを抽出したラフィネート等が挙げられる。 In the present invention, paraffins such as ethane, propane, butane, pentane, hexane, heptane, octane, and nonane; and / or cyclopentane, cyclopentene, methylcyclopentane, cyclohexane, methylcyclopentene, cyclohexene, cycloheptene, It does not matter if naphthenes such as cyclooctene and cyclohexadiene are mixed. Although these paraffins and naphthenes can be used as a raw material for aromatization, since the rate of aromatization is slower than that of olefins, the amount of paraffins and naphthenes mixed is preferably 50% by weight based on the total weight. Less than, more preferably less than 30% by weight. These olefins can be used alone or in combination of two or more. Examples of the mixture include the above-mentioned respective mixtures, C 4 fractions of thermal decomposition products such as naphtha, fractions obtained by removing butadiene from the C 4 fraction (S (hereinafter abbreviated as spent) -C4 or raffinate). 1 and referred to), the C 4 fraction from fraction excluding butadiene and i- butene (referred to as SS-C4 or raffinate 2), C 5 fraction of the pyrolysis products, such as naphtha, from the C 5 fraction Examples include distillate-excluded fraction (referred to as S-C5), pyrolysis gasoline, raffinate obtained by BTX extraction from pyrolysis gasoline, FCC cracked gas, FCC cracked gasoline, raffinate obtained by extracting BTX from reformate, and the like.
本発明のオレフィンの芳香族化による芳香族炭化水素の製造における反応形式は特に制限されず、任意の反応形式で行うことが可能である。例えば、固定床気相流通式、固定床液相流通式、または懸濁床回分式で行うことができる。これらのうち、芳香族炭化水素が効率的に得られること、さらに温和な条件で芳香族化反応を行うことができることから固定床液相流通式が好ましい。反応温度は特に制限はされないが、芳香族炭化水素へ効率的に変換できることから、好ましくは300〜700℃、さらに好ましくは400〜600℃である。反応圧力は特に制限されないが、通常、好ましくは絶対圧で0.01〜50MPaであり、さらに好ましくは0.05〜30MPaである。また、固定床液相流通式反応の際の液時間空間速度(LHSV)は、芳香族炭化水素へ効率的に変換できることから、好ましくは0.01〜100hr−1、さらに好ましくは0.5〜20hr−1である。ここで、液時間空間速度(LHSV)とは、単位触媒体積当たりの単位時間(hr)に対するオレフィン、パラフィンおよびナフテンの供給量の合計体積を表すものである。 The reaction mode in the production of aromatic hydrocarbons by aromatization of the olefin of the present invention is not particularly limited, and can be carried out in any reaction mode. For example, it can be carried out by a fixed bed gas phase flow type, a fixed bed liquid phase flow type, or a suspension bed batch type. Of these, the fixed bed liquid phase flow system is preferred because aromatic hydrocarbons can be obtained efficiently and the aromatization reaction can be carried out under mild conditions. The reaction temperature is not particularly limited, but is preferably 300 to 700 ° C., more preferably 400 to 600 ° C. because it can be efficiently converted into an aromatic hydrocarbon. The reaction pressure is not particularly limited, but is usually preferably 0.01 to 50 MPa in absolute pressure, and more preferably 0.05 to 30 MPa. The liquid hourly space velocity (LHSV) during the fixed bed liquid phase flow reaction is preferably 0.01 to 100 hr −1 , more preferably 0.5 to 0.5, because it can be efficiently converted into an aromatic hydrocarbon. 20 hr −1 . Here, the liquid hourly space velocity (LHSV) represents the total volume of olefin, paraffin and naphthene supplied per unit time (hr) per unit catalyst volume.
なお、オレフィン原料は、そのまま用いても、不活性ガスで希釈して用いても良い。不活性ガスとしては特に制限されるものではないが、例えば、窒素、ヘリウムまたはアルゴン等が挙げられ、これらの不活性ガスは単独で使用するのみならず、二種以上を混合して用いることも可能である。 The olefin raw material may be used as it is or diluted with an inert gas. Although it does not restrict | limit especially as an inert gas, For example, nitrogen, helium, or argon etc. are mentioned, These inert gas can be used not only by itself but in mixture of 2 or more types. Is possible.
ここで、生成する芳香族炭化水素は、例えば、ベンゼン、トルエン、キシレン、スチレン、キュメン、プロピルベンゼン、トリメチルベンゼン、インデン、ナフタレン、ジイソプロピルベンゼン、ビフェニル等が挙げられる。これらの芳香族炭化水素は公知の分離方法により分離され、石油化学、医薬、農薬原料として用いられる。また、炭素数1〜12のオレフィン、パラフィンおよびナフテン類が未反応原料として、また副反応性生物として生成するが、これら化合物は本発明のオレフィンの芳香族反応にリサイクルしてオレフィンの原料の一部としても用いてもよい。 Here, examples of the aromatic hydrocarbon to be generated include benzene, toluene, xylene, styrene, cumene, propylbenzene, trimethylbenzene, indene, naphthalene, diisopropylbenzene, and biphenyl. These aromatic hydrocarbons are separated by known separation methods and used as petrochemical, pharmaceutical and agricultural chemical raw materials. In addition, olefins having 1 to 12 carbon atoms, paraffins and naphthenes are produced as unreacted raw materials and by-products, but these compounds are recycled into the aromatic reaction of olefins of the present invention and are one of the raw materials for olefins. It may also be used as a part.
本発明の構造体は、構造体表層部に固体酸触媒として有効な結晶性多孔質アルミノシリケートが存在するため、反応原料および反応生成物の構造体中の滞留時間が短く、目的物の選択性が高く、また活性点の被毒や細孔の閉塞を生じにくいため、触媒活性が低下しにくく、さらに触媒寿命の長いという効果を有する。特に、本発明の構造体表層部に結晶性多孔質アルミノシリケートが存在し、構造体表層部を除く内部の層に無機支持体が存在する構造体に亜鉛および/またはガリウムが担持したことを特徴とする芳香族化反応用触媒は、構造体表層部に固体酸触媒として有効な結晶性多孔質アルミノシリケートが存在するため、オレフィン原料および反応生成物の触媒中の滞留時間が短くなる。したがって、コーク様物質の蓄積が少なくなり、高い触媒活性を長い時間維持できるという効果を有する。 The structure of the present invention has a crystalline porous aluminosilicate that is effective as a solid acid catalyst in the surface layer of the structure, so that the residence time of the reaction raw materials and reaction products in the structure is short, and the selectivity of the target product In addition, since it is difficult to cause poisoning of active sites and clogging of pores, the catalytic activity is unlikely to be lowered and the catalyst life is long. In particular, it is characterized in that crystalline porous aluminosilicate is present in the surface layer portion of the structure of the present invention, and zinc and / or gallium is supported on the structure in which the inorganic support is present in the inner layer excluding the structure surface layer portion. In the catalyst for aromatization reaction, since crystalline porous aluminosilicate effective as a solid acid catalyst is present in the surface layer of the structure, the residence time of the olefin raw material and reaction product in the catalyst is shortened. Accordingly, there is an effect that the accumulation of the coke-like substance is reduced and high catalytic activity can be maintained for a long time.
以下、実施例により本発明をさらに具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
以下の実施例に用いた測定法を示す。 The measurement methods used in the following examples are shown.
(構造体の結晶状態の確認)
得られた構造体の結晶状態は、粉末X線回折測定装置(XRD)(マックサイエンス社製、商品名M18XHF)を用い、電圧40kV、電流200mAで測定した。
(Confirmation of crystal state of structure)
The crystal state of the obtained structure was measured at a voltage of 40 kV and a current of 200 mA using a powder X-ray diffraction measurement apparatus (XRD) (manufactured by Mac Science, trade name: M18XHF).
(アルミニウムの深さ方向の担持分布および珪素/アルミニウム比の測定)
得られた構造体を、Poly/Bed(R)812(Polysciences,Inc.社製)、Nadic Methyl Anhydride(Polysciences,Inc.社製)、Dodecenylsuccinic Anhydride(Polysciences,Inc.社製)、2,4,6Tris(dimethylaminomethyl)phenol(Polysciences,Inc.社製)を原料とした樹脂に包埋し、ウルトラミクロトームで切削して得られた試料を、エックス線マイクロアナライザー(EPMA)(島津製作所製、商品名EPM−810)を用い電圧20kV、電流10nAにて粒子断面の深さ方向の線分析、面分析を行い、強度比から担持割合を算出した。
(Measurement of aluminum depth distribution and silicon / aluminum ratio)
The obtained structures were obtained from Poly / Bed (R) 812 (Polysciences, Inc.), Nadic Methyl Anhydride (Polysciences, Inc.), Dodecenylsuccinic Anhydride (PolyScience, Inc., PolyInc., Inc.). An X-ray microanalyzer (EPMA) (trade name EPM-, manufactured by Shimadzu Corporation) was prepared by embedding in a resin using 6Tris (dimethylaminomethyl) phenol (manufactured by Polysciences, Inc.) as a raw material and cutting with an ultramicrotome. 810), a line analysis in the depth direction of the particle cross section and a surface analysis were performed at a voltage of 20 kV and a current of 10 nA, and the loading ratio was calculated from the intensity ratio.
(ゼオライト骨格構造内のアルミニウムの確認)
27Al固体NMR(日本電子社製、商品名GSX−270)で測定し、ゼオライト骨格構造内の4配位アルミニウムに帰属する化学シフト(σ)=50〜70ppmの範囲に測定されるピークと、骨格構造から外れた格子外の6配位アルミニウムに帰属する化学シフト(σ)=0〜10ppmの範囲に測定されるピークで確認した。
(Confirmation of aluminum in zeolite framework structure)
Peak measured in 27 Al solid state NMR (trade name GSX-270, manufactured by JEOL Ltd.) and measured in the range of chemical shift (σ) = 50 to 70 ppm attributed to 4-coordinated aluminum in the zeolite framework structure; This was confirmed by a peak measured in the range of chemical shift (σ) = 0 to 10 ppm attributed to off-lattice 6-coordinated aluminum deviating from the skeletal structure.
(アルミニウム量の測定)
アルミニウム量は、誘導結合プラズマ発光分光分析装置(ICP)(京都光研製、商品名ICP−AES UOP−1 markII)にて定量分析し、算出した。
(Measurement of aluminum content)
The amount of aluminum was quantitatively analyzed and calculated using an inductively coupled plasma emission spectrometer (ICP) (trade name ICP-AES UOP-1 mark II, manufactured by Kyoto Koken).
(コーク生成量の測定)
反応終了後の触媒を熱天秤(SEIKO製SSC/5200)に約10mg乗せ、空気雰囲気下、10℃/分で800℃まで昇温させた。700℃での触媒重量に対し、300℃から700℃までの減少重量をコーク生成量とした。
(Measurement of coke production)
About 10 mg of the catalyst after completion of the reaction was placed on a thermobalance (SSC / 5200 manufactured by SEIKO) and heated to 800 ° C. at 10 ° C./min in an air atmosphere. With respect to the catalyst weight at 700 ° C., the reduced weight from 300 ° C. to 700 ° C. was defined as the amount of coke produced.
実施例1
20wt%テトラ−n−プロピルアンモニウムヒドロキシド水溶液12.2g(テトラ−n−プロピルアンモニウムヒドロキシド/珪素=0.07(モル比))に水酸化ナトリウム0.3g(ナトリウム/珪素比=0.04(原子比))を添加し溶解した。この水溶液にシリカビーズ(富士シリシア化学社製 「キャリアクトQ−50」、粒子形状:球状、粒子径:1.7〜4.0mm、表面積:80m2/g、平均細孔径50nm)11gを添加し、シリカビ−ズに水溶液を含浸した。
Example 1
20 wt% tetra-n-propylammonium hydroxide aqueous solution 12.2 g (tetra-n-propylammonium hydroxide / silicon = 0.07 (molar ratio)) and 0.3 g of sodium hydroxide (sodium / silicon ratio = 0.04) (Atom ratio)) was added and dissolved. To this aqueous solution, 11 g of silica beads (Fuji Silysia Chemical Co., Ltd. “Caractect Q-50”, particle shape: spherical, particle diameter: 1.7 to 4.0 mm, surface area: 80 m 2 / g, average pore diameter of 50 nm) is added. Then, silica beads were impregnated with an aqueous solution.
つぎに、硝酸アルミニウム・9水和物0.4g(ナトリウム/アルミニウム=6.7(原子比))を水12mlに溶解させ、75℃に加温した後、先の水酸化ナトリウム、テトラプロピルアンモニウムヒドロキシドを含浸したシリカビーズを添加し、30分攪拌した。撹拌後、減圧乾燥し、80℃窒素雰囲気下で5時間乾燥した。 Next, 0.4 g of aluminum nitrate nonahydrate (sodium / aluminum = 6.7 (atomic ratio)) was dissolved in 12 ml of water, heated to 75 ° C., and then sodium hydroxide, tetrapropylammonium. Silica beads impregnated with hydroxide were added and stirred for 30 minutes. After stirring, the mixture was dried under reduced pressure, and dried for 5 hours at 80 ° C. in a nitrogen atmosphere.
得られた球状のシリカ構造体のアルミニウムのライン分析の結果を図5に示す。担持したアルミニウムはシリカビーズ外表面から230μm以内に存在していることが解った。 FIG. 5 shows the result of aluminum line analysis of the obtained spherical silica structure. It was found that the supported aluminum was present within 230 μm from the outer surface of the silica beads.
テフロン(登録商標)の耐圧容器に0.5gの水を入れ、水に触れないようにテフロン(登録商標)の皿を起き、その上に水酸化ナトリウム、テトラ−n−プロピルアンモニウムヒドロキシド、アルミニウム源を担持したシリカビーズ11gを入れ、耐圧容器を密閉し、耐圧容器を180℃で8時間加熱し、結晶化処理を行った。 Put 0.5 g of water into a Teflon (registered trademark) pressure vessel, wake up a Teflon (registered trademark) dish so that it does not come in contact with water, and then add sodium hydroxide, tetra-n-propylammonium hydroxide, aluminum 11 g of silica beads carrying the source was added, the pressure vessel was sealed, and the pressure vessel was heated at 180 ° C. for 8 hours to perform crystallization treatment.
その後、蒸留水で洗浄後、110℃で一晩乾燥後、空気中540℃で焼成した。 Then, after washing with distilled water, drying was performed at 110 ° C. overnight, followed by firing at 540 ° C. in air.
得られた構造体の粉末X線回折測定の結果(図6)、MFI構造であることが解った。また、アルミニウムの面分析、ライン分析の結果(図7,8)より、アルミニウムは得られた構造体外表面から230μm以内に存在し、また、EPMAによる局所部分の成分分析の結果、得られた構造体の表層部のアルミニウム/珪素比(原子比)=0.020であり、構造体外表面から250μm付近、中心付近からはアルミニウムは検出限界以下であった。 As a result of the powder X-ray diffraction measurement of the obtained structure (FIG. 6), it was found to have an MFI structure. Further, from the results of aluminum surface analysis and line analysis (FIGS. 7 and 8), aluminum is present within 230 μm from the outer surface of the obtained structure, and the structure obtained as a result of component analysis of the local portion by EPMA. The aluminum / silicon ratio (atomic ratio) of the surface layer of the body was 0.020, and the aluminum was below the detection limit from around 250 μm from the outer surface of the structure and from near the center.
27Alの固体NMR測定の結果(図9)、化学シフト(σ)50〜70ppm範囲のピークのみが確認され、アルミニウムはゼオライト骨格構造内に存在していることがわかった。 As a result of solid-state NMR measurement of 27 Al (FIG. 9), only a peak in the chemical shift (σ) range of 50 to 70 ppm was confirmed, and it was found that aluminum was present in the zeolite framework structure.
このことから、構造体表層部230μmの厚さでMFI構造を持つ結晶性多孔質アルミノシリケートが存在し、構造体表層部を除く内部の層がMFI構造を持つ結晶性多孔質シリケートの無機支持体であり、粒子径1.7〜4.0mmの球状の構造体であることがわかった。 Accordingly, there is a crystalline porous aluminosilicate having an MFI structure with a thickness of 230 μm in the structure surface layer portion, and an inorganic support of the crystalline porous silicate in which the inner layer excluding the structure surface layer portion has the MFI structure It was found to be a spherical structure having a particle diameter of 1.7 to 4.0 mm.
実施例2
20wt%テトラ−n−プロピルアンモニウムヒドロキシド水溶液12.2g(テトラ−n−プロピルアンモニウムヒドロキシド/珪素=0.07(モル比))に水酸化ナトリウム0.5g(ナトリウム/珪素比=0.07(原子比))を添加し溶解した。この水溶液にシリカビーズ(富士シリシア化学社製 「キャリアクトQ−50」、粒子形状:球状、粒子径:1.7〜4.0mm、表面積:80m2/g、平均細孔径50nm)11gを添加し、シリカビ−ズに水溶液を含浸した。
Example 2
20 wt% tetra-n-propylammonium hydroxide aqueous solution 12.2 g (tetra-n-propylammonium hydroxide / silicon = 0.07 (molar ratio)) and sodium hydroxide 0.5 g (sodium / silicon ratio = 0.07) (Atom ratio)) was added and dissolved. To this aqueous solution, 11 g of silica beads (Fuji Silysia Chemical Co., Ltd. “Caractect Q-50”, particle shape: spherical, particle diameter: 1.7 to 4.0 mm, surface area: 80 m 2 / g, average pore diameter of 50 nm) is added. Then, silica beads were impregnated with an aqueous solution.
つぎに、硝酸アルミニウム・9水和物0.4g(ナトリウム/アルミニウム=11.7(原子比))を水12mlに溶解させ、75℃に加温した後、水酸化ナトリウム、テトラプロピルアンモニウムヒドロキシドを含浸したシリカビーズを添加し、30分攪拌した。撹拌後、上澄みを除去し、減圧乾燥した後、80℃窒素雰囲気下で5時間乾燥した。得られたシリカ構造体のアルミニウムのライン分析の結果を図10に示す。担持したアルミニウムはシリカビーズ外表面から20μm以内に存在していることが解った。 Next, 0.4 g of aluminum nitrate nonahydrate (sodium / aluminum = 11.7 (atomic ratio)) was dissolved in 12 ml of water, heated to 75 ° C., and then sodium hydroxide, tetrapropylammonium hydroxide. The silica beads impregnated with were added and stirred for 30 minutes. After stirring, the supernatant was removed, dried under reduced pressure, and then dried at 80 ° C. in a nitrogen atmosphere for 5 hours. The result of the line analysis of the aluminum of the obtained silica structure is shown in FIG. It was found that the supported aluminum was present within 20 μm from the outer surface of the silica beads.
テフロン(登録商標)の耐圧容器に0.5gの水を入れ、水に触れないようにテフロン(登録商標)の皿を起き、その上に水酸化ナトリウム、テトラ−n−プロピルアンモニウムヒドロキシド、アルミニウム源を担持したシリカビーズ11gを入れ、耐圧容器を密閉し、耐圧容器を180℃で8時間加熱し、結晶化処理を行った。 Put 0.5 g of water into a Teflon (registered trademark) pressure vessel, wake up a Teflon (registered trademark) dish so that it does not come in contact with water, and then add sodium hydroxide, tetra-n-propylammonium hydroxide, aluminum 11 g of silica beads carrying the source was added, the pressure vessel was sealed, and the pressure vessel was heated at 180 ° C. for 8 hours to perform crystallization treatment.
その後、蒸留水で洗浄後、110℃で一晩乾燥後、空気中540℃で焼成した。 Then, after washing with distilled water, drying was performed at 110 ° C. overnight, followed by firing at 540 ° C. in air.
得られた構造体の粉末X線回折測定の結果(図11)、MFI構造であることが解った。また、アルミニウムの面分析、ライン分析の結果(図12,13)より、アルミニウムは得られた構造体外表面から20μm以内に存在し、また、EPMAによる局所部分の成分分析の結果、得られた構造体の表層部のアルミニウム/珪素比(原子比)=0.016であり、構造体外表面から200μm付近、中心付近からはアルミニウムは検出限界以下であった。 As a result of the powder X-ray diffraction measurement of the obtained structure (FIG. 11), it was found to have an MFI structure. Further, from the results of aluminum surface analysis and line analysis (FIGS. 12 and 13), aluminum is present within 20 μm from the outer surface of the obtained structure, and the structure obtained as a result of component analysis of the local portion by EPMA. The aluminum / silicon ratio (atomic ratio) of the surface layer of the body was 0.016, and the aluminum was below the detection limit near 200 μm from the outer surface of the structure and from the center.
27Alの固体NMR測定の結果、化学シフト(σ)50〜70ppm範囲のピークのみが確認され、アルミニウムはゼオライト骨格構造内に存在していることがわかった。 As a result of solid-state NMR measurement of 27 Al, only a peak in the chemical shift (σ) range of 50 to 70 ppm was confirmed, and it was found that aluminum was present in the zeolite framework structure.
このことから、構造体表層部20μmの厚さでMFI構造をもつ結晶性多孔質アルミノシリケートが存在し、構造体表層部を除く内部の層がMFI構造をもつ結晶性多孔質シリケートの無機支持体である、粒子径1.7〜4.0mmの球状の構造体であることがわかった。 Accordingly, there is a crystalline porous aluminosilicate having a MFI structure with a thickness of 20 μm in the structure surface layer portion, and an inorganic support for the crystalline porous silicate in which the inner layer excluding the structure surface layer portion has the MFI structure It was found to be a spherical structure having a particle diameter of 1.7 to 4.0 mm.
比較例1
硝酸アルミニウム・9水和物0.4g(ナトリウム/アルミニウム=6.7(原子比))を水12mlに溶解させた水溶液に、シリカビーズ(富士シリシア化学社製 「キャリアクトQ−50」、粒子形状:球状、粒子径:1.7〜4.0mm、表面積:80m2/g、平均細孔径50nm)11gを添加し、シリカビ−ズに水溶液を含浸し、2時間撹拌した後、蒸発乾固し、110℃で乾燥した。
Comparative Example 1
In an aqueous solution in which 0.4 g of aluminum nitrate nonahydrate (sodium / aluminum = 6.7 (atomic ratio)) was dissolved in 12 ml of water, silica beads (“CARTIACT Q-50” manufactured by Fuji Silysia Chemical Ltd., particles) (Shape: spherical, particle diameter: 1.7-4.0 mm, surface area: 80 m 2 / g, average pore diameter 50 nm) 11 g was added, silica beads were impregnated with an aqueous solution, stirred for 2 hours, and then evaporated to dryness. And dried at 110 ° C.
つぎに、テトラ−n−プロピルアンモニウムヒドロキシド12.2g(テトラ−n−プロピルアンモニウムヒドロキシド/珪素=0.07(モル比))、水酸化ナトリウム0.3g(ナトリウム/珪素比=0.04(原子比))を溶解した水溶液にアルミニウム源を担持したシリカビーズを添加し、2時間攪拌した後、蒸発乾固した。80℃窒素雰囲気下で5時間乾燥した。得られたシリカ構造体のアルミニウムのライン分析の結果を図14に示す。担持したアルミニウムはシリカビーズに均一に担持していた。 Next, 12.2 g of tetra-n-propylammonium hydroxide (tetra-n-propylammonium hydroxide / silicon = 0.07 (molar ratio)), 0.3 g of sodium hydroxide (sodium / silicon ratio = 0.04) Silica beads carrying an aluminum source were added to an aqueous solution in which (atomic ratio) was dissolved, and the mixture was stirred for 2 hours and then evaporated to dryness. It dried for 5 hours in 80 degreeC nitrogen atmosphere. The result of the line analysis of the aluminum of the obtained silica structure is shown in FIG. The supported aluminum was uniformly supported on the silica beads.
テフロン(登録商標)の耐圧容器に0.5gの水を入れ、水に触れないようにテフロン(登録商標)の皿を起き、その上に水酸化ナトリウム、テトラプロピルアンモニウムヒドロキシド、アルミニウム源を担持したシリカビーズ11gを入れ、耐圧容器を密閉し、耐圧容器を180℃で8時間加熱し、結晶化処理を行った。 Put 0.5 g of water in a Teflon (registered trademark) pressure vessel, raise a Teflon (registered trademark) dish so that it does not touch the water, and carry sodium hydroxide, tetrapropylammonium hydroxide, and aluminum source on it. 11 g of the silica beads were added, the pressure vessel was sealed, and the pressure vessel was heated at 180 ° C. for 8 hours for crystallization treatment.
その後、蒸留水で洗浄後、110℃で一晩乾燥後、540℃で焼成した。 Then, after washing with distilled water, drying at 110 ° C. overnight and baking at 540 ° C.
得られた構造体の粉末X線回折測定の結果(図15)、MFI構造であることが解った。また、ライン分析の結果(図16)より、アルミニウムは構造体全体に存在していた。 As a result of the powder X-ray diffraction measurement of the obtained structure (FIG. 15), it was found to have an MFI structure. Further, from the result of line analysis (FIG. 16), aluminum was present in the entire structure.
実施例3
実施例1で得た構造体を、20倍重量の1mol/Lの塩化アンモニウム水溶液に浸漬し、80℃で1.5時間放置した。次いで、該構造体をろ別し、塩化アンモニウム水溶液から取り出した。この操作をさらに3回繰り返した後、得られた構造体を水洗し、120℃で一晩乾燥し、アンモニウム型の構造体を得た。
Example 3
The structure obtained in Example 1 was immersed in a
硝酸亜鉛六水和物4.4gを11gの水に溶解した水溶液を乾燥したアンモニウム型構造体10gにふりかけた後、真空中50℃で水を蒸発させて硝酸亜鉛を含浸担持した。硝酸亜鉛を担持した構造体は、電気炉にて空気流通下500℃で5時間焼成し、亜鉛が9.0重量%担持され、さらにプロトン型になった構造体を得た。 An aqueous solution in which 4.4 g of zinc nitrate hexahydrate was dissolved in 11 g of water was sprinkled on 10 g of the dried ammonium structure, and then water was evaporated at 50 ° C. in a vacuum to impregnate and carry zinc nitrate. The structure supporting zinc nitrate was fired in an electric furnace at 500 ° C. for 5 hours under air flow to obtain 9.0 weight% zinc supported and a proton type structure.
該構造体10mlを反応管に充填し、温度を530℃に、内圧を0.5MPa−Gに設定し、1−ブテンをLHSV=2.7h−1で供給し、芳香族化反応を実施した。結果を表1に示す。コークの生成量は1.1%と少なかった。 10 ml of the structure was filled in a reaction tube, the temperature was set to 530 ° C., the internal pressure was set to 0.5 MPa-G, and 1-butene was supplied at LHSV = 2.7 h −1 to carry out the aromatization reaction. . The results are shown in Table 1. The amount of coke produced was as low as 1.1%.
比較例2
特公昭46−10064号公報に準拠してナトリウム型のZSM−5を調製した。30重量%シリカゾル(日産化学製、商品名コロイダルシリカN)76gを2.2mol/lのテトラ−n−プロピルアンモニウムヒドロキシド水溶液108gと混合した。次いで、3.2gのアルミン酸ナトリウムを水54mlに溶かし、この水溶液と前記溶液をSUS製オートクレーブに入れた。この混合物を自圧で150℃、6日間攪拌しながら加熱された。冷却後、生成したスラリーをろ別し、蒸留水100mlを用い洗浄し、この洗浄操作を5回繰り返した。次いで、110℃で一晩乾燥後、空気中540℃で焼成し、白色のナトリウム型のZSM−5を得た。粉末X線回折測定の結果、MFI型すなわちZSM−5形構造を有することがわかった。得られたZSM−5のアルミニウム/珪素比(原子比)=0.051であった。
Comparative Example 2
Sodium type ZSM-5 was prepared according to Japanese Patent Publication No. 46-10064. 76 g of 30 wt% silica sol (manufactured by Nissan Chemical Co., Ltd., trade name colloidal silica N) was mixed with 108 g of 2.2 mol / l tetra-n-propylammonium hydroxide aqueous solution. Next, 3.2 g of sodium aluminate was dissolved in 54 ml of water, and the aqueous solution and the solution were put in a SUS autoclave. This mixture was heated at 150 ° C. for 6 days with self-pressure and stirring. After cooling, the produced slurry was filtered off and washed with 100 ml of distilled water, and this washing operation was repeated 5 times. Subsequently, after drying at 110 degreeC overnight, it baked at 540 degreeC in the air, and obtained white sodium-type ZSM-5. As a result of powder X-ray diffraction measurement, it was found to have an MFI type, that is, ZSM-5 type structure. The obtained ZSM-5 had an aluminum / silicon ratio (atomic ratio) of 0.051.
ナトリウム型のZSM−5を20倍重量の1mol/Lの塩化アンモニウム水溶液中で攪拌し、80℃で1.5時間放置した。次いで、該構造体をろ別し、塩化アンモニウム水溶液から取り出した。この操作をさらに3回繰り返した後、得られたZSM−5を水洗し、120℃で一晩乾燥し、アンモニウム型ZSM−5の粉体を得た。該粉体2.0g、硝酸亜鉛六水和物4.4g、および30重量%シリカゾル(日産化学製、商品名コロイダルシリカN)27.3gを混合し、次いで80℃で水を蒸発させながら混練し、白色の粘調物をシリンジを用い押し出し成形した。成形体を粉砕し、ふるいを用い、約3mmの柱状のサイズにそろえた後、120℃で乾燥し、電気炉にて空気流通下500℃で5時間焼成し、亜鉛が9.0重量%担持され、さらにプロトン型になったZSM−5を得た。
Sodium type ZSM-5 was stirred in 20
アルミニウムのライン分析の結果、アルミニウムが構造体内部に均一に分散していることから、得られた構造体は結晶性アルミのシリケートが均一に構造体内部に分散したものであった。 As a result of aluminum line analysis, aluminum was uniformly dispersed inside the structure. Therefore, the obtained structure was a crystalline aluminum silicate uniformly dispersed inside the structure.
該ZSM−5 10mlを反応管に充填し、温度を530℃に、内圧を0.5MPa−Gに設定し、1−ブテンをLHSV=2.7h−1で供給し、芳香族化反応を実施した。結果を表1に示す。コークの生成量は27.1%と非常に多く、ブテン転化率も急速に低下した。 The ZSM-5 (10 ml) was charged into a reaction tube, the temperature was set to 530 ° C., the internal pressure was set to 0.5 MPa-G, and 1-butene was supplied at LHSV = 2.7 h −1 to carry out the aromatization reaction. did. The results are shown in Table 1. The amount of coke produced was very high at 27.1%, and the butene conversion rate also decreased rapidly.
実施例4
シリカビーズ(富士シリシア化学社製 「キャリアクトQ−40C」、粒子形状:球状、粒子径:1.7〜4.0mm、表面積:73m2/g、平均細孔径40nm)13gに、1Nのテトラ−n−プロピルアンモニウムヒドロキシド水溶液21.0g(テトラ−n−プロピルアンモニウムヒドロキシド/珪素=0.10(モル比))水溶液を減圧下でシリカビ−ズに含浸した。10分撹拌した後、減圧下、70℃で3時間溶媒を蒸発させた。
Example 4
13 g of silica beads (Fuji Silysia Chemical "Caratact Q-40C", particle shape: spherical, particle diameter: 1.7-4.0 mm, surface area: 73 m 2 / g,
つぎに、硝酸アルミニウム・9水和物1.3g(テトラプロピルアンモニウムヒドロキシド/アルミニウム=6(原子比))をエタノール10mlに溶解させ、50℃に加温した後、テトラプロピルアンモニウムヒドロキシドを含浸したシリカビーズを添加し、20分攪拌した。撹拌後、減圧乾燥し、空気中540℃で5時間焼成した。 Next, 1.3 g of aluminum nitrate nonahydrate (tetrapropylammonium hydroxide / aluminum = 6 (atomic ratio)) was dissolved in 10 ml of ethanol, heated to 50 ° C., and impregnated with tetrapropylammonium hydroxide. The silica beads were added and stirred for 20 minutes. After stirring, it was dried under reduced pressure and baked in air at 540 ° C. for 5 hours.
得られたシリカ構造体のアルミニウムのライン分析の結果を図17に示す。担持したアルミニウムはシリカビーズ外表面から400μm以内に存在していることが解った。 The result of the line analysis of the aluminum of the obtained silica structure is shown in FIG. It was found that the supported aluminum was present within 400 μm from the outer surface of the silica beads.
次に、先に得られたアルミニウムを担持したシリカビーズ12.2gに、1Nのテトラ−n−プロピルアンモニウムヒドロキシド水溶液14.2g(テトラ−n−プロピルアンモニウムヒドロキシド/珪素=0.07(モル比))に水酸化ナトリウム0.3g(ナトリウム/珪素比=0.04(原子比))を溶解した水溶液を減圧下で含浸させ、常圧で20時間撹拌した。撹拌後、減圧下50℃で1時間溶媒を蒸発させた後、80℃窒素雰囲気下で5時間乾燥した。 Next, 14.2 g of 1N tetra-n-propylammonium hydroxide aqueous solution (tetra-n-propylammonium hydroxide / silicon = 0.07 (mol) was added to 12.2 g of the silica beads carrying aluminum previously obtained. Ratio)) was impregnated with 0.3 g of sodium hydroxide (sodium / silicon ratio = 0.04 (atomic ratio)) under reduced pressure and stirred at normal pressure for 20 hours. After stirring, the solvent was evaporated at 50 ° C. under reduced pressure for 1 hour, and then dried at 80 ° C. in a nitrogen atmosphere for 5 hours.
テフロン(登録商標)の耐圧容器に0.5gの水を入れ、水に触れないようにテフロン(登録商標)の皿を起き、その上に水酸化ナトリウム、テトラ−n−プロピルアンモニウムヒドロキシド、アルミニウム源を担持したシリカビーズを入れ、耐圧容器を密閉し、耐圧容器を180℃で20時間加熱し、結晶化処理を行った。 Put 0.5 g of water into a Teflon (registered trademark) pressure vessel, wake up a Teflon (registered trademark) dish so that it does not come in contact with water, and then add sodium hydroxide, tetra-n-propylammonium hydroxide, aluminum Silica beads carrying the source were put in, the pressure vessel was sealed, and the pressure vessel was heated at 180 ° C. for 20 hours for crystallization treatment.
その後、蒸留水で洗浄後、110℃で一晩乾燥後、空気中540℃で焼成した。 Then, after washing with distilled water, drying was performed at 110 ° C. overnight, followed by firing at 540 ° C. in air.
得られた構造体の粉末X線回折測定の結果、MFI構造であることが解った。また、ライン分析の結果(図18)より、アルミニウムは得られた構造体外表面から400μm以内に存在し、また、EPMAによる局所部分の成分分析の結果、得られた構造体の表層部のアルミニウム/珪素比(原子比)=0.02であり、中心付近からはアルミニウムは検出限界以下であった。 As a result of the powder X-ray diffraction measurement of the obtained structure, it was found that the structure had an MFI structure. Further, from the result of the line analysis (FIG. 18), the aluminum is present within 400 μm from the outer surface of the obtained structure, and as a result of the component analysis of the local part by EPMA, the aluminum / The silicon ratio (atomic ratio) was 0.02, and aluminum was below the detection limit from the vicinity of the center.
このことから、構造体表層部400μmの厚さでMFI構造をもつ結晶性多孔質アルミノシリケートが存在し、構造体表層部を除く内部の層がMFI構造を持つ結晶性多孔質シリケートの無機支持体である、粒子径1.7〜4.0mmの球状の構造体であることがわかった。 Therefore, there is a crystalline porous aluminosilicate having a MFI structure with a thickness of 400 μm in the surface layer of the structure, and an inorganic support for the crystalline porous silicate in which the inner layer excluding the structure surface layer has the MFI structure. It was found to be a spherical structure having a particle diameter of 1.7 to 4.0 mm.
実施例5
実施例4で得た構造体を、20倍重量の1mol/Lの塩化アンモニウム水溶液に浸漬し、80℃で1.5時間放置した。次いで、該構造体を塩化アンモニウム水溶液から取り出した。この操作をさらに3回繰り返した後、得られた構造体を水洗し、120℃で一晩乾燥し、アンモニウム型の構造体を得た。
Example 5
The structure obtained in Example 4 was immersed in a
硝酸亜鉛六水和物3.5gを7.7gの水に溶解した水溶液を乾燥したアンモニウム型構造体8.0gに含浸後、減圧下50℃で水を蒸発させて硝酸亜鉛を含浸担持した。硝酸亜鉛を担持した構造体は、電気炉にて空気流通下540℃で5時間焼成し、亜鉛が9.0重量%担持され、さらにプロトン型になった構造体を得た。 An aqueous solution obtained by dissolving 3.5 g of zinc nitrate hexahydrate in 7.7 g of water was impregnated in 8.0 g of a dried ammonium structure, and then water was evaporated at 50 ° C. under reduced pressure to impregnate and carry zinc nitrate. The structure supporting zinc nitrate was baked in an electric furnace at 540 ° C. for 5 hours under air flow to obtain a structure in which zinc was supported by 9.0% by weight and further became proton type.
該構造体10mlを反応管に充填し、温度を530℃に、内圧を0.5MPa−Gに設定し、1−ブテンをLHSV=2.7h−1で供給し、芳香族化反応を実施した。結果を表2に示す。 10 ml of the structure was filled in a reaction tube, the temperature was set to 530 ° C., the internal pressure was set to 0.5 MPa-G, and 1-butene was supplied at LHSV = 2.7 h −1 to carry out the aromatization reaction. . The results are shown in Table 2.
1 結晶性多孔質アルミノシリケート
2 結晶性多孔質シリケート
1 Crystalline
Claims (12)
An olefin is aromatized by using the catalyst according to claim 11, and a method for producing an aromatic hydrocarbon.
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- 2005-08-19 JP JP2005238648A patent/JP5055726B2/en not_active Expired - Fee Related
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JP2002166172A (en) * | 2000-09-20 | 2002-06-11 | Toyota Motor Corp | Catalyst for cleaning exhaust gas |
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JP2003062466A (en) * | 2001-08-29 | 2003-03-04 | Kobe Steel Ltd | Catalyst particle and method for manufacturing aromatic derivative using the same |
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