JP2013523582A - 表面修飾したゼオライトおよびその調製方法 - Google Patents
表面修飾したゼオライトおよびその調製方法 Download PDFInfo
- Publication number
- JP2013523582A JP2013523582A JP2013502648A JP2013502648A JP2013523582A JP 2013523582 A JP2013523582 A JP 2013523582A JP 2013502648 A JP2013502648 A JP 2013502648A JP 2013502648 A JP2013502648 A JP 2013502648A JP 2013523582 A JP2013523582 A JP 2013523582A
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- JP
- Japan
- Prior art keywords
- zeolite
- hybrid polymer
- contacting
- dried
- calcined
- 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
Links
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 204
- 238000002360 preparation method Methods 0.000 title description 4
- 239000010457 zeolite Substances 0.000 claims abstract description 203
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 170
- 229920000642 polymer Polymers 0.000 claims abstract description 66
- 238000000034 method Methods 0.000 claims abstract description 31
- -1 silicon alkoxide Chemical class 0.000 claims abstract description 26
- 239000000725 suspension Substances 0.000 claims abstract description 26
- 239000011734 sodium Substances 0.000 claims abstract description 22
- 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 claims abstract description 21
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 21
- 239000010703 silicon Substances 0.000 claims abstract description 20
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims description 11
- 150000004706 metal oxides Chemical class 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 11
- 229910052726 zirconium Inorganic materials 0.000 claims description 10
- 238000007334 copolymerization reaction Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical compound CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 claims description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 claims description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 4
- 229940095070 tetrapropyl orthosilicate Drugs 0.000 claims description 4
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 3
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 claims description 3
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical group [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 claims description 3
- TURITJIWSQEMDB-UHFFFAOYSA-N 2-methyl-n-[(2-methylprop-2-enoylamino)methyl]prop-2-enamide Chemical compound CC(=C)C(=O)NCNC(=O)C(C)=C TURITJIWSQEMDB-UHFFFAOYSA-N 0.000 claims description 2
- YBKWKURHPIBUEM-UHFFFAOYSA-N 2-methyl-n-[6-(2-methylprop-2-enoylamino)hexyl]prop-2-enamide Chemical compound CC(=C)C(=O)NCCCCCCNC(=O)C(C)=C YBKWKURHPIBUEM-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 230000002708 enhancing effect Effects 0.000 claims description 2
- UARGAUQGVANXCB-UHFFFAOYSA-N ethanol;zirconium Chemical compound [Zr].CCO.CCO.CCO.CCO UARGAUQGVANXCB-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- YQXQWFASZYSARF-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC YQXQWFASZYSARF-UHFFFAOYSA-N 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims 3
- GRMNJXQBRPJVQV-JCYAYHJZSA-N (2r,3r)-2,3-dihydroxybutanediamide Chemical compound NC(=O)[C@H](O)[C@@H](O)C(N)=O GRMNJXQBRPJVQV-JCYAYHJZSA-N 0.000 claims 1
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 claims 1
- TVRFATNTQOKKEA-UHFFFAOYSA-N C(C)(C)OC(C)C.[Ti+4] Chemical compound C(C)(C)OC(C)C.[Ti+4] TVRFATNTQOKKEA-UHFFFAOYSA-N 0.000 claims 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 claims 1
- AYGYHGXUJBFUJU-UHFFFAOYSA-N n-[2-(prop-2-enoylamino)ethyl]prop-2-enamide Chemical compound C=CC(=O)NCCNC(=O)C=C AYGYHGXUJBFUJU-UHFFFAOYSA-N 0.000 claims 1
- 229960005235 piperonyl butoxide Drugs 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 12
- 229910000323 aluminium silicate Inorganic materials 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 6
- 238000005342 ion exchange Methods 0.000 description 6
- 238000000151 deposition Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical group 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 244000180534 Berberis hybrid Species 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910003849 O-Si Inorganic materials 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 229910003872 O—Si Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- CHWXPKUEMUZYKK-UHFFFAOYSA-N aluminum;2-propan-2-yloxypropane Chemical compound [Al].CC(C)OC(C)C CHWXPKUEMUZYKK-UHFFFAOYSA-N 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910001423 beryllium ion Inorganic materials 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- DGEYTDCFMQMLTH-UHFFFAOYSA-N methanol;propan-2-ol Chemical compound OC.CC(C)O DGEYTDCFMQMLTH-UHFFFAOYSA-N 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- YQCFXPARMSSRRK-UHFFFAOYSA-N n-[6-(prop-2-enoylamino)hexyl]prop-2-enamide Chemical compound C=CC(=O)NCCCCCCNC(=O)C=C YQCFXPARMSSRRK-UHFFFAOYSA-N 0.000 description 1
- 229910052605 nesosilicate Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004762 orthosilicates Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 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
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/026—After-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
【選択図】図1
Description
本発明は一般に、表面修飾したゼオライトとその調製に関し、より詳細には、表面修飾したゼオライトと所望の表面特性を与えるためのハイブリッド重合体を用いたゼオライトの表面修飾方法に関する。
以下の本発明の詳細な説明は、本質的に単なる例示であって、本発明や本発明の用途および使用を限定するものではない。さらに、上記本発明の背景または以下の本発明の詳細な説明に示されているどんな理論によっても束縛されるものではない。
以下は、本明細書に記載されている例示的な態様に係る表面修飾したゼオライトの調製の実施例である。本実施例は、例示のためにのみ提供するものであり、決して本発明の様々な態様を限定するものではない。
ナトリウム型MFIゼオライト粉末(UOP LLC社(米国イリノイ州デスプレーンズ)から入手可能)からゼオライト押出し物を形成するために、60グラム(g)の結合剤をNa型MFIゼオライト粉末に添加して、押し出したMFIゼオライトを形成した。結合剤は、アルミナ、アルミノリン酸塩(ALPO)およびシリカを含んでいた。Na型MFIゼオライト粉末に対する結合剤の重量比は、15重量%〜60重量%の範囲であった。
得られたゼオライト押出し物を、硝酸アンモニウム(NH4NO3)で3回イオン交換し、550℃でか焼して、水素型ゼオライトを形成した。
150gの乾燥した押出し物および400gの乾燥ヘキサンを、1000ccのフラスコ内で一緒にした。
A.シリコンとチタンの二種類の金属からなるハイブリッド重合体
200gのオルトケイ酸テトラエチル(0.96mol)および2gのチタン酸テトラブチル(0.00588mol)を、400gのエタノール溶液に添加した。7.5gの25%NH4OH溶液を、激しく撹拌しながら添加して室温で24時間撹拌し、シリコンとチタンの二種類の金属からなるハイブリッド重合体を形成した。
200gのオルトケイ酸テトラエチルおよび2gのジルコン酸テトラプロピルを、400gのエタノール溶液に添加した。7.5gの25%NH4OH溶液を、激しく撹拌しながら添加して室温で24時間撹拌し、シリコンとジルコニウムの二種類の金属からなるハイブリッド重合体を形成した。
ゼオライト懸濁液を、撹拌機、還流冷却器および加熱装置を備えた1リットルの3口フラスコに添加した。各ハイブリッド重合体に対して、63gのハイブリッド重合体をフラスコに添加した。押出し物/ヘキサン/ハイブリッド重合体混合物を2時間加熱した。次いで、ハイブリッド重合体の処理済固体押出し物を濾過し、120℃で一晩乾燥した後、2℃/分の加熱速度を用いて、空気流中550℃で4時間か焼した。550℃で4時間後、試料を冷却して、表面修飾したMFI型ゼオライト押出し物を生成した。表面修飾したMFI型ゼオライト押出し物を、同じ重量比のハイブリッド重合体/押出し物/ヘキサン(例えば、63gのSiとTiのハイブリッド重合体溶液/150gの押出し物/400gのヘキサン)を用いる複数の選択性向上化順序に曝した。
Claims (10)
- 表面修飾したゼオライトを調製するための選択性向上化方法(10)であって、
ケイ素アルコキシドと金属アルコキシド、共重合用単量体、またはその両方から形成されたハイブリッド重合体を、該ハイブリッド重合体をゼオライトの外表面に堆積させるのに十分な条件で、溶媒およびアンモニウム型ゼオライト、水素型ゼオライトおよびナトリウム型ゼオライトからなる群から選択されるゼオライトからなるゼオライト懸濁液に接触させて、処理済ゼオライトを形成する工程(40、50および70)と、
該処理済ゼオライトから該溶媒を除去する工程(80)と、
該処理済ゼオライトを乾燥およびか焼して、乾燥・か焼処理済ゼオライトを形成する工程(90および100)と、を含み、
該ゼオライト懸濁液の形成、および接触、除去、乾燥およびか焼工程が、該アンモニウム型ゼオライトおよび該水素型ゼオライトから表面修飾したゼオライトを生成する選択性向上化順序を構成し、
該乾燥・か焼処理済ゼオライトがナトリウム型ゼオライトである場合、
該乾燥・か焼処理済ゼオライトのイオン交換可能な部位のナトリウムをアンモニウムで交換する工程(110)と、
該乾燥・か焼処理済ゼオライトをさらに乾燥およびか焼する工程(120および130)と、をさらに含む、方法。 - 乾燥・か焼処理済ゼオライトを少なくとも1つのさらなる選択性向上化順序に曝して該乾燥・か焼処理済ゼオライトの外表面にハイブリッド重合体を堆積させる工程(105)をさらに含み、
該少なくとも1つのさらなる選択性向上化順序が、
該乾燥・か焼処理済ゼオライトの外表面にさらなるハイブリッド重合体を堆積させるのに十分な条件で、さらなるハイブリッド重合体を、該乾燥・か焼処理済ゼオライトとさらなる溶媒から形成されたゼオライト懸濁液に接触させる工程と、
該さらなる溶媒を除去する工程と、
該乾燥・か焼処理済ゼオライトの外表面に堆積した該さらなるハイブリッド重合体を乾燥およびか焼する工程と、
を含み、
該曝露工程を該交換工程およびさらなる乾燥およびか焼工程の前に行う、
請求項1に記載の方法。 - ケイ素アルコキシドから形成されたハイブリッド重合体を接触させる工程(70)が、オルトケイ酸テトラメチル(TMOS)、オルトケイ酸テトラエチル(TEOS)、オルトケイ酸テトラプロピル(TPOS)およびそれらの組み合わせからなる群から選択されるオルトケイ酸テトラアルキルから形成されたハイブリッド重合体を接触させることを含む、請求項1に記載の方法。
- ハイブリッド重合体を接触させる工程(70)が、チタンアルコキシド、ジルコニウムアルコキシドまたはその両方を含む金属アルコキシドから形成されたハイブリッド重合体を接触させることを含み、該チタンアルコキシドが、チタン(IV)メトキシド、チタン(IV)n−ブトキシド、チタン(IV)t−ブトキシド、チタン(IV)i−プロピルオキシドおよびチタン(IV)エトキシドおよびそれらの組み合わせからなる群から選択され、該ジルコニウムアルコキシドが、ジルコニウム(IV)n−ブトキシド、ジルコニウム(IV)t−ブトキシド、ジルコニウム(IV)エトキシド、ジルコニウム(IV)プロポキシドおよびそれらの組み合わせからなる群から選択される、請求項1に記載の方法。
- ハイブリッド重合体を接触させる工程(70)が、(a)ビスアクリルアミド、(b)ビスメタクリルアミド、(c)ビスアクリラート、(d)エチレングリコール=メタクリラートまたはジメタクリラート、および(e)ジアリル酒石酸ジアミドおよびそれらの組み合わせからなる群から選択される共重合用単量体から形成されたハイブリッド重合体を接触させることを含み、(a)は、Ν,Ν’−メチレンビスアクリルアミド、N,N’−エチレンビスアクリルアミド、Ν,Ν’−ヘキサメチレンビスアクリルアミドまたはグリオキサール−ビスアクリルアミドであり、(b)は、N,N’−メチレンビスメタクリルアミド、Ν,Ν’−エチレンビスメタクリルアミドまたはN,N’−ヘキサメチレンビスメタクリルアミドであり、(c)は、N−ジエチルメタクリラートまたはジメチルメタクリラートである、請求項1に記載の方法。
- ハイブリッド重合体を接触させる工程(70)が、該ハイブリッド重合体を、成形ゼオライトおよび溶媒からなるゼオライト懸濁液に接触させることを含み、該成形ゼオライトが、ゼオライトと結合剤を含み、該結合剤が、シリカ、アルミナ、アルミノリン酸塩(ALPO)およびそれらの組み合わせからなる群から選択される、請求項1に記載の方法。
- ハイブリッド重合体を接触させる工程(70)が、該ハイブリッド重合体を、ゼオライトおよび溶媒からなるゼオライト懸濁液に接触させることを含み、該ゼオライトが、構造型MFI、MEL、MTW、TON、MTT、FER、EUO、FAU、EMT、IMF、TUN、MEI、MSEおよびBEAからなる群から選択される、請求項1に記載の方法。
- ハイブリッド重合体を接触させる工程(70)が、1時間〜24時間にわたって、該ハイブリッド重合体および該ゼオライト懸濁液を室温から該溶媒の沸点まで加熱することを含む、請求項1に記載の方法。
- ハイブリッド重合体を接触させる工程(70)が、有機溶媒、アルコール/水混合液またはそれらの組み合わせを含んでなる溶媒中で該ハイブリッド重合体をゼオライト懸濁液に接触させることを含み、該有機溶媒が、アセトン、ジメチルエーテル、テトラヒドロフラン、ペンタン、ヘキサン、トルエン、キシレン、ヘプタン、オクタンおよびそれらの組み合わせからなる群から選択され、該アルコール/水混合液中の該アルコールが、エタノール、メタノール、1−プロパノール、1−ブタノールおよびそれらの組み合わせからなる群から選択され、アルコールに対する水の重量%が1重量%〜20重量%を占める、請求項1に記載の方法。
- 金属酸化物で富化された外表面を有する表面修飾したゼオライトであって、
外表面を有する選択性向上化ゼオライトと、
SiO2、SiO2及びTiO2、SiO2及びZrO2、ならびに、SiO2、TiO2及びZrO2、からなる群から選択される金属酸化物からなる外表面コーティングと、
を含む表面修飾したゼオライト。
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US20130296160A1 (en) | 2013-11-07 |
EP2552833A2 (en) | 2013-02-06 |
WO2011126738A2 (en) | 2011-10-13 |
RU2506226C1 (ru) | 2014-02-10 |
TW201141608A (en) | 2011-12-01 |
US8575055B2 (en) | 2013-11-05 |
US20110245067A1 (en) | 2011-10-06 |
CN102822096A (zh) | 2012-12-12 |
CN102822096B (zh) | 2015-09-23 |
EP2552833A4 (en) | 2017-03-15 |
US8748333B2 (en) | 2014-06-10 |
WO2011126738A3 (en) | 2012-01-19 |
JP5624670B2 (ja) | 2014-11-12 |
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