CN1171676C - 沸石/氧化铝催化剂载体组合物及其制备方法 - Google Patents
沸石/氧化铝催化剂载体组合物及其制备方法 Download PDFInfo
- Publication number
- CN1171676C CN1171676C CNB008179212A CN00817921A CN1171676C CN 1171676 C CN1171676 C CN 1171676C CN B008179212 A CNB008179212 A CN B008179212A CN 00817921 A CN00817921 A CN 00817921A CN 1171676 C CN1171676 C CN 1171676C
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- Prior art keywords
- zeolite
- alumina
- composite
- oxide
- catalyst
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 239000003054 catalyst Substances 0.000 title claims abstract description 97
- 239000010457 zeolite Substances 0.000 title claims abstract description 91
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 88
- 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 88
- 239000000203 mixture Substances 0.000 title claims description 41
- 238000004519 manufacturing process Methods 0.000 title description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000002131 composite material Substances 0.000 claims abstract description 54
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 28
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 25
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 21
- 239000010948 rhodium Substances 0.000 claims abstract description 20
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 17
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 12
- 239000002912 waste gas Substances 0.000 claims abstract description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 5
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 39
- 230000003197 catalytic effect Effects 0.000 claims description 37
- 239000000919 ceramic Substances 0.000 claims description 35
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 24
- 239000000853 adhesive Substances 0.000 claims description 24
- 230000001070 adhesive effect Effects 0.000 claims description 24
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 20
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 18
- 229910001593 boehmite Inorganic materials 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 239000003381 stabilizer Substances 0.000 claims description 14
- 229920000609 methyl cellulose Polymers 0.000 claims description 12
- 239000001923 methylcellulose Substances 0.000 claims description 12
- 235000010981 methylcellulose Nutrition 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 11
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical group [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 6
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 5
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 5
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical group [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 5
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 4
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 claims description 4
- -1 hydroxybutyl Chemical group 0.000 claims description 4
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 4
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 4
- RPZANUYHRMRTTE-UHFFFAOYSA-N 2,3,4-trimethoxy-6-(methoxymethyl)-5-[3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxyoxane;1-[[3,4,5-tris(2-hydroxybutoxy)-6-[4,5,6-tris(2-hydroxybutoxy)-2-(2-hydroxybutoxymethyl)oxan-3-yl]oxyoxan-2-yl]methoxy]butan-2-ol Chemical compound COC1C(OC)C(OC)C(COC)OC1OC1C(OC)C(OC)C(OC)OC1COC.CCC(O)COC1C(OCC(O)CC)C(OCC(O)CC)C(COCC(O)CC)OC1OC1C(OCC(O)CC)C(OCC(O)CC)C(OCC(O)CC)OC1COCC(O)CC RPZANUYHRMRTTE-UHFFFAOYSA-N 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 3
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 3
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 claims description 3
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920006184 cellulose methylcellulose Polymers 0.000 claims description 3
- 230000020335 dealkylation Effects 0.000 claims description 3
- 238000006900 dealkylation reaction Methods 0.000 claims description 3
- 101150107144 hemC gene Proteins 0.000 claims description 3
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 3
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 3
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 3
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 2
- 239000001856 Ethyl cellulose Substances 0.000 claims description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 2
- 229920001249 ethyl cellulose Polymers 0.000 claims description 2
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims 6
- 239000000395 magnesium oxide Substances 0.000 claims 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 2
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims 2
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 2
- ISSXKNWTCLRPJY-UHFFFAOYSA-N O.O.[O-2].[Zr+4].[O-2] Chemical compound O.O.[O-2].[Zr+4].[O-2] ISSXKNWTCLRPJY-UHFFFAOYSA-N 0.000 claims 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims 1
- 239000000292 calcium oxide Substances 0.000 claims 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims 1
- 239000011232 storage material Substances 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 abstract description 6
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 229910002090 carbon oxide Inorganic materials 0.000 abstract 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 238000010304 firing Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 238000007598 dipping method Methods 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 235000012239 silicon dioxide Nutrition 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 239000012876 carrier material Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- 229920003108 Methocel™ A4M Polymers 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000001154 acute effect Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007850 degeneration Effects 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- 229910001723 mesolite Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229920003086 cellulose ether Polymers 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- QYMFNZIUDRQRSA-UHFFFAOYSA-N dimethyl butanedioate;dimethyl hexanedioate;dimethyl pentanedioate Chemical compound COC(=O)CCC(=O)OC.COC(=O)CCCC(=O)OC.COC(=O)CCCCC(=O)OC QYMFNZIUDRQRSA-UHFFFAOYSA-N 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920003091 Methocel™ Polymers 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- JEWHCPOELGJVCB-UHFFFAOYSA-N aluminum;calcium;oxido-[oxido(oxo)silyl]oxy-oxosilane;potassium;sodium;tridecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.[Na].[Al].[K].[Ca].[O-][Si](=O)O[Si]([O-])=O JEWHCPOELGJVCB-UHFFFAOYSA-N 0.000 description 1
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- CRQQGFGUEAVUIL-UHFFFAOYSA-N chlorothalonil Chemical compound ClC1=C(Cl)C(C#N)=C(Cl)C(C#N)=C1Cl CRQQGFGUEAVUIL-UHFFFAOYSA-N 0.000 description 1
- 229910001603 clinoptilolite Inorganic materials 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229910052675 erionite Inorganic materials 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910001743 phillipsite Inorganic materials 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
- B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
本发明公开了沸石/氧化铝复合材料以及其制备方法,该用作催化剂基材或催化剂载体的复合材料包含二氧化硅/氧化铝比值大于300的沸石和比表面积大于100m2/g的γ-氧化铝。该沸石/氧化铝复合材料的断裂模量至少为750psi。此外,本发明还针对用来从废气中除去烃、一氧化碳和氮的氧化物的三元催化净化剂(TWC)体系,该TWC体系包含以下组分:(1)沸石/氧化铝复合材料催化剂载体,其断裂模量至少为750psi,该载体包含二氧化硅/沸石比值至少为300的沸石和包含γ-氧化铝的氧化铝,所述γ-氧化铝的比表面积大于100m2/g,(2)浸渍在催化剂载体上的贵金属催化剂,所述贵金属选自铂、铑、铱和钯。
Description
本申请要求Faber等人申请日为1999年12月28日题为“沸石/氧化铝催化剂载体组合物及其制备方法”(Zeolite/Alumina Catalyst Support Compositionsand Method of Making the Same)的美国临时申请60/173,365的权益。
发明背景
1.发明领域
本发明涉及一种具有高强度和高表面积,具体是足以适合于催化剂浸渍的高表面积的沸石/氧化铝复合材料。
本发明还涉及该组合物的制备方法及其用途,尤其是在催化领域,不论是用于转化车辆废气的催化剂和/或催化剂载体。
2.背景技术及相关技术探讨
1970年的清洁空气法要求在汽车上安装催化转化器以净化废气流。催化转化器能同时除去废气中的未燃烧汽油、一氧化碳和氮的氧化物。常规的催化转化器由多通道陶瓷蜂窝体构成,且包括高表面积的材料以及洗涤涂覆(washcoat)在陶瓷材料上的实际催化材料(例如三元催化净化剂(TWC))。整块陶瓷蜂窝体在满足机械和热性能要求以外,还提供用于催化剂的牢固基材。然而,催化剂基材作为惰性结构体,不应参与除去未燃烧烃、一氧化碳和氮的氧化物的化学反应。
美国专利Re.34,804揭示了形成包含永久粘合剂有机硅树脂组分的挤出沸石蜂窝体。美国专利5,492,883(Wu)揭示了制备沸石体的改进方法,在该方法中将沸石材料与有机硅树脂水乳液和一种临时粘合剂(如甲基纤维素)混合,将此混合物挤出形成蜂窝体生坯,然后干燥并烧结。美国专利5,633,217(Lynn)揭示了另一种制备沸石体的改进方法,该方法使用二价酸酯作为有机硅树脂的溶剂,并使用甲基纤维素临时粘合剂。最后,美国专利5,565,394(Lachman等)揭示了改进的沸石体,它包含一种热膨胀控制组分(如硅酸钙)、永久粘合剂(如二氧化硅或氧化铝)以及临时粘合剂(如甲基纤维素)。尽管Wu,Lynn和Lachman这些人的参考文献中揭示的沸石不是惰性的,且能够用作催化剂材料,但是这些沸石都要施涂贵金属洗涤涂层,以用作三元催化净化剂将烃、氮的氧化物和一氧化碳转化成无毒的相应气态产物。
催化剂领域中熟知,通道尺寸较小和通道壁厚较薄的催化转化器中催化剂几何表面积就增加,从而增强了污染物扩散进入催化剂并与其接触,即无需显著增加背压就能提高通量。其次,通道密度高的蜂窝体的通道尺寸小,这就增大了污染物扩散至催化剂表面的浓度梯度。这使得到达催化剂表面的污染气流通量高。
从催化剂角度来看,要求用尽可能少量的催化剂将污染气体转化为对环境良好的气体。由此得出,在污染气体扩散方面较理想的是具有薄壁和薄催化剂洗涤涂层的高通道密度蜂窝体,即几何表面积高或有提高。然而,由于蜂窝体的通道尺寸减小,因此不再适合用常规洗涤涂覆方法将含催化剂的浆液洗涤涂覆在高通道密度的陶瓷蜂窝体上。而且在薄壁、高通道密度的基材上施涂较厚的洗涤涂层会显著增加壁厚。洗涤涂层厚度/壁厚的增加又会使背压增加,这是不希望的。因此,包含具有洗涤涂层的高通道密度陶瓷蜂窝体的催化转化器并非是增加催化转化器转化效率的最佳方式。
因此,就明确提出了这样一种需求,也是本发明的目的:提供一种催化剂载体材料,它能够挤出成催化剂载体,该催化剂载体的通道密度高、通道壁薄且强度足够用于催化用途,且具有足够大的几何表面积用于贵金属催化剂浸渍,而无需催化剂/高表面积材料洗涤涂层组分。
发明概述
本发明的目的是解决已有技术的上述问题,提供一种方法用来制备高表面积的催化剂载体,该载体能够挤出成高通道密度、薄壁的蜂窝体,然后用贵金属催化剂材料浸渍。
具体而言,本发明针对一种用作催化剂基材或催化剂载体的沸石/氧化铝复合材料,该材料包含二氧化硅/氧化铝比值至少为300的沸石和比表面积大于100m2/g的γ-氧化铝。沸石/氧化铝复合材料的断裂模量至少为52.7kg/cm2(750psi)。
本发明还涉及具有高表面积的挤出的整块蜂窝体的制备方法,该方法包括将以下各组分混合成基本均匀的批料:
(i)沸石,其二氧化硅/氧化铝的比至少为300∶1,表面积至少为250m2/g;
(ii)比表面积大于100m2/g的γ-氧化铝组分,其至少一部分是用作永久粘合剂的勃姆石;
(iii)临时粘合剂,选自甲基纤维素、乙基纤维素、羟丁基纤维素、羟丁基甲基纤维素、羟乙基纤维素、羟甲基纤维素、羟丙基纤维素、羟丙基甲基纤维素、羟乙基甲基纤维素,以及它们的混合物,和
(iv)水;
在原料混合之后,该方法包括将混合物挤出形成蜂窝结构体生坯,然后加热该结构体5-30分钟形成无裂缝的干燥结构体。该挤出体经干燥后,该方法接着包括将经干燥的蜂窝结构体在500-1000℃加热,加热的时间足以形成高表面积和高机械强度的烧结结构体。
本发明还针对一种三元催化净化剂(TWC)体系,用来从废气中除去烃、一氧化碳和氮的氧化物,该TWC体系包括以下组分:
(1)沸石/氧化铝复合材料催化剂载体,其断裂模量至少为52.7kg/cm2(750psi),其中沸石的二氧化硅/氧化铝比值至少为300,氧化铝包含比表面积大于100m2/g的γ-氧化铝;
(2)浸渍在催化剂载体上的贵金属催化剂,所述贵金属选自铂、铑、铱和钯。
发明的详细说明
本发明的产品是用作催化剂基材或催化剂载体的沸石/氧化铝复合材料,具体是这样一种复合材料,其中沸石的二氧化硅/氧化铝比值至少为300,γ-氧化铝的比表面积大于100m2/g。本发明复合材料的断裂模量至少为52.7kg/cm2(750psi),较好至少是70.3kg/cm2(1000psi)。以重量份表示,本发明的沸石氧化铝复合材料特征性地包含约30-70重量份沸石和约30-70重量份γ-氧化铝。
一般来说,沸石包括大约数微米的大颗粒,具有规则阵列的可进入其内的微孔,这两点结合起来提供了沸石的高表面特性,这是沸石在烧结之后仍然保持的特性。具有至少为100m2/g的高表面积的γ-氧化铝组分也有助于使整个复合体能很好地满足催化剂载体许多用途对表面积的要求。这些用途通常要求相当大的总表面积,至少为20m2/g,较好大于100m2/g,最好大于150-200m2/g。本发明的沸石/γ-氧化铝复合材料能够挤出成高通道密度、薄壁的整块物体,例如蜂窝结构体,它每平方英寸至少具有600个通道(cell),表面积至少为100m2/g,很容易获得超过200m2/g的表面积。
本领域中熟知,当用非晶态形式的二氧化硅作为永久粘合剂时,该二氧化硅的存在为贵金属(precious group metals,PGM)如铂提供了可移动载体。高温时可移动的二氧化硅使PGM分散或者“沉入”到二氧化硅内,即PGM不相容性。这一现象最终导致PGM的催化性能发生不希望有的下降。因此对于高温催化应用,要求不含二氧化硅粘合剂的复合材料。然而,所述复合材料中仍然需要永久粘合剂来提供足够的强度。有一部分γ-氧化铝组分存在就提供了这一粘合剂功能。具体而言,勃姆石形式的γ-氧化铝前体在烧制时转化为γ-氧化铝,同时仍然可在本发明复合材料中用作永久粘合剂。用勃姆石代替二氧化硅作为永久粘合剂使得形成的复合体能与贵金属催化材料相容。这一相容性和前述的高表面积使得该复合体特别适合用作催化剂载体材料,贵金属催化剂可以加入其中而无需使用洗涤涂层,该洗涤涂层是不希望有的,因为会增加载体的壁厚,降低催化转化器的通量或催化活性。
该复合体适用于催化剂载体的其它特征包括热膨胀较低和热稳定性高,热膨胀低于5×10-6/℃,热稳定性可高达至少1000℃。
本领域技术人员知道制备多孔烧结基材的通常方法如下;混合批料,掺混该混合物,形成生坯,随后将生坯烧结成硬质多孔结构体。为了制备生坯,在混合步骤期间将多种润滑剂(如硬脂酸锌和硬脂酸钠)和有机粘合剂加入批料中,用来在烧制之前提供粘度控制和强度,并且为随后烧制成的结构体提供孔隙率。
用于制备本文所述的本发明复合体(具有高表面积的整块挤出蜂窝体)的一种特别好的方法包括将能够形成上述复合材料的一些特定原料混合成基本上均匀的批料。具体而言,能形成复合材料的原料中,沸石组分的二氧化硅/氧化铝比至少是300∶1,表面积至少是250m2/g二氧化硅,γ-氧化铝组分的比表面积大于100m2/g。至少一部分氧化铝原料应为勃姆石,用作永久粘合剂从而向复合材料提供所需的强度。批料混合物应包含临时有机粘合剂和水,这是形成陶瓷结构体的标准做法。坯体成形的较佳方法包括将批料挤出形成蜂窝结构体生坯。一旦形成蜂窝体,就加热该挤出的生坯5-30分钟进行干燥,形成无裂缝的干燥结构体。经干燥的蜂窝结构体的烧结包括加热即烧结至500-1000℃一段足以形成高表面积烧结结构体的时间。
该结构体在烧结之前放入温度为50-100℃,较好是90-100℃的烘箱内进行干燥步骤。在一个特别好的实例中,将结构体生坯放入介电烘箱内一段足以形成无裂缝、自支持结构体的时间来完成干燥步骤。生坯在介电烘箱内干燥的时间较好不大于60分钟,更好是5-30分钟。
沸石/氧化铝复合材料的孔隙率应足以使得能够通过通道壁接触到催化剂,总孔隙率和孔径应保持在一定范围内。所选的范围可以变化以容纳拟定的流出物。孔隙率取决于原料和烧制温度,温度越高则所得结构体越致密。对于催化剂和/或催化剂载体用途,本发明的沸石/氧化铝结构体的总孔隙率至少约为30%,孔隙的直径至少约为20nm,较好至少约为20-200nm。
复合材料的沸石组分宜为高二氧化硅含量的沸石,其SiO2/Al2O3的摩尔比至少为300。具有所需高二氧化硅/氧化铝比值的沸石能使得复合材料在低温吸附烃而在高温解吸附烃。更具体来说,高二氧化硅含量的沸石确保沸石组分在废气环境通常所处的高温条件下具有热稳定性。换而言之,沸石的高二氧化硅含量使得复合材料能够在高温时保持其结构。另一方面,沸石中的氧化铝含量低确保了沸石不会遇到湿气类型的问题,而高氧化铝含量的沸石通常会遇到这类问题:高温时在湿气存在的条件下通常会脱铝酸盐(de-aluminate)。此外,沸石的结晶二氧化硅相在高温时得以保持,其负热膨胀系数(CTE)特性结果能起到补偿作用,降低复合体的总体热膨胀。结果可以向沸石/氧化铝催化载体中加入高热膨胀的催化材料,这样所得的催化体就具有用于高温汽车废气环境所必需的恰当热膨胀。
合适的沸石包括任何具有所需非常高的二氧化硅/氧化铝比的以二氧化硅为基的沸石。可用于本发明的高二氧化硅/氧化铝比的沸石可以是选自以下的沸石:丝光沸石、超稳定的Y(USY)、ZSM-5、ZSM-8、ZSM-11、ZSM-12、HyperY、β-沸石、H-镁碱沸石、H-硅铝钾沸石、HL粉末、八面沸石、X沸石、L型沸石、针沸石、EMC-2,以及它们的组合,优选是硅质岩,以及任何天然沸石,包括毛沸石、斜发沸石、菱沸石(chanazite)和钙十字沸石。具有所需高含量二氧化硅的一种商购沸石是得自PQ Corporation的CBV 3002。
氧化铝的存在使沸石基的复合结构体具有载体功能。特别是γ-氧化铝提供了使贵金属催化剂与结构体结合的必需部位,使得该复合体用于与废气有关的恶劣环境时,其催化活性和寿命高出只含沸石的结构体。此外,贵金属通常位于其上的氧化铝应具有足够的孔隙率,具有足够高表面积的多孔结构,用来抑制存在的贵金属烧结,并使得贵金属能够与废气接触。具体而言,高表面积的γ-氧化铝能确保复合体的表面积大大增加,达到100至大于200m2/gm的范围。最后,如上所述,至少一部分氧化铝原料采用γ-氧化铝前体勃姆石的形式,它用作永久粘合剂从而向复合体提供所需的强度。勃姆石的存在确保了不含二氧化硅粘合剂的复合体的弯曲强度(即断裂模量)至少为52.7kg/cm2(750psi),更好是大于77.3kg/cm2(1100psi),使其适用于催化剂载体用途。
适用于形成该复合体的γ-氧化铝包括那些煅烧后提供所需γ-氧化铝相且具有足以适用于催化剂载体材料的高表面积的氧化铝。具有所需高表面积特性的合适的商购γ-氧化铝是LaRoche Industries提供的GL-25。
γ-氧化铝前体勃姆石不仅只是用作永久粘合剂,它还具有其它特性:在烧制后提供所需的γ-氧化铝,与非勃姆石的γ-氧化铝一起显示用作催化剂载体材料所需的表面积。合适的商购勃姆石材料包括Vista Chemical Co.提供的CatapalB和Laroche Industries提供的Versal 700。
有机粘合剂的目的是在成形时提供塑性,并在干燥后提供一定的生坯强度。本发明的有机粘合剂是指纤维素醚型粘合剂和/或其衍生物,其中一些是可热胶凝的。本发明一些典型的有机粘合剂是甲基纤维素、羟丁基纤维素、羟丁基甲基纤维素、羟乙基纤维素、羟甲基纤维素、羟丙基纤维素、羟丙基甲基纤维素、羟乙基甲基纤维素、羧基甲基纤维素钠,以及它们的混合物。通常用于实施本发明的是甲基纤维素和/或甲基纤维素衍生物。特别好的是甲基纤维素、羟丙基甲基纤维素及其组合。纤维素醚和/或其衍生物的较佳来源是DowChemical Co.的Methocel A4M、F4M和F240M。Methocel A4M是一种甲基纤维素粘合剂,其凝胶温度是50-55℃,凝胶强度是5000g/cm2(65℃,2%溶液)。Methocel F4M和F240M都是羟丙基甲基纤维素。
在一个较佳实例中,复合体包含第三种组分氧化锆,用来向催化剂载体提供额外的氧贮存官能度。以重量份表示,本发明的沸石氧化铝复合体特征性地含有约20-30重量%氧化锆。氧化锆还包括稳定剂。本发明可以单独使用或者掺混使用的稳定剂例如包含选自以下的元素:稀土金属,特别是铈、钇、镧、镨和钕;碱土金属,特别是钙、镁、钡和钛。这些稳定剂中特别好的是包含铈和钇。氧化铈的存在量最多为80%,氧化钇的存在量最多为20%,两者均为以锆总量计的重量百分数。
在另一个实例中,复合催化剂载体应包含稳定的氧化锆和稳定的高表面积氧化铝。这两种组分的存在有助于在汽车废气环境中保持催化剂的催化活性。稳定的氧化锆具有增强的氧贮存能力。稳定的氧化铝应包含一定量的稳定剂,这些稳定剂选自氧化镧(La2O3)或其等同物,包括氧化钡、氧化锶和氧化钇。已知这些稳定剂可用来稳定氧化铝的比表面,而纯的氧化铝在高温时通常不稳定。具体而言,稳定剂抑制了高温时氧化铝的相转变,从而增强了氧化铝的高温稳定性。稳定剂通常以预掺杂物的形式在复合材料配料之前混入氧化铝中,更好是在烧制后通过浸渍方法将稳定剂加入到复合材料中。
用于氧化铝的较佳稳定剂是氧化镧(La2O3),它通过浸渍方法混入到复合材料的γ-氧化铝组分中。镧浸渍是使得复合材料包含占氧化铝总量0.5-20重量%,较好是4-6重量%的氧化镧。若镧的加入量小于该范围,那么就观察不到由于其加入而产生活性增加的有益效果。
在本发明的另一个实例中,向催化剂载体的结构内混入贵金属催化剂,从而形成三元催化净化剂(TWC)体系,用于从废气中除去烃、一氧化碳和氮的氧化物。具体而言,该TWC体系催化剂包含上述沸石/氧化铝复合催化剂载体,其中沸石的二氧化硅/氧化铝比至少为300,氧化铝包含比表面积大于100m2/g的γ-氧化铝。
在第一个实例中,贵金属催化剂浸渍在催化剂载体上,这些贵金属选自铂、铑、铱和钯。在第二个实例中,贵金属催化剂以粉末形式加入到最初的批料中,整个批料混合物(包括粉末状贵金属催化剂)挤出形成TWC。所得的TWC中,贵金属催化剂成为氧化铝催化剂载体组分的组成部分。
上述TWC催化剂特别有用于通道密度非常高(600-2000cpsi)的催化转化器,以满足严格的汽车ULEV排放标准。具体而言,具有高通道密度和薄壁的TWC催化剂能提供非常大的几何催化剂表面,这使得废气污染物能相当快地扩散。此外,该挤出催化剂能降低废气流的背压。具有浸渍贵金属催化剂的催化剂载体材料提供了更加多的催化剂支承材料来散布活性组分(如贵金属),该催化剂在废气体系的高温下不太会烧结。薄壁TWC催化剂的热容量低得多,这使催化剂能迅速地达到点火温度(lightoff temperature),从而减少了冷起动排放物。
在一个较佳实例中,本发明的TWC催化剂体系包含0.142-1.70g/m3(5-60g/ft3)的贵金属催化剂,更好是铂和铑的混合物(铂/铑比约为5)。一种较佳混合物包含最多为1.13g/m3(40g/ft3)的铂和最多为0.23g/m3(8g/ft3)的铑,更好是0.94g/m3(33.3g/ft3)的铂和0.19g/m3(6.6g/ft3)的Rh。
由于如上所述铂和铑需要浸渍在不同的支承材料上,因此浸渍过程最好由两步组成。第一步是将铂浸渍在氧化铝和氧化锆(如果存在)上。在酸性溶液(如六氯铂酸)中,铂物质的存在形式是带负电荷的络合物,而氧化锆和氧化铝的表面带正电荷。在干燥和煅烧之后,第二步是用铑络合物溶液浸渍挤出的铂催化剂,该溶液带有负电荷,pH值约为7。在这种条件下,铑主要浸渍在氧化铝表面上,然而铑并不与已浸渍在氧化铝表面上的铂金属形成合金,从而得到分离的催化剂(segregated catalyst),这是优选的。若所得结构体的孔隙率更高,则表面积增加,那么该结构体烧制后的催化剂含量会更高。
实施例
为了进一步说明本发明的原理,将描述一些按照本发明形成的沸石/氧化铝复合体的实施例以及沸石/二氧化硅与纯氧化铝复合体的比较例。然而应理解,这些实施例只是用来说明的,本发明并不局限于此。在不偏离本发明精神的情况下可以对本发明作出许多改动和变化。
实施例1
将包含450克SiO2/Al2O3比值为300的ZSM-5沸石(CBV-3002,得自PQCorporation)、270克γ-氧化铝(TA 2300,得自Sumitomo Chemical,掺有4重量%镧且表面积为110m2/g)、180克勃姆石(Catapal B,得自Vista Chemical Co.,表面积为250m2/g)和54克甲基纤维素临时粘合剂(Methocel A4M,得自DowChemical Co.)的批料混合物,用2重量%乙酸(Aldrich Chemical Company Inc.)处理之后在Littleford干混机中混合。然后将混合批料转移到研磨机中,向批料中加入350毫升水用来均匀地塑化该批料。
用柱塞式挤出机挤出形成通道壁厚约7密耳、通道密度为400通道/英寸2的蜂窝体和长度为6英寸的棒。将挤出的蜂窝体和棒生坯在湿润烘箱(90%的相对湿度)于95℃干燥24小时。干燥后,挤出的蜂窝体和棒在空气中于850℃烧制4小时。烧制体的组成见表I。
得到的棒用来测定机械性能,如MOR、CTE和E模量。根据下式计算抗温度急变性TSR:TSR=MOR/(E模量×CTE)。用常规压汞法孔隙测量仪测量蜂窝体的孔隙率和平均孔径。棒和蜂窝体的所有这些物理性能详细列于表I。
用氯铂酸浸渍所得的蜂窝体,得到标称的0.94g/m3(33.3g/ft3)的铂,然后于550℃烧制3小时。然后用硝酸铑化的溶液浸渍负载有铂的蜂窝体,得到0.19g/m3(6.6g/ft3)的Rh,再于550℃烧制3小时。最后得到的负载有催化剂的蜂窝体的催化剂总含量约为1.13g/m3(40g/ft3),Pt/Rh比约为5。
接着,使负载有催化剂的蜂窝体与模拟废气混合物一起在位于对开管式炉内的石英管反应器中进行汽车催化活性的试验。气体混合物由以下组分组成:0.77%O2、14%CO2、0.33%H2、0.0333%C3H6、0.0167%C3H8、1%CO、0.1%NO、0.0023%SO2、10%H2O以及余量的氮气。催化反应的空速为50,000hr-1。反应器的温度以1℃/分钟的速率升高,直至最终温度为600℃,氧气浓度保持恒定,使得在整个试验过程中将气流的氧化还原比保持在1.095。测量经催化剂浸渍的蜂窝体的催化活性,具体是测量CO、NOx和烃都达到50%转化率时的温度,即催化剂对于各有毒气体的点火温度。催化活性的结果列于表II。
实施例2
将包含360克沸石、360克γ-氧化铝、180克勃姆石和54克甲基纤维素临时粘合剂的批料进行混合,并挤出形成蜂窝体和棒,所用的方法和具体材料与实施例1中所用的相同。挤出的沸石/氧化铝复合材料的物理和机械性能示于表II。
以与实施例1相同的方法用铂和铑再次对蜂窝体基材进行催化剂负载。用与实施例1相同的混合物、温度和氧化还原比对经负载的样品进行催化活性试验,结果示于表II。
实施例3
将包含2270克沸石、450克γ-氧化铝、180克勃姆石(Versal 700,得自LaRoche Industries)、54克甲基纤维素临时粘合剂和2重量%的乙酸的批料混合在一起,挤出形成蜂窝体和棒,所用的方法和具体材料(除勃姆石以外)与实施例1中所用的相同。物理和机械性能示于表I。如实施例1所述使挤出的蜂窝体负载以催化剂,同样测试其催化活性,具体是测量CO、NOx和HC半转化率的温度(即点火温度)。催化结果示于表II。
比较例4
如下制备批料混合物:将720克ZSM-5沸石(CBV-3002,得自PQCorporation)与523.2克浓缩有机硅树脂(Dow Corning的6-2230树脂以树脂/溶剂比为3/1溶解在二价酸酯溶液中,得到20%的二氧化硅永久粘合剂)混合。将良好混合的批料转移到研磨机中,加入260克水。然后用柱塞式挤出机挤出塑化批料,形成蜂窝体和棒,再次测量其机械和物理性能。对挤出的蜂窝体负载催化剂,按实施例1中所述方式在模拟废气流中测试转化率性能。
比较例5
将包含720克γ-氧化铝(GH-22,得自LaRoche Industries)和180克勃姆石(Versal 700,得自LaRoche Industries)的批料混合物加入4重量%乙酸和390克水后进行研磨,得到塑化批料。如前所述,将塑化批料挤出成蜂窝体和棒,用来测量机械和物理性能。用实施例1所述方式使蜂窝体负载催化剂,然后根据实施例1所述方法测试其催化性能。
实施例6-11
这些实施例的组成详细列于表I,按上述方法将这些组分形成塑化批料,再制成蜂窝体。一个显著的例外是实施例11,该实施例的组合物中加入的是两种不同勃姆石原料混合物的勃姆石组分,该勃姆石混合物是上述Catapal B和Versal 700勃姆石材料的50/50混合物。
如前所述,将按实施例1所述方式负载催化剂的蜂窝体用实施例1所述方法测试其催化性能,每个实施例对于CO、NOx和HC的催化半转化率温度均示于表II。
表I
1 | 2 | 3 | 4* | 5* | 6 | 7 | 8 | |
批料混合物(克) | ||||||||
沸石 | 450 | 360 | 270 | 720 | 270 | 450 | 270 | |
γ-氧化铝 | 270 | 360 | 450 | 720 | 450 | 270 | 450 | |
勃姆石 | 180 | 180 | 180 | 180 | 180 | 180 | 180 | |
有机硅树脂 | 523.2 | |||||||
临时粘合剂 | 54 | 54 | 54 | 54 | 54 | 54 | 54 | |
水 | 350 | 365 | 385 | 260 | 390 | 380 | 355 | 360 |
烧制组成 | ||||||||
沸石百分数 | 50 | 40 | 30 | 80 | -- | 30 | 50 | 30 |
γ-氧化铝百分数 | 50 | 60 | 70 | -- | 100 | 70 | 50 | 70 |
二氧化硅百分数 | -- | -- | -- | 20 | -- | -- | -- | -- |
性能 | ||||||||
表面积(m2/g) | 215 | 215 | 205 | 235 | 205 | .74 | 210 | 205 |
孔隙率(%) | 31.2 | 33.0 | 39.0 | 35.4 | 67.0 | 40.4 | 35.4 | 35.4 |
平均孔径(nm) | 40 | 30 | 20 | 470 | 12 | 20 | 40 | 20 |
断裂模量kg/cm2(psi) | 77.9(1109) | 61.8(879) | 98.2(1397) | 239.6(3410) | 103.2(1469) | 98.2(1398) | 77.9(1109) | 98.2(1398) |
弹性模量×10-8kg/cm2(×10-6psi) | 3.86(0.55) | 3.72(0.53) | 13.4(1.90) | 5.76(0.82) | 3.72(0.53) | 4.00(0.57) | 9.91(1.41) | |
平均热膨胀系数(×10-7/℃) | 15.0 | 24.0 | 39.4 | 13.8 | 64.5 | 39.4 | 15.0 | 36.5 |
计算的抗温度急变性(℃) | 1290 | 461 | 670 | 1301 | 324 | 670 | 1290 | 272 |
*比较例
表I(续)
9 | 10 | 11 | |
批料混合物(克) | |||
沸石 | 180 | 360 | 360 |
γ-氧化铝 | 450 | 270 | 270 |
勃姆石 | 270 | 270 | 270 |
有机硅树脂 | |||
临时粘合剂 | 54 | 54 | 54 |
水 | 385 | 370 | 370 |
烧制组成 | |||
沸石百分数 | 20 | 40 | 40 |
γ-氧化铝百分数 | 80 | 60 | 60 |
二氧化硅百分数 | -- | -- | -- |
性能 | |||
表面积(m2/g) | 220 | 280 | 170-260 |
孔隙率(%) | 26.4 | 31.0 | -- |
平均孔径(nm) | 40 | 80 | -- |
断裂模量kg/cm2(psi) | 145.0(2063) | 66.0(939) | ~70.3(1000) |
弹性模量×10-8kg/cm2(×10-6psi) | 8.85(1.26) | 4.15(0.59) | |
平均热膨胀系数(×10-7/℃) | 51.2 | 21.3 | ~25.0 |
计算的抗温度急变性(℃) | 320 | 747 | -- |
表II
1 | 2 | 3 | 4* | 5* | 6 | 7 | 8 | |
点火温度(℃) | ||||||||
CO | 228 | 222 | 205 | 260 | 230 | 205 | 288 | 186 |
NOx | 228 | 228 | 188 | 250 | 230 | 188 | 288 | 198 |
HC's | 260 | 247 | 188 | 285 | 240 | 188 | 260 | 223 |
表II(续)
9 | 10 | 11 | |
点火温度(℃) | |||
CO | 185 | 230 | |
NOx | 188 | 230 | |
HC's | 205 | 247 |
*比较例
从表I可见,所有样品的表面积基本相同,而样品的孔隙率却相当剧烈地变化。与比较例4的沸石/二氧化硅样品不同,实施例1-3中的粘合剂勃姆石被认为能有效地与材料的表面的OH基团互相作用。在干燥过程中,勃姆石在脱水时发生形变并收缩,将所有颗粒聚集在一起,从而获得小的平均孔径。
实施例1-3的热膨胀均小于比较例5的100%氧化铝样品。纯氧化铝样品显示足够高的热膨胀,所以往往不能抵抗典型的汽车废气流的热循环。可以认为,负热膨胀的沸石组分的存在是本发明沸石/氧化铝的热膨胀低于纯氧化铝样品的主要原因。
从表II可见,比较例5的100%氧化铝样品的催化性能低于本发明实施例1-3和实施例6-11的样品。具体来说,比较例5催化剂的点火温度低于200℃。可以认为,尽管孔隙率高,但尺寸非常小孔隙的存在限制了催化性能,因为废气污染物分子扩散经过这些细孔很困难。
参见比较例4具有二氧化硅粘合剂的挤出沸石,由表I可见该样品对氧化CO和HC's以及还原NOx的催化活性均低。尽管该样品的平均孔径大,但通常存在于沸石晶体中5.4×5.6埃的通道尺寸限制了污染物分子扩散到催化剂活性部位,从而导致高点火温度。
尽管不想受到理论的束缚,但推测本发明沸石/氧化铝复合体的催化性能高于挤出的纯氧化铝,部分是因为氧化铝组分的存在。氧化铝的存在被认为是增强催化活性的至少部分原因,使催化活性高于典型的沸石基催化剂,后者的催化活性通常被认为是较低的。此外,本发明沸石/氧化铝复合体的孔径比氧化铝大,这被认为是造成点火温度低的一个重要因素,而复合体中包含沸石组分使得平均孔径增加。
应该理解,尽管本发明详细说明了一些说明性的具体实例,但本发明并不局限于这些实例,因为在不偏离权利要求书所限定的本发明广泛宗旨和范围的情况下可以对其作出许多变化。
Claims (22)
1.一种用作催化剂基材或催化剂载体的沸石/氧化铝复合材料,该材料包含30-70重量份二氧化硅/氧化铝比值至少为300的沸石和30-70重量份比表面积大于100m2/g的γ-氧化铝,该复合材料的断裂模量至少为52.7kg/cm2。
2.如权利要求1所述的沸石/氧化铝复合材料,其特征在于所述复合材料的断裂模量至少为70.3kg/cm2。
3.如权利要求1所述的沸石/氧化铝复合材料,其特征在于所述复合材料的表面积至少为100m2/g。
4.如权利要求1所述的沸石/氧化铝复合材料,其特征在于所述复合材料的表面积至少为200m2/g。
5.如权利要求1所述的沸石/氧化铝复合材料,其特征在于所述复合材料的热膨胀小于5×10-6/℃。
6.如权利要求1所述的沸石/氧化铝复合材料,其特征在于所述复合材料在高达至少1000℃的温度时显示热稳定性。
7.如权利要求1所述的沸石/氧化铝复合材料,其特征在于所述沸石/氧化铝复合材料是每平方英寸至少具有600个通道的蜂窝结构体。
8.如权利要求1所述的沸石/氧化铝复合材料,其特征在于所述复合材料还包含稳定的氧化锆氧贮存材料,其含量为氧化锆占沸石氧化铝复合材料的20-30重量%。
9.如权利要求7所述的沸石/氧化铝复合材料,其特征在于所述稳定的氧化锆中包含选自氧化铈、氧化钛、氧化钇、氧化镁、氧化镨、氧化钙、氧化镁、氧化钡和/或它们混合物的掺杂剂。
10.如权利要求8所述的沸石/氧化铝复合材料,其特征在于所述稳定的氧化锆中包含一种掺杂剂混合物,以氧化锆的总量计,该混合物包含最多80重量%的氧化铈和最多20重量%的氧化钇。
11.如权利要求1所述的沸石/氧化铝复合材料,其特征在于所述氧化铝中包含选自氧化镧、氧化钡、氧化锶和氧化钇的稳定剂。
12.一种制备权利要求1所述复合材料的方法,所述复合材料是具有高表面积的挤出的整块蜂窝体,该方法包括:
(a)将下列各组分混合成基本均匀的批料
(i)沸石,其二氧化硅/氧化铝的比至少为300∶1,表面积至少为250m2/g二氧化硅;
(ii)比表面积大于100m2/g的γ-氧化铝组分,其至少一部分是勃姆石;
(iii)临时粘合剂,选自甲基纤维素、乙基纤维素、羟丁基纤维素、羟丁基甲基纤维素、羟乙基纤维素、羟甲基纤维素、羟丙基纤维素、羟丙基甲基纤维素、羟乙基甲基纤维素,以及它们的混合物,
(iv)水;
(b)将批料挤出形成蜂窝结构体生坯;
(c)将该结构体生坯加热5-30分钟形成无裂缝的干燥结构体;
(d)在500-1000℃加热即烧结经干燥的蜂窝结构体,加热的时间足以形成高表面积的烧结结构体。
13.如权利要求12所述的方法,其特征在于该方法还包括向基本均匀的批料中混入一定量的氧化锆。
14.如权利要求12所述的方法,其特征在于所述氧化锆中包含一定量的稳定剂,选自氧化铈、氧化钛、氧化钇、氧化镁、氧化镨和/或它们混合物。
15.如权利要求12所述的方法,其特征在于所述稳定剂是氧化铈和氧化钇的混合物。
16.如权利要求12所述的方法,其特征在于所述氧化铝中包含选自氧化镧、氧化钡、氧化锶和氧化钇的稳定剂。
17.一种三元催化净化剂(TWC)体系,用来从废气中除去烃、一氧化碳和氮的氧化物,该TWC体系包括:
(1)催化剂载体,它是权利要求1所述的沸石/氧化铝复合材料,
(2)浸渍在催化剂载体上的贵金属催化剂,所述贵金属选自铂、铑、铱和钯。
18.如权利要求17所述的TWC催化净化剂体系,其特征在于所述复合材料的断裂模量至少为70.3kg/cm2。
19.如权利要求17所述的TWC催化净化剂体系,其特征在于所述催化净化剂体系包含0.142-1.70g/m3的贵金属催化剂。
20.如权利要求17所述的TWC催化净化剂体系,其特征在于所述催化净化剂体系包含铂和铑的混合物,铂/铑的重量比在5-10的范围内。
21.如权利要求20所述的TWC催化净化剂体系,其特征在于铂的存在量最多为1.13g/m3,铑的存在量最多为0.23g/m3。
22.如权利要求20所述的TWC催化净化剂体系,其特征在于铂的存在量为0.94g/m3,铑的存在量为0.19g/m3。
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-
2000
- 2000-11-03 BR BR0016776-2A patent/BR0016776A/pt not_active Application Discontinuation
- 2000-11-03 KR KR1020027008399A patent/KR20020061011A/ko not_active Application Discontinuation
- 2000-11-03 CN CNB008179212A patent/CN1171676C/zh not_active Expired - Fee Related
- 2000-11-03 JP JP2001548218A patent/JP2003518434A/ja active Pending
- 2000-11-03 AU AU14612/01A patent/AU1461201A/en not_active Abandoned
- 2000-11-03 EP EP00976904A patent/EP1242183A1/en not_active Ceased
- 2000-11-03 WO PCT/US2000/030357 patent/WO2001047634A1/en not_active Application Discontinuation
- 2000-11-03 MX MXPA02006446A patent/MXPA02006446A/es not_active Application Discontinuation
- 2000-12-12 US US09/735,207 patent/US6413898B1/en not_active Expired - Fee Related
-
2002
- 2002-05-09 US US10/143,411 patent/US6780805B2/en not_active Expired - Lifetime
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107810058A (zh) * | 2015-06-29 | 2018-03-16 | 康宁股份有限公司 | 减少排放物的多孔陶瓷体 |
CN107810058B (zh) * | 2015-06-29 | 2022-01-25 | 康宁股份有限公司 | 减少排放物的多孔陶瓷体 |
Also Published As
Publication number | Publication date |
---|---|
CN1414883A (zh) | 2003-04-30 |
MXPA02006446A (es) | 2002-11-29 |
WO2001047634A1 (en) | 2001-07-05 |
EP1242183A1 (en) | 2002-09-25 |
US6780805B2 (en) | 2004-08-24 |
US20020183191A1 (en) | 2002-12-05 |
AU1461201A (en) | 2001-07-09 |
US6413898B1 (en) | 2002-07-02 |
BR0016776A (pt) | 2002-08-27 |
JP2003518434A (ja) | 2003-06-10 |
KR20020061011A (ko) | 2002-07-19 |
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