CN1303737A - Preparation process for composite metal oxide and composite metal catalyst - Google Patents
Preparation process for composite metal oxide and composite metal catalyst Download PDFInfo
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- CN1303737A CN1303737A CN 00100913 CN00100913A CN1303737A CN 1303737 A CN1303737 A CN 1303737A CN 00100913 CN00100913 CN 00100913 CN 00100913 A CN00100913 A CN 00100913A CN 1303737 A CN1303737 A CN 1303737A
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- composite metal
- catalyst
- hydrolysis
- metal oxide
- titanium
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- 239000002131 composite material Substances 0.000 title claims abstract description 161
- 239000003054 catalyst Substances 0.000 title claims abstract description 120
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 72
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 72
- 229910052751 metal Inorganic materials 0.000 title claims description 50
- 239000002184 metal Substances 0.000 title claims description 50
- 238000002360 preparation method Methods 0.000 title claims description 38
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 82
- 239000010936 titanium Substances 0.000 claims abstract description 36
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 26
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000004411 aluminium Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000003960 organic solvent Substances 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000002738 chelating agent Substances 0.000 claims abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 73
- 238000006460 hydrolysis reaction Methods 0.000 claims description 45
- 230000007062 hydrolysis Effects 0.000 claims description 44
- 238000010304 firing Methods 0.000 claims description 33
- 229910000510 noble metal Inorganic materials 0.000 claims description 28
- -1 alkoxyl aluminum Chemical compound 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 21
- 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 claims description 15
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims description 14
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical class CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 150000002739 metals Chemical class 0.000 claims description 10
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 8
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 7
- 150000003608 titanium Chemical class 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 claims description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 20
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 18
- 125000003545 alkoxy group Chemical group 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 2
- 150000001398 aluminium Chemical class 0.000 abstract 2
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 60
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 55
- 230000000052 comparative effect Effects 0.000 description 54
- 229910018575 Al—Ti Inorganic materials 0.000 description 51
- 238000005259 measurement Methods 0.000 description 39
- 238000002485 combustion reaction Methods 0.000 description 33
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 27
- BYFGZMCJNACEKR-UHFFFAOYSA-N Al2O Inorganic materials [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 20
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 20
- 238000002441 X-ray diffraction Methods 0.000 description 17
- 229910052788 barium Inorganic materials 0.000 description 14
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 14
- 239000007789 gas Substances 0.000 description 14
- 239000003643 water by type Substances 0.000 description 14
- OHMBHFSEKCCCBW-UHFFFAOYSA-N hexane-2,5-diol Chemical compound CC(O)CCC(C)O OHMBHFSEKCCCBW-UHFFFAOYSA-N 0.000 description 13
- 229910010413 TiO 2 Inorganic materials 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 229910052717 sulfur Inorganic materials 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 230000014509 gene expression Effects 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 8
- 231100000572 poisoning Toxicity 0.000 description 8
- 230000000607 poisoning effect Effects 0.000 description 8
- 239000013049 sediment Substances 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000002950 deficient Effects 0.000 description 5
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000035800 maturation Effects 0.000 description 4
- 235000011056 potassium acetate Nutrition 0.000 description 4
- 238000004088 simulation Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 150000004645 aluminates Chemical class 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229910003086 Ti–Pt Inorganic materials 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- ZOAIGCHJWKDIPJ-UHFFFAOYSA-M caesium acetate Chemical compound [Cs+].CC([O-])=O ZOAIGCHJWKDIPJ-UHFFFAOYSA-M 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000035784 germination Effects 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon 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
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 2
- OBROYCQXICMORW-UHFFFAOYSA-N tripropoxyalumane Chemical compound [Al+3].CCC[O-].CCC[O-].CCC[O-] OBROYCQXICMORW-UHFFFAOYSA-N 0.000 description 2
- UOFGSWVZMUXXIY-UHFFFAOYSA-N 1,5-Diphenyl-3-thiocarbazone Chemical compound C=1C=CC=CC=1N=NC(=S)NNC1=CC=CC=C1 UOFGSWVZMUXXIY-UHFFFAOYSA-N 0.000 description 1
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 description 1
- ZXVONLUNISGICL-UHFFFAOYSA-N 4,6-dinitro-o-cresol Chemical group CC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O ZXVONLUNISGICL-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 229910002703 Al K Inorganic materials 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- APIDIPGVBRXKEJ-UHFFFAOYSA-N acetic acid titanium Chemical compound [Ti].CC(O)=O.CC(O)=O APIDIPGVBRXKEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JGUQDUKBUKFFRO-CIIODKQPSA-N dimethylglyoxime Chemical compound O/N=C(/C)\C(\C)=N\O JGUQDUKBUKFFRO-CIIODKQPSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-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
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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Abstract
A method for preparing composite metal oxide includes the following steps: mixing the substituted aluminium alcoholate whose at least one or several alkoxyls substituted by chelating agent and titanium or titanium alcoholate mixed into on organic solvent to prepare a solution, then hydrolyzing the above-mentioned components, drying and roasting. Beause the hydrolyzing rates of substituted aluminium alcoholate and titanium or titanium alcoholate are basically identical so that it can inhibit the productino of free Al2O3, there fore the obtained composite metal oxide possesses completely uniformly formed high specific surface area. Said invention also discloses three methods for preparing catalyst for preparing said composite metal oxide catalyst and their various steps.
Description
The present invention relates to the method that a kind of preparation can be used as the composite metal oxide or the analog of catalyst carrier for purifying vehicle tail gas; And a kind of method for preparing composite metal catalyst, wherein, for example be attached in the carrier the gained composite metal oxide.
As the carrier of cleaning catalyst for tail gases of automobiles, use mostly to have high-specific surface area and highly active aluminium oxide (Al
2O
3).Such technical task has appearred recently, that is, and and the nitrogen oxide (NO in the tail gas
x) should in the excessive poor gas atmosphere of oxygen, purify.Therefore, disclosed as open (KOKAI) 5-317652 of Japanese unexamined patent publication No. etc., developed a kind of catalyst, wherein will be selected from the NO of alkali metal and alkaline-earth metal
xStoring element loads on by Al together with noble metal
2O
3On the carrier of making.According to this catalyst, NO
xUnder the poor gas atmosphere, can be adsorbed on NO
xStore on the element.On the stoichiometric point or under rich combustion gas atmosphere, adsorbed NO
xThe reducing gas that is released with HC and so on reacts, thereby is purified.Therefore, even under the poor gas atmosphere, also can suppress NO
xDischarging and reach high NO
xPurifying property.
But there is following defective in the catalyst for wherein alkaline-earth metal such as barium (Ba) and platinum (Pt) being loaded on the active aluminum oxide carrier.That is, alkaline-earth metal and aluminium oxide can react about 800 ℃, have so just reduced NO because generate the crystalline aluminium hydrochlorate
xStorage capacity.Therefore and hear resistance is not enough in addition, this catalyst.
Therefore, Japanese unexamined patent publication No. open (KOKAI) 8-057312 discloses a kind of catalyst, comprises amorphous aluminate and the noble metal that loads on the amorphous aluminate as carrier.This amorphous aluminate is made up of composite metal oxide, comprising NO
xStore element, at least a alkali metal and the alkaline-earth metal of being selected from; And aluminium.By making carrier, just can suppress at high temperature to generate the crystalline aluminium hydrochlorate by this composite metal oxide.Therefore, this catalyst is improved on hear resistance.
Simultaneously, comprise the SO that produces by fuel institute sulfur-bearing in the tail gas
2, and its can be on noble metal with the poor gas atmosphere in oxygen react, be transformed into SO
x, as SO
3Gained SO
xChange into sulfuric acid by the steam in the tail gas easily.SO
xWith sulfuric acid and alkaline NO
xStore element and react, generate sulphite and sulfate.Have been found that sulphite and sulfate can reduce NO
xStore the effect of element.This phenomenon is called " sulfur poisoning ".In addition, because Al
2O
3And so on porous carrier often tend to adsorb SO
x, the problem that sulfur poisoning therefore occurred aggravating.
But because TiO
2Do not adsorb SO
2, so the present inventor expects adopting TiO
2Carrier is also tested.The result is as follows.Because SO
2Can not be adsorbed on TiO
2Go up also and in fact flow to the downstream, and have only the SO of direct contact noble metal
2Just oxidized, so the sulfur poisoning degree is lower.But adopt TiO
2The initial NO of the catalyst of carrier
xIt is lower to purify activity, therefore is not suitable for use in cleaning catalyst for tail gases of automobiles.
Therefore, Japanese unexamined patent publication No. open (KOKAI) 8-099034 has proposed a kind of composite metal catalyst, and it adopts by composite metal oxide, as TiO
2-Al
2O
3The carrier of making, and wherein with NO
xStoring element and noble metal loads on this carrier.According to this catalyst, can suppress NO
xStore element generation sulfur poisoning, even and after this catalyst stands endurancing, also can guarantee high NO
xPurifying property.
As a kind of method for preparing this composite metal oxide, for example, can from open (KOKOKU) 2-033644 of Japanese unexamined patent, learn a kind of preparation method.This preparation method is characterised in that, will contain two or more and contain the oxygen organo-metallic compound and sneak in a kind of solvent, wherein comprises the polar compound with multidentate ligand or crosslinked coordination ability; They change into gel by hydrolysis; Dry then gained gel is also fired.According to this preparation method, can prepare the composite metal oxide of even matter easily.Can load on the carrier of forming by composite metal oxide by noble metal like this and make composite metal catalyst platinum and so on.
Open (KOKOKU) 2-033644 of Japan's unexamined patent has enumerated metal alcoholate as containing the oxygen organo-metallic compound.Therefore, if adopt aforementioned preparation method to prepare the Al-Ti composite oxides, can consider to use aluminum alcoholate and alcoholization titanium so.
But aluminum alcoholate has different hydrolysis reaction with the alcoholization titanium.Therefore, as described later,, be difficult to prepare Al-Ti composite oxides with even matter composition by the open disclosed preparation method of (KOKOKU) 2-033644 of Japanese unexamined patent.
Therefore, if catalyst has adopted the Al-Ti composite oxides of making by the open disclosed preparation method of (KOKOKU) 2-033644 of Japanese unexamined patent as carrier, TiO so
2Just can not fully produce the sulfur poisoning inhibitory action.Therefore, this catalyst can not fully suppress NO after standing endurancing
xThe reduction of conversion ratio.
In addition, according to the inventor's research, disclosed following content.If use aluminum alcoholate to synthesize composite metal oxide, the gained composite metal oxide is with regard to the hear resistance deficiency so, and its specific area descends inevitably.If this composite metal oxide is attached in the carrier, and load NO thereon
xStore element or compound with it, the gained catalyst then has following defective so.That is, if this catalyst experiences high temperature, NO so in use
xThe dispersiveness that stores element just reduces, and causes NO
xStore the crystallization of element.As a result, the NO of this catalyst
xThe purifying property variation.
Therefore, as mentioned above, if use aluminum alcoholate to synthesize composite metal oxide, the gained composite metal oxide is with regard to the hear resistance deficiency so, and its specific area descends inevitably.Therefore, if will be attached in the carrier by the composite metal oxide of preparation method's gained disclosed in the aforementioned patent, and on this carrier load NO
xStore element and noble metal to constitute catalyst, the gained catalyst then has following defective so.That is, if this catalyst experiences high temperature, NO so in use
xThe dispersiveness that stores element and noble metal just reduces, and causes noble metal to form particle and NO gradually
xStore the element crystallization.As a result, the three-element catalytic activity and the NO of this catalyst
xThe purifying property variation.
In addition, if with composite metal oxide, as the open disclosed TiO of (KOKAI) 8-099034 of Japanese unexamined patent publication No.
2-Al
2O
3Be attached in the carrier, and noble metal loaded on this carrier make catalyst, the germination effect of noble metal in the high temperature durability test is just not low so, because this carrier does not have enough composition uniformly.Therefore, the three-element catalytic of gained catalyst is active just not enough.
The present invention develops according to afore-mentioned.Therefore, an object of the present invention is easily and stably to prepare and wherein will have enough the catalyst that the Al-Ti composite oxides of evenly forming are made carrier.Even another object of the present invention is to make catalyst also have high-fire resistance and high purifying property after standing the high temperature durability test.
The method for preparing composite metal oxide that claim 1 proposed has solved aforementioned technical problem, it is characterized in that, it may further comprise the steps:
Prepare a kind of solution, wherein will replace aluminum alcoholate and titanium salt and at least a the sneak into organic solvent of alcoholization in the titanium, wherein said replacement aluminum alcoholate is for its at least one or a plurality of alkoxyl aluminum alcoholate that agent replaced that is chelated; Then
Each component of solution is carried out drying and fired after hydrolysis.
The method for preparing composite metal oxide that claim 2 proposed is further specialized the composite metal oxide preparation method that claim 1 proposed, and it is characterized in that it may further comprise the steps:
Prepare a kind of solution, wherein substituted propanol aluminium and titanium tetraisopropylate sneaked into organic solvent, wherein said substituted propanol aluminium for its at least one or a plurality of isopropoxy by aluminum isopropylate that ethyl acetoacetate replaced; Then
These alkoxide are carried out drying and fire after hydrolysis.
The method for preparing composite metal catalyst that claim 3 proposed has solved aforementioned technical problem, it is characterized in that, it may further comprise the steps:
Prepare a kind of solution, wherein will replace aluminum alcoholate and titanium salt and at least a the sneak into organic solvent of alcoholization in the titanium, wherein said replacement aluminum alcoholate is for its at least one or a plurality of alkoxyl aluminum alcoholate that agent replaced that is chelated;
Each component of solution is carried out drying and fired after hydrolysis, can form carrier like this; Then
At least noble metal loads on this carrier.
The method for preparing composite metal catalyst that claim 4 proposed is further specialized the preparation method of the composite metal catalyst that claim 3 proposed, and it is characterized in that it may further comprise the steps:
Prepare a kind of solution, wherein substituted propanol aluminium and titanium tetraisopropylate sneaked into organic solvent, wherein said substituted propanol aluminium for its at least one or a plurality of isopropoxy by aluminum isopropylate that ethyl acetoacetate replaced;
These alcoholates are carried out drying and fire after hydrolysis, can form carrier like this; Then
At least noble metal loads on this carrier.
The composite metal catalyst preparation method that claim 5 proposed is characterised in that it may further comprise the steps:
To replace aluminum alcoholate and a kind of soluble compound is sneaked into organic solvent, wherein said replacement aluminum alcoholate is for its at least one or a plurality of alkoxyl aluminum alcoholate that agent replaced that is chelated, and described soluble compound dissolves in this organic solvent, and comprises by NO
xStore the catalyst metals element of at least a composition in element and the noble metal, described NO
xStore element and be and be selected from least a in alkali metal, alkaline-earth metal and the rare earth element; Then
After described replacement aluminum alcoholate hydrolysis to the major general, drying and each component of firing this mixture.
The composite metal catalyst preparation method that claim 6 proposed is characterised in that in the preparation method of the composite metal catalyst that claim 5 proposed, described chelating agent is an ethyl acetoacetate.
According to the preparation method of composite metal oxide of the present invention, can guarantee to prepare and have even composition and the good composite metal oxide of hear resistance.
According to the preparation method of composite metal oxide of the present invention, can be easily and stably prepare the high catalyst of specific area, wherein NO
xThe dispersiveness that stores element and noble metal is improved, and the hear resistance of this catalyst and anti-sulfur poisoning are good.
By the reference the following detailed description, and in conjunction with the accompanying drawings and describe in detail, can more completely understand the present invention and many advantages thereof, can understand better simultaneously, all these contents all are parts of the present invention:
Fig. 1 is in an example according to preparation method of the present invention, is used to illustrate the wherein schematic diagram of step.
Fig. 2 is the histogram that is used to illustrate the specific area of embodiment 1-10 and Comparative Examples 1-4 gained Al-Ti composite oxides.
Fig. 3 is used to illustrate embodiment 1,3,5 and 7 and the x-ray diffraction pattern of the X-ray diffraction pattern of Comparative Examples 1 and 3 gained Al-Ti composite oxides.
Fig. 4 is used to illustrate embodiment 2,4,6 and 8 and the x-ray diffraction pattern of the X-ray diffraction pattern of Comparative Examples 2 and 4 gained Al-Ti composite oxides.
After general description the present invention, can be by further understanding with reference to specific preferred embodiment, these embodiments provided by the present invention only are used for explanation, therefore can not be used for limiting the scope of claims.
The present inventor examines the disclosed preparation method of patent disclosure (KOKOKU) 2-033644 for the preparation of going out the Al-Ti composite oxides by research with Japan. If but adopted this preparation method to prepare the Al-Ti composite oxides, following phenomenon will appear so. That is, when gained Al-Ti composite oxides were fired under about 900 ℃, its specific area descended. Fire and generate α-Al2O
3 About these phenomenons, find not consist of the free Al of composite oxides2O
3Remain in a large number in the Al-Ti composite oxides of gained. That is, free Al2O
3At high temperature change into α-Al2O
3, so the specific area of Al-Ti composite oxides descends. Therefore, if use the Al-Ti composite oxides in catalyst, the defective that the gained catalyst activity reduces so just appears.
Further studied the reason of this unfavorable phenomenon. The result thinks that having generated does not have and TiO2Compound free Al2O
3, because the hydrolysis rate of aluminum alcoholate will be higher than the hydrolysis rate that refines titanium. That is, if aluminum alcoholate and alcoholization titanium are hydrolyzed under coexistence state, aluminum alcoholate is faster than the hydrolysis of alcoholization titanium so. Therefore, after firing the Al-Ti composite oxides of gained, do not participate in compound Al2O
3Just remain in the Al-Ti composite oxides.
Therefore, preparation method of the present invention has adopted and has replaced aluminum alcoholate as one of precursor of composite metal oxide, and it is a kind of its at least a or a plurality of alkoxyls aluminum alcoholates that agent replaces that are chelated.
This replacement aluminum alcoholate is characterised in that its hydrolysis rate will be lower than the hydrolysis rate of aluminum alcoholate. Therefore, the hydrolysis rate of this replacement aluminum alcoholate just equals for example to refine the hydrolysis rate of titanium. Therefore, Al2O
3And TiO2Facilitate compound. Think that in addition by using this replacement aluminum alcoholate, the composition metal element of Al and Ti and so on just can combine by chelating agent. In addition, because this replacement aluminum alcoholate stable existence is in organic solvent, therefore the higher aluminum alcoholate of hydrolysis rate can not appear because the disassociation of chelating agent and separated defective.
In addition, if adopt substituted propanol aluminium (it is a kind of its one or more isopropyls by the aluminum isopropylate that ethyl acetoacetate replaced) and titanium tetraisopropylate, the hydrolysis rate of substituted propanol aluminium and titanium tetraisopropylate is just mutually very approaching so. Therefore, can further suppress not consist of the free Al of composite oxides2O
3Remain in the gained Al-Ti composite oxides. Therefore, can obtain having high specific surface area and the even Al-Ti composite oxides that form.
In addition, because its isopropoxy can at room temperature be dissolved in the 2-propyl alcohol by the substituted propanol aluminium that ethyl acetoacetate replaced, therefore produced such advantage, the productive rate of Al-Ti composite oxides is brought up to 2 times when not using this substituted propanol aluminium.
In addition, if soluble compound (is dissolved in organic solvent, and comprises by NOxStore the catalyst metals element of at least a composition in element and the noble metal) and the replacement aluminum alcoholate sneak in the organic solvent, and be hydrolyzed at least subsequently this replacement aluminum alcoholate, so this replacement aluminum alcoholate is characterised in that its hydrolysis rate is lower than the hydrolysis rate of aluminum alcoholate. Therefore, compare with the situation of using aluminum alcoholate, this replacement aluminum alcoholate facilitates with soluble compound compound.
Owing to these reasons, can suppress does not have compound free Al2O
3Remain in the gained Al-Ti composite oxides, and in formed complex, aluminium and catalyst metals element are evenly compound. Therefore, the gained composite metal oxide has high-specific surface area and forms uniformly. Like this, NOxThe dispersiveness that stores element and noble metal just obtains improving, and its heat resistance also is improved.
About being used as Al2O
3The aluminum alcoholate in source, its alkoxyl have the alcoholates of 1-5 carbon atom because easy drying etc. are former thereby preferred. For example, can adopt aluminium methoxide, aluminium ethylate, aluminium propoxide, aluminium isopropoxide, aluminium butoxide and isobutanol aluminum.
In preparation method of the present invention, adopted a kind of like this replacement aluminum alcoholate, wherein at least one alkoxyl of aforementioned replacement aluminum alcoholate agent that is chelated replaces. Agent replaces if all alkoxyls of this aluminum alcoholate all are chelated, and can cause so the specific area of gained composite metal oxide to reduce. Therefore, adopt wherein one or two alkoxyl to be chelated replacement aluminum alcoholate that agent replaces. In replacing aluminum alcoholate, preferred wherein two alkoxyls replacement aluminum alcoholate that agent replaces that is chelated is because its hydrolysis rate can further reduce.
About chelating agent, can adopt dimethylglyoxime, dithizone, ethyl acetoacetate, acetylacetone,2,4-pentanedione, glycine, EDTA and NTA. If adopt ethyl acetoacetate as chelating agent, hydrolysis rate will be best. Therefore, the specific area of gained composite metal oxide just especially is improved.
About being used as TiO2The titanium salt in source adopts the titanium salt that dissolves in organic solvent. For example, can adopt Titanium Nitrate, titanium chloride, acetic acid titanium, titanium acid ammonium and titanium complex.
About being used as TiO2The alcoholization titanium in source, its alkoxyl have the alcoholates of 1-5 carbon atom because easy drying etc. are former thereby preferred. For example, can adopt methyl alcohol titanium, titanium ethanolate, titanium propanolate, isopropyl titanate, butanols titanium and titanium isobutoxide.
Al
2O
3Source and TiO2The mixing ratio in source is determined according to the composition of target Al-Ti composite oxides. If adopt the Al-Ti composite oxides as the carrier of tail gas clean-up catalyst, preferably with Al2O
3Source and TiO2Mix in the source, so that Al2O
3/TiO
2Ratio is 1/30 to 30/1 (that is, Al2O
3/TiO
2=1/30-30/1)。
About the catalyst metals element, can select NOxStore at least a in element (be selected from alkali metal, alkaline-earth metal and the rare earth element at least a) and the noble metal. About alkali metal, can enumerate lithium, sodium, potassium and caesium. Alkaline-earth metal is the element of periodic table of elements 2A family, can enumerate magnesium, calcium, strontium and barium. About rare earth element, can be exemplified as scandium, yttrium, lanthanum, cerium, praseodymium and neodymium. About noble metal, can be exemplified as platinum (Pt), rhodium (Rh), palladium (Pd) and iridium (Ir).
For example, if select NOxStore element as the catalyst metals element, so can be by dip loading method or absorption load method, with noble-metal-supported on formed composite metal oxide and make catalyst. In addition, if select noble metal as the catalyst metals element, can pass through the dip loading method so, with NOxStoring element loads on the formed composite metal oxide and makes catalyst. In addition, if select simultaneously NOxStore element and precious metal element as the catalyst metals element, owing to can be made into wherein NOxStore all homodisperse catalyst of element and precious metal element, and avoided load step subsequently, so this scheme is especially preferred.
NO
xStore element preferably with the amount of relative aluminium oxide (making by replacing aluminum alcoholate) 2-50% mole, carry out compound with composite metal oxide or load thereon. If its amount is lower than this scope, so NOxPurifying property is just because NOxStore active not enough and descend. If its amount surpasses this scope, NOxThe effect that stores element is saturated, and NO soxStore element and react with aluminium oxide easily, cause heat resistance decline.
Noble metal is preferably with the amount of relative aluminium oxide (making by replacing aluminum alcoholate) 0.1-20% weight, carry out compound with composite metal oxide or load thereon. If its amount is lower than this scope, purifying property is low. Carry out load if noble metal surpasses this scope, the effect of noble metal will be saturated so, and the cost of gained catalyst rises.
Note, except aluminium, can adopt the metal of titanium, zirconium and silicon and so on. In this case, the metal of titanium, zirconium and silicon and so on can be mixed as the oxide powder, or supply as alcoholates, it can carry out compound with aluminium and catalyst metals element like this. In addition, preferably the storage oxygen of ceria and ceria-zirconia and so on-release oxygen element is sneaked into or compound. By further with titanium carry out compound, NOxThe sulfur poisoning that stores element can further be inhibited.
Soluble compound (comprise the catalyst metals element, and dissolve in organic solvent) can be a kind of compound that dissolves in used organic solvent. Can adopt organo-metallic compound, such as alcoholates, metal nitrate, metal acetate, metalammine and metal chloride.
About organic solvent, can adopt the solvent that can dissolve described replacement aluminum alcoholate, titanium salt and alcoholization titanium or soluble compound. Can adopt methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, butanols, isobutanol, sec-butyl alcohol and the tert-butyl alcohol.
For with the alcoholates hydrolysis in solution, can adopt moisture contained in the air, but preferred under predetermined temperature, stir in this solution, water is added in this solution.Owing to react rapidly, can further increase the specific area of gained composite metal oxide.
About the addition of water, the too low then hydrolysis time of addition is longer.If addition is too high, then be difficult to even hydrolysis, cause the composition of gained composite metal oxide irregular.Therefore, with used alcoholates, the mol ratio of the addition of water is preferably 0.5-20, especially 1-10 relatively.
In order further to promote hydrolysis, preferably in this solution, add a kind of hydrolytic accelerating agent, comprise alkaline matter, as ammonium, ammonium carbonate and amine; Or acid, as formic acid, oxalic acid and tartaric acid.
The preferred 35-150 of the heating-up temperature of hydrolysing step ℃.If be lower than 35 ℃, react hydrolysis owing to reaction rate is lower longer.If the reaction time is too short, there is not compound free Al so
2O
3Then residual in a large number.If heating-up temperature surpasses 150 ℃, alcoholates can decompose.Especially it is desirable to, heating-up temperature is 40-100 ℃.
After the hydrolysis, drying precipitate is removed solvent etc., fire then, can obtain composite metal oxide like this.As required, can be with NO
xStore one of element and noble metal and load on the described composite metal oxide, can obtain composite metal catalyst thus.Drying condition is not particularly limited.The preferred 500-1200 of firing temperature ℃.If firing temperature is lower than 500 ℃, be difficult to form stable composite metal catalyst.If firing temperature surpasses 1200 ℃, the specific area of gained composite metal catalyst can descend.
Describe the present invention in detail with Comparative Examples by the following examples.
According to shown in Figure 1, prepare the Al-Ti composite oxides.
At first, will be as Al
2O
3The 154.6 gram ethyl acetoacetate aluminum-diisopropoxide (Al-EAA) (a kind of replacement aluminum alcoholate) and in source as TiO
2The 40.1 gram titanium tetraisopropylate (Ti (O-i-C in source
3H
7)
4) add in the 423.4 gram 2-propyl alcohol, stir 2 hours to dissolve (Fig. 1 (A)) down at 82 ℃ then.
Then, gained solution is kept down refluxing at 82 ℃.In agitating solution, 121.9 gram-ion exchanged waters are added drop-wise in the solution with the hydrolysis alcoholates.In addition this solution was stirred 4 hours under 82 ℃ of counterflow conditions, can carry out slaking (Fig. 1 (B)) like this.
Then, the solution for vacuum drying to remove solvent, is descended in addition dry 12 hours (Fig. 1 (C)) with the gained sediment at 120 ℃ then.
Then, sediment was calcined 4 hours down at 480 ℃, fired in 800 ℃ of air then 5 hours (Fig. 1 (D)), this can obtain the A1-Ti composite oxides of this embodiment.
The specific area of gained Al-Ti composite oxides determines that by the BET method result provides in Fig. 2.In addition, these Al-Ti composite oxides are carried out the X-ray diffraction analysis, the gained x-ray diffraction pattern provides in Fig. 3.
Obtain the Al-Ti composite oxides of embodiment 2 according to the same way as of embodiment 1, just firing temperature is set in 900 ℃ rather than 800 ℃.Same way as according to embodiment 1 is come measurement the specific area, and the result provides in Fig. 2.In addition, x-ray diffraction pattern provides in Fig. 4.
Obtain the Al-Ti composite oxides of embodiment 3 according to the same way as of embodiment 1, just the heating-up temperature with dissolving step, hydrolysing step and maturation stage is set in 35 ℃ rather than 82 ℃.Same way as according to embodiment 1 is come measurement the specific area, and the result provides in Fig. 2.In addition, x-ray diffraction pattern provides in Fig. 3.
Embodiment 4
Obtain the Al-Ti composite oxides of embodiment 4 according to the same way as of embodiment 3, just firing temperature is set in 900 ℃ rather than 800 ℃.Same way as according to embodiment 1 is come measurement the specific area, and the result provides in Fig. 2.In addition, x-ray diffraction pattern provides in Fig. 4.
Obtain the Al-Ti composite oxides of embodiment 5 according to the same way as of embodiment 1, just the heating-up temperature with dissolving step, hydrolysing step and maturation stage is set in 50 ℃ rather than 82 ℃.Same way as according to embodiment 1 is come measurement the specific area, and the result provides in Fig. 2.In addition, x-ray diffraction pattern provides in Fig. 3.
Obtain the Al-Ti composite oxides of embodiment 6 according to the same way as of embodiment 5, just firing temperature is set in 900 ℃ rather than 800 ℃.Same way as according to embodiment 1 is come measurement the specific area, and the result provides in Fig. 2.In addition, x-ray diffraction pattern provides in Fig. 4.
Embodiment 7
Obtain the Al-Ti composite oxides of embodiment 7 according to the same way as of embodiment 1, just the heating-up temperature with dissolving step, hydrolysing step and maturation stage is set in 65 ℃ rather than 82 ℃.Same way as according to embodiment 1 is come measurement the specific area, and the result provides in Fig. 2.In addition, x-ray diffraction pattern provides in Fig. 3.
Obtain the Al-Ti composite oxides of embodiment 8 according to the same way as of embodiment 7, just firing temperature is set in 900 ℃ rather than 800 ℃.Same way as according to embodiment 1 is come measurement the specific area, and the result provides in Fig. 2.In addition, x-ray diffraction pattern provides in Fig. 4.
Obtain the Al-Ti composite oxides of embodiment 9 according to the same way as of embodiment 1, just adopt 26.7 gram TiCl
4As TiO
2Source rather than 40.1 gram titanium tetraisopropylate (Ti (O-i-C
3H
7)
4).Same way as according to embodiment 1 is come measurement the specific area, and the result provides in Fig. 2.
Embodiment 10
Obtain the Al-Ti composite oxides of embodiment 10 according to the same way as of embodiment 9, just firing temperature is set in 900 ℃ rather than 800 ℃.Same way as according to embodiment 1 is come measurement the specific area, and the result provides in Fig. 2.
Comparative Examples 1
Will be as Al
2O
3The 115.1 gram aluminum isopropylate (Al (O-i-C in source
3H
7)
3) and as TiO
2The 40.1 gram titanium tetraisopropylate (Ti (O-i-C in source
3H
7)
4) add in the 423.4 gram 2-propyl alcohol, stir 2 hours to dissolve down at 82 ℃ then.
Then, gained solution is remained on 82 ℃.In agitating solution, with 28.2 grams 2,4-pentanedione (acetylacetone,2,4-pentanedione) is added drop-wise in this solution.This solution was stirred 2 hours down in addition at 82 ℃.Then, solution is remained on 82 ℃.In agitating solution, 121.9 gram-ion exchanged waters are added drop-wise in the solution with the hydrolysis alcoholates.In addition this solution was stirred 4 hours down in addition at 82 ℃, carry out slaking thus.
Then, the solution for vacuum drying is to remove solvent, following dry 12 hours in addition at 120 ℃ with the gained sediment then.Then, sediment was calcined 4 hours down at 480 ℃, in 800 ℃ of air, fired 5 hours then, obtain the Al-Ti composite oxides of this Comparative Examples.Then, come measurement the specific area according to the same way as of embodiment 1, the result provides in Fig. 2.In addition, x-ray diffraction pattern provides in Fig. 3.
Comparative Examples 2
Obtain the Al-Ti composite oxides of Comparative Examples 2 according to the same way as of Comparative Examples 1, just firing temperature is set in 900 ℃ rather than 800 ℃.Same way as according to embodiment 1 is come measurement the specific area, and the result provides in Fig. 2.In addition, x-ray diffraction pattern provides in Fig. 4.
Comparative Examples 3
Obtain the Al-Ti composite oxides of Comparative Examples 3 according to the same way as of Comparative Examples 1, just drip 36.7 gram ethyl acetoacetates rather than 28.2 grams 2,4-pentanedione (acetylacetone,2,4-pentanedione).Same way as according to embodiment 1 is come measurement the specific area, and the result provides in Fig. 2.In addition, x-ray diffraction pattern provides in Fig. 3.
Comparative Examples 4
Obtain the Al-Ti composite oxides of Comparative Examples 4 according to the same way as of Comparative Examples 3, just firing temperature is set in 900 ℃ rather than 800 ℃.Same way as according to embodiment 1 is come measurement the specific area, and the result provides in Fig. 2.In addition, x-ray diffraction pattern provides in Fig. 4.
Assessment
Table 1 has gathered the kind of the used chelating agent of the Al-Ti composite oxides that are used to prepare embodiment and Comparative Examples, the heating-up temperature of dissolving step, hydrolysing step and maturation stage, and firing temperature.
Table 1
| Embodiment | Comparative Examples | |||||||||||||
| ????1 | ????2 | ????3 | ????4 | ????5 | ????6 | ????7 | ????8 | ????9 | ????10 | ????1 | ????2 | ????3 | ????4 | |
| ?Al 2O 3The source | Ethyl acetoacetate aluminum-diisopropoxide (Al-EAA) | ??Al(O-i-C 3H 7) 3 | ||||||||||||
| ?TiO 2The source | Titanium tetraisopropylate (Ti (O-i-C 3H 7) 4) | ??TiCl 4 | ????Ti(O-i-C 3H 7) 4 | |||||||||||
| Chelating agent | Ethyl acetoacetate | Acetylacetone,2,4-pentanedione | Ethyl acetoacetate | |||||||||||
| Heating-up temperature (℃) | ??82 | ??82 | ??35 | ??35 | ??50 | ??50 | ??65 | ??65 | ??82 | ??82 | ?- | ??- | ?- | ??- |
| Firing temperature (℃) | ??800 | ??900 | ??800 | ??900 | ??800 | ??900 | ??800 | ??900 | ??800 | ??900 | ??800 | ??900 | ??800 | ??900 |
According to Fig. 2, if fire under 800 ℃, 3 of embodiment show minimum specific area in these embodiments so.But should be appreciated that the specific area of the specific area of the Al-Ti composite oxides of embodiment 3 and Comparative Examples 1 and Comparative Examples 3 is suitable, and the specific area of the Al-Ti composite oxides of other embodiment is than the height of Comparative Examples 1 and Comparative Examples 3.If fire under 900 ℃, the specific area of Al-Ti composite oxides (except embodiment 4) that should be appreciated that these embodiment is all than the height of Comparative Examples.
Therefore, following content is obvious.That is, if firing temperature is 800 ℃, and if heating-up temperature be set in 35 ℃ or higher; In addition, if firing temperature is 900 ℃, and if heating-up temperature be set in 50 ℃ or higher; The specific area of the Al-Ti composite oxides that preparation method so of the present invention is made is equivalent to or is higher than the Al-Ti composite oxides of making by conventional preparation method.
In Fig. 4, all observed α-Al in all Al-Ti composite oxides
2O
3The peak.Because α-Al
2O
3When the common aluminium oxide of heating, generate, so α-Al
2O
3Existence proof the free alumina that does not get transformed into the Al-Ti composite oxides is arranged.But Al in these embodiments,
2O
3Peak intensity reduce along with the rising of heating-up temperature.For example, the peak intensity of embodiment 6 is equivalent to the peak intensity of Comparative Examples 2 and Comparative Examples 4.Therefore, from the homogeneity of Al-Ti composite oxides, embodiment 6 is equivalent to Comparative Examples 2 and 4.The heating-up temperature of embodiment 8 and embodiment 2 is 65 ℃ and 82 ℃, so embodiment 8 and embodiment 2 show than Comparative Examples 2 and 4 higher homogeneity.
That is, if heating-up temperature is set in 50 ℃ or higher, and if firing temperature be set in 900 ℃, can prepare the Al-Ti composite oxides that on homogeneity, are equivalent to or are higher than the Comparative Examples that adopts conventional preparation method so.This result with Fig. 2 is consistent, and specific area and α-Al
2O
3Obviously there is a kind of close correlation between the content.In addition, conventional relatively preparation method, preparation method of the present invention obviously can guarantee to prepare the Al-Ti composite oxides with higher even composition.
In Fig. 3, do not observe α-Al in all Al-Ti composite oxides in addition
2O
3The peak.Therefore, be set in 35 ℃, obviously can prepare the Al-Ti composite oxides suitable with the Comparative Examples homogeneity if firing temperature is up to 800 ℃ and heating-up temperature.
That is, if will make carrier, and if should carrier loadedly go up precious metal element or NO by the Al-Ti composite oxides that preparation method of the present invention makes
xStore element with the preparation composite metal catalyst, so this composite metal catalyst has high activity owing to its specific area is high, and it has good anti-sulfur poisoning.Even stand the high temperature durability test, the specific area that also can suppress this carrier descends.Therefore, can suppress because of specific area the descend germination or the NO of the noble metal cause
xStore the crystallization of element.Therefore, this composite metal catalyst can keep the high activity that purifies.
Embodiment 11
At first, (wherein, will be with 572.76 gram solution as Al
2O
3The ethyl acetoacetate aluminum-diisopropoxide (Al-EAA) in source (a kind of replacement aluminum alcoholate) is dissolved in the 2-propyl alcohol with the amount of 75% weight) and 26.7 gram diisopropanol barium (Ba (O-i-C
3H
7)
2) sneak in the 877.8 gram 2-propyl alcohol, stir 2 hours to dissolve down at 82 ℃ then.
Then, gained solution is kept down refluxing at 82 ℃.In agitating solution, 268.5 gram-ion exchanged waters are added drop-wise in the solution with the hydrolysis alcoholates.In addition this solution was refluxed 5 hours down at 82 ℃, carry out slaking thus.
Then, the solution for vacuum drying is to remove solvent, following dry 12 hours in addition at 120 ℃ with the gained sediment then.Then, sediment was calcined 4 hours down at 480 ℃, in 1100 ℃ of air, fired 5 hours then, obtain a kind of composite metal oxide.The specific area of gained composite metal oxide is measured by 1 BET method, and the result provides in table 2.
The dinitro two ammino platinum aqueous solution of predetermined concentration are infiltrated up in the gained composite metal oxide with scheduled volume.Under 120 ℃,, then composite metal oxide is fired 1 hour with supporting Pt under 250 ℃ with dry 1 hour of composite metal oxide.In addition, this composite metal oxide is molded into the bead shape, so just prepares the composite metal catalyst of this embodiment by commonsense method.This composite metal catalyst comprises a kind of carrier and the Pt that loads on this carrier, and described carrier comprises the composite metal oxide of being made up of aluminium oxide and barium monoxide.
The spherical catalyst of gained is placed on comprises 600ppmSO
2The air-flow of poor combustion simulation gas in.Then, carry out durability and handle, wherein should heat 5 hours down at 700 ℃ by spherical catalyst.After durability is handled, measure this spherical catalyst and become in the process of poor combustion NO in atmosphere by the richness combustion
xMaximum conversion rate.The result provides in table 2.
Embodiment 12
Prepare the composite metal oxide of embodiment 12 according to the same way as of embodiment 11, just dissolve 477.2 grams, the 75% ethyl acetoacetate diisopropanol aluminum solutions identical with embodiment 11,44.5 gram diisopropanol barium and 796.8 restrain the 2-propyl alcohol, in hydrolysing step, drip 235.4 gram-ion exchanged waters, and firing temperature is set in 900 ℃.
Then, come measurement the specific area according to the same way as of embodiment 11.In addition, Pt in the same load prepares the spherical catalyst that comprises embodiment 12 composite metal catalysts.The maximum NO of this spherical catalyst of similar measurement after durability is handled
xConversion ratio.The result provides in table 2.
Embodiment 13
Prepare the composite metal oxide of embodiment 13 according to the same way as of embodiment 11, different is dissolving 620.7 grams and embodiment 11 identical 75% ethyl acetoacetate diisopropanol aluminum solutions, 27.8 restrain potassium acetate (CH
3COOK) (alternative diisopropanol barium) and 1036.4 gram 2-propyl alcohol drip 306.3 gram-ion exchanged waters, and firing temperature are set in 1000 ℃ in hydrolysing step.
Then, come measurement the specific area according to the same way as of embodiment 11.In addition, Pt in the same load prepares the spherical catalyst of the composite metal catalyst that comprises embodiment 13.The maximum NO of this spherical catalyst of similar measurement after durability is handled
xConversion ratio.The result provides in table 2.
Embodiment 14
Prepare the composite metal oxide of embodiment 14 according to the same way as of embodiment 11, different is dissolving 557.6 grams and embodiment 11 identical 75% ethyl acetoacetate diisopropanol aluminum solutions, 25.0 gram potassium acetates (substituting diisopropanol barium), 36.2 restrain titanium tetraisopropylate (Ti (O-i-C
3H
7) 4) and 1007.5 gram 2-propyl alcohol, in hydrolysing step, drip 302.6 gram-ion exchanged waters, and firing temperature is set in 900 ℃.
Then, come measurement the specific area according to the same way as of embodiment 11.In addition, Pt in the same load prepares the spherical catalyst of the composite metal catalyst that comprises embodiment 14.The maximum NO of this spherical catalyst of similar measurement after durability is handled
xConversion ratio.The result provides in table 2.
Embodiment 15
Prepare the composite metal oxide of embodiment 15 according to the same way as of embodiment 11, different is dissolving 528.5 grams and embodiment 11 identical 75% ethyl acetoacetate diisopropanol aluminum solutions, 23.7 gram potassium acetates (substituting diisopropanol barium), 54.4 restrain four zirconium iso-propoxides (Zr (O-i-C
3H
7)
4) and 954.9 gram 2-propyl alcohol, in hydrolysing step, drip 286.8 gram-ion exchanged waters, and firing temperature is set in 900 ℃.
Then, come measurement the specific area according to the same way as of embodiment 11.In addition, Pt in the same load prepares the spherical catalyst of the composite metal catalyst that comprises embodiment 15.The maximum NO of this spherical catalyst of similar measurement after durability is handled
xConversion ratio.The result provides in table 2.
Prepare the composite metal oxide of embodiment 16 according to the same way as of embodiment 11, different is dissolving 467.4 grams and embodiment 11 identical 75% ethyl acetoacetate diisopropanol aluminum solutions, 73.2 restrain lanthanum acetate ((CH
3COO)
3La) (alternative diisopropanol barium) and 467.4 gram 2-propyl alcohol drip 230.6 gram-ion exchanged waters, and firing temperature are set in 900 ℃ in hydrolysing step.
Then, come measurement the specific area according to the same way as of embodiment 11.In addition, Pt in the same load prepares the spherical catalyst of the composite metal catalyst that comprises embodiment 16.The maximum NO of this spherical catalyst of similar measurement after durability is handled
xConversion ratio.The result provides in table 2.
Embodiment 17
Prepare the composite metal oxide of embodiment 17 according to the same way as of embodiment 11, different is dissolving 612.5 grams and embodiment 11 identical 75% ethyl acetoacetate diisopropanol aluminum solutions, 28.8 restrain diisopropanol strontium (Sr (O-i-C
3H
7)
2) (substituting diisopropanol barium) and 938.9 gram 2-propyl alcohol, in hydrolysing step, drip 287.1 gram-ion exchanged waters, and firing temperature is set in 1000 ℃.
Then, come measurement the specific area according to the same way as of embodiment 11.In addition, Pt in the same load prepares the spherical catalyst of the composite metal catalyst that comprises embodiment 17.The maximum NO of this spherical catalyst of similar measurement after durability is handled
xConversion ratio.The result provides in table 2.
Embodiment 18
Prepare the composite metal oxide of embodiment 18 according to the same way as of embodiment 11, different is dissolving 490.4 grams and embodiment 11 identical 75% ethyl acetoacetate diisopropanol aluminum solutions, 43.0 restrain cesium acetate (CH
3COOCs) (alternative diisopropanol barium) and 818.9 gram 2-propyl alcohol drip 242.0 gram-ion exchanged waters, and firing temperature are set in 1000 ℃ in hydrolysing step.
Then, come measurement the specific area according to the same way as of embodiment 11.In addition, Pt in the same load prepares the spherical catalyst of the composite metal catalyst that comprises embodiment 18.The maximum NO of this spherical catalyst of similar measurement after durability is handled
xConversion ratio.The result provides in table 2.
Embodiment 19
75% ethyl acetoacetate, the two aluminium propoxide solution and 41.1 that 633.5 grams are identical with embodiment 11 restrain titanium tetraisopropylate (Ti (O-i-C
3H
7)
4) sneak in the 971.0 gram 2-propyl alcohol, stir 2 hours to dissolve down at 82 ℃ then.
Then, above-mentioned solution is kept down refluxing at 82 ℃.In agitating solution, 312.59 gram dinitros, the two ammino platinum aqueous solution that will comprise 1.1 gram Pt are added drop-wise in this solution with the hydrolysis alcoholates.This solution is descended other stirring and refluxing 5 hours at 82 ℃, carry out slaking thus.Then, prepare embodiment 19 composite metal oxides according to the same way as of embodiment 11, just firing temperature is set in 800 ℃.Wherein the content of contained Pt is 2% weight.
Then, come measurement the specific area according to the same way as of embodiment 11.In addition, this composite metal oxide is molded into the bead shape, so just prepares a kind of spherical catalyst, comprise the composite metal catalyst of embodiment 19 by commonsense method.The spherical catalyst of gained is placed in the poor combustion simulated atmosphere.Then, carry out durability and handle, wherein should heat 5 hours down at 800 ℃ by spherical catalyst.After durability is handled, measure this spherical catalyst respectively in being equivalent to the simulation air-flow of desirable air-fuel ratio, NO
x, HC and CO maximum conversion rate.The result provides in table 2.
Prepare the composite metal oxide of embodiment 20 according to the same way as of embodiment 19, different is dissolving 559.0 grams and embodiment 11 identical 75% ethyl acetoacetate diisopropanol aluminum solutions, 48.0 restrain four isopropyl alcohol cerium (Ce (O-i-C
3H
7)
4) (substituting titanium tetraisopropylate) and 856.8 gram 2-propyl alcohol, 275.8 gram dinitros, the two ammino platinum aqueous solution that will comprise 1.1 gram Pt are added drop-wise in this solution with the hydrolysis alcoholates.Wherein the content of contained Pt is 2% weight.
Then, come measurement the specific area according to the same way as of embodiment 11.In addition, by commonsense method,, prepare the spherical catalyst of the composite metal catalyst that comprises embodiment 20 by this composite metal oxide.According to the same way as of embodiment 19, measure after durability is handled NO respectively
x, HC and CO maximum conversion rate.The result provides in table 2.
Comparative Examples 5
With 320.3 gram aluminum isopropylate (Al (O-i-C
3H
7)
3) and 26.7 gram diisopropanol barium sneak in the 941.0 gram 2-propyl alcohol, stir 2 hours down to dissolve at 82 ℃ then.
Then, gained solution is kept down refluxing at 82 ℃.In agitating solution, drip 68.0 grams 2, the 4-pentanedione.This solution was stirred under 82 ℃ 2 hours again.Then, this solution is kept down refluxing at 82 ℃.In agitating solution, 268.5 gram-ion exchanged waters are added drop-wise in the solution with the hydrolysis alcoholates.This solution is descended other stirring and refluxing 5 hours at 82 ℃, carry out slaking thus.
Then, this solution of vacuum drying to be removing solvent, and with the gained sediment 120 ℃ in addition dry 12 hours down.Subsequently, sediment was calcined 4 hours down at 480 ℃, and in 1100 ℃ air, fired 5 hours, obtain the composite metal oxide of this Comparative Examples.
Then, come measurement the specific area according to the same way as of embodiment 11.In addition, Pt in the same load prepares spherical catalyst.The maximum NO of this spherical catalyst of similar measurement after durability is handled
xConversion ratio.The result provides in table 2.
Comparative Examples 6
Prepare the composite metal oxide of Comparative Examples 6 according to the same way as of Comparative Examples 5, different is that 266.8 gram aluminum isopropylates and 44.5 gram diisopropanol barium are dissolved in the 849.3 gram 2-propyl alcohol, drip 61.0 grams 2, in hydrolysing step, drip 235.4 gram-ion exchanged waters after the 4-pentanedione, and firing temperature is set in 900 ℃.
Then, come measurement the specific area according to the same way as of embodiment 11.In addition, Pt in the same load prepares spherical catalyst.The maximum NO of this spherical catalyst of similar measurement after durability is handled
xConversion ratio.The result provides in table 2.
Comparative Examples 7
Prepare the composite metal oxide of Comparative Examples 7 according to the same way as of Comparative Examples 5, different is dissolving 311.8 gram aluminum isopropylates, 25.0 gram potassium acetates (substituting diisopropanol barium), 36.2 gram titanium tetraisopropylates and 1069.0 gram 2-propyl alcohol, drip 76.4 grams 2, after the 4-pentanedione in hydrolysing step in dripping 302.6 gram-ion exchanged waters, and firing temperature is set in 900 ℃.
Then, come measurement the specific area according to the same way as of embodiment 11.In addition, Pt in the same load prepares spherical catalyst.The maximum NO of this spherical catalyst of similar measurement after durability is handled
xConversion ratio.The result provides in table 2.
Comparative Examples 8
Prepare the composite metal oxide of Comparative Examples 8 according to the same way as of Comparative Examples 5, different is dissolving 274.3 gram aluminum isopropylates, 43.0 gram cesium acetates (substituting diisopropanol barium) and 872.9 gram 2-propyl alcohol, dripping 62.7 grams 2, in hydrolysing step, drip 242.0 gram-ion exchanged waters after the 4-pentanedione, and firing temperature is set in 1000 ℃.
Then, come measurement the specific area according to the same way as of embodiment 11.In addition, Pt in the same load prepares spherical catalyst.The maximum NO of this spherical catalyst of similar measurement after durability is handled
xConversion ratio.The result provides in table 2.
Comparative Examples 9
354.3 gram aluminum isopropylates, 41.1 gram titanium tetraisopropylates and 1040.8 gram 2-propyl alcohol are mixed, stir 2 hours to dissolve down at 82 ℃ then.
Then, gained solution is kept down refluxing at 82 ℃.In agitating solution, drip 75.3 grams 2, the 4-pentanedione.This solution was stirred under 82 ℃ 2 hours again.Then, this solution is kept down refluxing at 82 ℃.In agitating solution, 312.6 gram dinitros, the two ammino platinum aqueous solution that will comprise 1.1 gram Pt are added drop-wise in the described solution with the hydrolysis alcoholates.This solution is descended other stirring and refluxing 4 hours at 82 ℃, carry out slaking thus.Then, according to the same way as of embodiment 11, prepare the composite metal oxide of Comparative Examples 9, just firing temperature is set in 800 ℃.Wherein the content of contained Pt is 2% weight.
Then, come measurement the specific area according to the same way as of embodiment 11.In addition, by commonsense method,, prepare spherical catalyst by this composite metal oxide.The spherical catalyst of gained is placed in the poor combustion simulation air-flow.Then, carry out durability and handle, wherein spherical catalyst was heated 5 hours down at 800 ℃.After durability is handled, measure this spherical catalyst respectively in the simulation air-flow that is equivalent to desirable air-fuel ratio (stoichiometric point), NO
x, HC and CO maximum conversion rate.The result provides in table 2.
Comparative Examples 10
Prepare the composite metal oxide of Comparative Examples 10 according to the same way as of embodiment 11, different is dissolving 312.6 gram aluminum isopropylates, 48.0 grams, four isopropyl alcohol ceriums (substituting titanium tetraisopropylate) and 918.4 gram 2-propyl alcohol, the 262.0 gram dinitros two ammino platinum aqueous solution that will comprise 1.1 gram Pt are added drop-wise in the solution with the hydrolysis alcoholates, and firing temperature is set in 800 ℃.Wherein the content of contained Pt is 2% weight.
Then, come measurement the specific area according to the same way as of embodiment 11.In addition, by commonsense method,, prepare spherical catalyst by this composite metal oxide.According to the same way as of Comparative Examples 9, measure the spherical catalyst of gained respectively after durability is handled, NO
x, HC and CO maximum conversion rate.The result provides in table 2.
Table 2
| Catalyst is formed | ?M.C. *7(％) | ||||||||
| ????C.M.O. *1 | ??L.E. *2 | ????B.T. *3(℃) | ????S.S.A. *4(m 2/g) | ?D.T.C. *5 | ??E.G. *6 | ??NO x | ??HC | ??CO | |
| Embodiment #11 | ????Al-Ba | ????Pt | ????1100 | ????135 | ?SO 2700 ℃ of poor combustions | Fu Ran-poor combustion | ??57 | ??- | ??- |
| Embodiment #12 | ????Al-Ba | ????Pt | ????900 | ????144 | ?SO 2700 ℃ of poor combustions | Fu Ran-poor combustion | ??51 | ??- | ??- |
| Embodiment #13 | ????Al-K | ????Pt | ????1000 | ????62 | ?SO 2700 ℃ of poor combustions | Fu Ran-poor combustion | ??61 | ??- | ??- |
| Embodiment #14 | ????Al-K-Ti | ????Pt | ????900 | ????136 | ?SO 2700 ℃ of poor combustions | Fu Ran-poor combustion | ??64 | ??- | ??- |
| Embodiment #15 | ????Al-K-Zr | ????Pt | ????900 | ????127 | ?SO 2700 ℃ of poor combustions | Fu Ran-poor combustion | ??60 | ??- | ??- |
| Embodiment #16 | ????Al-La | ????Pt | ????900 | ????76 | ?SO 2700 ℃ of poor combustions | Fu Ran-poor combustion | ??53 | ??- | ??- |
| Embodiment #17 | ????Al-Sr | ????Pt | ????1000 | ????138 | ?SO 2700 ℃ of poor combustions | Fu Ran-poor combustion | ??58 | ??- | ??- |
| Embodiment #18 | ????Al-Cs | ????Pt | ????1000 | ????68 | ?SO 2700 ℃ of poor combustions | Fu Ran-poor combustion | ??60 | ??- | ??- |
| Embodiment #19 | ????Al-Ti-Pt | ????- | ????800 | ????265 | 800 ℃ of poor combustions | ??S.P. *8 | ??59 | ??56 | ??61 |
| Embodiment #20 | ????Al-Ce-Pt | ????- | ????800 | ????198 | 800 ℃ of poor combustions | ??S.P. *8 | ??55 | ??57 | ??60 |
| Comparative Examples #5 | ????Al-Ba | ????Pt | ????1100 | ????108 | ?SO 2700 ℃ of poor combustions | Fu Ran-poor combustion | ??26 | ??- | ??- |
| Comparative Examples #6 | ????Al-Ba | ????Pt | ????900 | ????125 | ?SO 2700 ℃ of poor combustions | Fu Ran-poor combustion | ??24 | ??- | ??- |
| Comparative Examples #7 | ????Al-K-Ti | ????Pt | ????900 | ????110 | ?SO 2700 ℃ of poor combustions | Fu Ran-poor combustion | ??43 | ??- | ??- |
| Comparative Examples #8 | ????Al-Cs | ????Pt | ????1000 | ????48 | ?SO 2700 ℃ of poor combustions | Fu Ran-poor combustion | ??42 | ??- | ??- |
| Comparative Examples #9 | ????Al-Ti-Pt | ????- | ????800 | ????223 | 800 ℃ of poor combustions | ??S.P. *8 | ??46 | ??44 | ??48 |
| Comparative Examples #10 | ????Al-Ce-Pt | ????- | ????800 | ????167 | 800 ℃ of poor combustions | ??S.P. *8 | ??47 | ??42 | ??46 |
Assessment
By with embodiment 11 and 12 and Comparative Examples 5 and 6 compare, embodiment 14 is compared with Comparative Examples 7, and embodiment 18 is compared with Comparative Examples 8, obviously draw following content.That is, the specific area of gained composite metal oxide increases as a kind of raw material by adopting the replacement aluminum alcoholate, even and also have high NO after durability is handled
xThe catalyst of conversion ratio can obtain by Pt is loaded on this composite metal oxide.
With embodiment 19 and 20 and Comparative Examples 9 and 10 compare, obviously draw following content.That is, though Pt is compound, even the catalyst that also has high ternary catalytic activity after durability is handled can obtain as a kind of raw material by adopting the replacement aluminum alcoholate.
Described the present invention now in detail, those of ordinary skills obviously can carry out many changes and improvements, and do not deviate from the subject or scope of the present invention that comprise claims.
Claims (12)
1. method for preparing composite metal oxide, it may further comprise the steps:
Prepare a kind of solution, wherein will replace aluminum alcoholate and titanium salt and at least a the sneak into organic solvent of alcoholization in the titanium, wherein said replacement aluminum alcoholate is for its at least one or a plurality of alkoxyl aluminum alcoholate that agent replaced that is chelated; Then
Each component of solution is carried out drying and fired after hydrolysis.
2. method for preparing composite metal oxide, it may further comprise the steps:
Prepare a kind of solution, wherein substituted propanol aluminium and titanium tetraisopropylate sneaked into organic solvent, wherein said substituted propanol aluminium for its at least one or a plurality of isopropoxy by aluminum isopropylate that ethyl acetoacetate replaced; Then
These alcoholates are carried out drying and fire after hydrolysis.
3. method for preparing composite metal catalyst, it may further comprise the steps:
Prepare a kind of solution, wherein will replace aluminum alcoholate and titanium salt and at least a the sneak into organic solvent of alcoholization in the titanium, wherein said replacement aluminum alcoholate is for its at least one or a plurality of alkoxyl aluminum alcoholate that agent replaced that is chelated;
Each component of solution is carried out drying and fired after hydrolysis, can form carrier like this; Then
Load on this carrier to major general's noble metal.
4. method for preparing composite metal catalyst, it may further comprise the steps:
Prepare a kind of solution, wherein substituted propanol aluminium and titanium tetraisopropylate sneaked into organic solvent, wherein said substituted propanol aluminium for its at least one or a plurality of isopropoxy by aluminum isopropylate that ethyl acetoacetate replaced;
These alcoholates are carried out drying and fire after hydrolysis, can form carrier like this; Then
Load on this carrier to major general's noble metal.
5. method for preparing composite metal catalyst, it may further comprise the steps:
To replace aluminum alcoholate and a kind of soluble compound is sneaked into organic solvent, wherein said replacement aluminum alcoholate is for its at least one or a plurality of alkoxyl aluminum alcoholate that agent replaced that is chelated, and described soluble compound dissolves in this organic solvent, and comprises by NO
xStore the catalyst metals element of at least a composition in element and the noble metal, described NO
xStore element and be and be selected from least a in alkali metal, alkaline-earth metal and the rare earth element; Then
After described replacement aluminum alcoholate hydrolysis to the major general, drying and each component of firing this mixture.
6. according to the preparation method of the composite metal catalyst of claim 5, wherein said chelating agent is an ethyl acetoacetate.
7. according to the preparation method of the composite metal oxide of claim 1, wherein said hydrolysis is to carry out under 35-150 ℃ temperature.
8. according to the preparation method of the composite metal oxide of claim 1, wherein said hydrolysis is to carry out under 40-100 ℃ temperature.
9. according to the preparation method of the composite metal oxide of claim 2, wherein said hydrolysis is to carry out under 50-82 ℃ temperature.
10. according to the preparation method of the composite metal catalyst of claim 3 and claim 5, wherein said hydrolysis is to carry out under 35-150 ℃ temperature.
11. according to the preparation method of the composite metal catalyst of claim 3 and claim 5, wherein said hydrolysis is to carry out under 40-100 ℃ temperature.
12. according to the preparation method of the composite metal catalyst of claim 4 and claim 6, wherein said hydrolysis is to carry out under 50-82 ℃ temperature.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003037787A1 (en) * | 2001-11-01 | 2003-05-08 | Beijing University Of Chemical Technology | NON-EQUILIBRIUM PROCESS FOR PREPARING A Mg-Al TYPE BISHYDROXY COMPOSITE METAL OXIDE |
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2000
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Cited By (1)
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|---|---|---|---|---|
| WO2003037787A1 (en) * | 2001-11-01 | 2003-05-08 | Beijing University Of Chemical Technology | NON-EQUILIBRIUM PROCESS FOR PREPARING A Mg-Al TYPE BISHYDROXY COMPOSITE METAL OXIDE |
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