CN106925265A - A kind of transition metal composite oxide catalytic agent - Google Patents
A kind of transition metal composite oxide catalytic agent Download PDFInfo
- Publication number
- CN106925265A CN106925265A CN201511018830.8A CN201511018830A CN106925265A CN 106925265 A CN106925265 A CN 106925265A CN 201511018830 A CN201511018830 A CN 201511018830A CN 106925265 A CN106925265 A CN 106925265A
- Authority
- CN
- China
- Prior art keywords
- transition metal
- oxide
- chloride
- ruthenium
- copper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 39
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 37
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 37
- 239000002905 metal composite material Substances 0.000 title claims abstract description 32
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 65
- 239000003054 catalyst Substances 0.000 claims abstract description 46
- 239000002131 composite material Substances 0.000 claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 26
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 22
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 21
- 238000010276 construction Methods 0.000 claims abstract description 19
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims abstract description 18
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 15
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 14
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 53
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 47
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- 229910052684 Cerium Inorganic materials 0.000 claims description 27
- 238000010992 reflux Methods 0.000 claims description 24
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 10
- 238000010521 absorption reaction Methods 0.000 claims description 10
- 238000005119 centrifugation Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 230000004044 response Effects 0.000 claims description 9
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 8
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 8
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000011565 manganese chloride Substances 0.000 claims description 8
- 235000002867 manganese chloride Nutrition 0.000 claims description 8
- 229940099607 manganese chloride Drugs 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 8
- 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 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- -1 Acyl acetone copper Chemical compound 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- 229940011182 cobalt acetate Drugs 0.000 claims description 5
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 5
- 239000003546 flue gas Substances 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- GYUPBLLGIHQRGT-UHFFFAOYSA-N pentane-2,4-dione;titanium Chemical compound [Ti].CC(=O)CC(C)=O GYUPBLLGIHQRGT-UHFFFAOYSA-N 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 230000002079 cooperative effect Effects 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- 238000005660 chlorination reaction Methods 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- YLPJWCDYYXQCIP-UHFFFAOYSA-N nitroso nitrate;ruthenium Chemical compound [Ru].[O-][N+](=O)ON=O YLPJWCDYYXQCIP-UHFFFAOYSA-N 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- HYZQBNDRDQEWAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese(3+) Chemical compound [Mn+3].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O HYZQBNDRDQEWAN-LNTINUHCSA-N 0.000 claims description 2
- DGOFDXKSKYTBGX-UHFFFAOYSA-L 2-carboxyphenolate;nickel(2+) Chemical class [Ni+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O DGOFDXKSKYTBGX-UHFFFAOYSA-L 0.000 claims description 2
- VAIVGJYVKZVQAA-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;nickel Chemical compound [Ni].OC(=O)CC(O)(C(O)=O)CC(O)=O VAIVGJYVKZVQAA-UHFFFAOYSA-N 0.000 claims description 2
- JXSRRBVHLUJJFC-UHFFFAOYSA-N 7-amino-2-methylsulfanyl-[1,2,4]triazolo[1,5-a]pyrimidine-6-carbonitrile Chemical compound N1=CC(C#N)=C(N)N2N=C(SC)N=C21 JXSRRBVHLUJJFC-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims description 2
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 claims description 2
- SZKXDURZBIICCF-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O SZKXDURZBIICCF-UHFFFAOYSA-N 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- YRNNKGFMTBWUGL-UHFFFAOYSA-L copper(ii) perchlorate Chemical compound [Cu+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O YRNNKGFMTBWUGL-UHFFFAOYSA-L 0.000 claims description 2
- SVOAENZIOKPANY-CVBJKYQLSA-L copper;(z)-octadec-9-enoate Chemical compound [Cu+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O SVOAENZIOKPANY-CVBJKYQLSA-L 0.000 claims description 2
- CMRVDFLZXRTMTH-UHFFFAOYSA-L copper;2-carboxyphenolate Chemical compound [Cu+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O CMRVDFLZXRTMTH-UHFFFAOYSA-L 0.000 claims description 2
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 claims description 2
- 150000004816 dichlorobenzenes Chemical class 0.000 claims description 2
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 239000012229 microporous material Substances 0.000 claims description 2
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 239000002070 nanowire Substances 0.000 claims description 2
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 claims description 2
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical compound [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 claims description 2
- ZLQBNKOPBDZKDP-UHFFFAOYSA-L nickel(2+);diperchlorate Chemical compound [Ni+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O ZLQBNKOPBDZKDP-UHFFFAOYSA-L 0.000 claims description 2
- JMWUYEFBFUCSAK-UHFFFAOYSA-L nickel(2+);octadecanoate Chemical compound [Ni+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O JMWUYEFBFUCSAK-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- PXFAWKNRNHXITF-KVVVOXFISA-N nickel;(z)-octadec-9-enoic acid Chemical compound [Ni].CCCCCCCC\C=C/CCCCCCCC(O)=O PXFAWKNRNHXITF-KVVVOXFISA-N 0.000 claims description 2
- MCCIMQKMMBVWHO-UHFFFAOYSA-N octadecanoic acid;titanium Chemical compound [Ti].CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O MCCIMQKMMBVWHO-UHFFFAOYSA-N 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 claims description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 230000009466 transformation Effects 0.000 claims description 2
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 229940102001 zinc bromide Drugs 0.000 claims description 2
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 claims 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 claims 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- XMOKRCSXICGIDD-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O XMOKRCSXICGIDD-UHFFFAOYSA-N 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
- 229910052794 bromium Inorganic materials 0.000 claims 1
- BJYLNGGDLHKELP-UHFFFAOYSA-N copper;formic acid Chemical compound [Cu].OC=O BJYLNGGDLHKELP-UHFFFAOYSA-N 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000000956 alloy Substances 0.000 abstract 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 17
- 230000004048 modification Effects 0.000 description 17
- 238000012986 modification Methods 0.000 description 17
- 239000000243 solution Substances 0.000 description 12
- 239000002585 base Substances 0.000 description 11
- 239000002114 nanocomposite Substances 0.000 description 11
- DEPMYWCZAIMWCR-UHFFFAOYSA-N nickel ruthenium Chemical compound [Ni].[Ru] DEPMYWCZAIMWCR-UHFFFAOYSA-N 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 6
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 5
- 229910052720 vanadium Inorganic materials 0.000 description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 5
- QDNPJNIUNGYXPA-UHFFFAOYSA-N [Co].[Cu].[Ru] Chemical compound [Co].[Cu].[Ru] QDNPJNIUNGYXPA-UHFFFAOYSA-N 0.000 description 4
- OUFLLVQXSGGKOV-UHFFFAOYSA-N copper ruthenium Chemical compound [Cu].[Ru].[Ru].[Ru] OUFLLVQXSGGKOV-UHFFFAOYSA-N 0.000 description 4
- QNZRVYCYEMYQMD-UHFFFAOYSA-N copper;pentane-2,4-dione Chemical compound [Cu].CC(=O)CC(C)=O QNZRVYCYEMYQMD-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- DPGAAOUOSQHIJH-UHFFFAOYSA-N ruthenium titanium Chemical compound [Ti].[Ru] DPGAAOUOSQHIJH-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 229910015189 FeOx Inorganic materials 0.000 description 3
- KRSZDIGCQWBYNU-UHFFFAOYSA-N [Mn].[Ru] Chemical compound [Mn].[Ru] KRSZDIGCQWBYNU-UHFFFAOYSA-N 0.000 description 3
- AVAYXTKDRHARSR-UHFFFAOYSA-N [Zn].[Ru] Chemical compound [Zn].[Ru] AVAYXTKDRHARSR-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- ITXSHZFXAHDNMK-UHFFFAOYSA-N iron ruthenium Chemical compound [Fe].[Ru] ITXSHZFXAHDNMK-UHFFFAOYSA-N 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012458 free base Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 150000003658 tungsten compounds Chemical class 0.000 description 1
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- 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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
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- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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Abstract
The invention discloses a kind of transition metal composite catalyst, Preparation Method And The Use, the catalyst is made up of main active component A and auxiliary agent B two parts, wherein, component A refers to cerium oxide, or the composite oxides at least one of both cerium oxide and tungsten oxide and molybdenum oxide, auxiliary agent B is the composite oxides of a kind of hollow-core construction transition metal M and ruthenium；The preparation method is comprised the following steps：The hollow alloy material that transition metal M and ruthenium are constituted first is prepared with oleyl amine reducing process, main active component A is then carried on, washed, dried, calcining is obtained transition metal composite oxide catalytic agent；The above-mentioned catalyst that the present invention is provided, preparation method is simple, and yield is high, low cost, with outstanding advantages such as catalysis activity higher, excellent nitrogen generation selectivity and operating temperature ranges wider, is had broad application prospects in catalytic field.
Description
Technical field
The present invention relates to the transition metal composite oxide catalytic agent and its preparation of a kind of catalyzing and reducing nitrogen oxides
Method, be specifically related to one kind such as, should apply in diesel oil in nitrous oxides selectivity catalysis reduction field
The transition in the fields such as the catalytic purifications of nitrogen oxides such as tail gas, coal-burning power plant, oil plant and smeltery's flue gas
Metal composite oxide catalyst and preparation method thereof, belongs to environmentally conscious materialses, environmental catalysis and environmental protection skill
Art field.
Background technology
In recent years, with the fast development of science and technology and greatly improving for people's living standard, thing followed ring
Border pollution problem is increasingly serious, wherein, as the nitrogen oxides (NO of Air Pollutant Dischargex), such as N2O,
NO, N2O3, N2O4, NO2Etc. be to be formed acid rain, damage the ozone layer, produce photochemical pollution it is main into
Cause, the ecology that the above-mentioned problem of environmental pollution triggered by nitrogen oxides is depended on for existence to the health of people and people
The huge threat of environment structure, countries in the world are to NOxDischarge formulated very strict standard.
China is the developing country with fire coal as main energy sources, wherein, the NO for only being discharged by coal-burning power plantx
Account for national NOxThe 67% of total emission volumn.Therefore, in the flue gases such as coal-burning power plant, smeltery, oil plant
Nitrogen oxides carries out catalytic purification treatment, to China NOxIt is very that total emission volumn carries out strict effective control
It is necessary and important.In addition, China moves the NO of source emissionxAbout 65% comes from diesel vehicle, with China's machine
Motor-car recoverable amount increases sharply, and carrying out effective purified treatment to the nitrogen oxides of exhaust gas from diesel vehicle is even more control
China NO processedxThe key link of total emission volumn.
In purification of nitrogen oxides removing sulfuldioxide, ammonia SCR technology (NH3- SCR) it is fixed
Removal of nitrogen oxide in source coal-burning power plant, oil plant and smeltery's flue gas and moving source diesel vehicle vehicle exhaust
Major technique, wherein, catalyst is the core of the technique.At present, wide variety of catalyst is to use
WO3Or MoO3Modified V2O5/TiO2Catalyst.On the one hand, the catalyst is between 300~400 DEG C
Middle-temperature section has excellent removal of nitrogen oxide rate and anti-SO2Performance, but in high temperature, easily generation is a large amount of
N2O, so as to cause nitrogen selective to reduce；On the other hand, due to V2O5Oxidisability it is stronger, very
Easily cause the SO in reacting gas2To SO3Conversion, these SO in lower temperature3Meeting and NH3Reaction
Generation (NH4)2SO4Or NH4HSO4, so that the duct of catalyst blocks, and then cause to urge
Agent loses activity.In addition, such catalyst is relatively costly, and the selectivity under high temperature to nitrogen is poor,
And active component V2O5Presoma toxicity it is very big, in the tail gas nitrogen oxide of the moving sources such as diesel vehicle
It is susceptible to distil or come off in subtractive process, is easily detrimental to health and surrounding environment can be produced dirty
Dye, many developed countries have forbidden catalytic component based on vanadium for the catalytic purification of exhaust gas from diesel vehicle nitrogen oxides.
In the last few years, many researchers started to be devoted to NH3The research and development of the non-catalytic component based on vanadium of-SCR, non-vanadium base
Removal of nitrogen oxide catalyst including noble metal (Pt, Pd and Ag etc.) catalyst and metal oxide (Mn,
Fe, Cu and Co etc.) catalyst.Noble metal catalyst has a good catalysis activity, but high cost,
Reaction temperature window narrows, to SO2Sensitivity, is restricted its scale application in the industry.Therefore,
Metal oxide NH3- SCR catalyst is an important developing direction, although such catalyst does not put into also
Commercial applications, but because it has, preparation method is simple, performance controllability is strong and is easy to large-scale promotion
Using many advantages, such as, have become at present people research and development emphasis.
Research shows that rare-earth oxide shows uniqueness due to the 4f tracks with underfill electronics
Performance, the presence of rare earth component can effectively adjust the acid-base property of catalyst surface, modification catalytic active center
Structure, improve catalyst storage/oxygen release ability.Wherein, ceria (CeO2) as rare earth catalyst material
Most important composition in material, for CeO2It is the Engineering of Supported Metal Oxide Catalysts of pure carrier, on the one hand,
Active component can disperse in apparent height；On the other hand, due to excellent redox property, appropriate
Surface acidity and storage higher/oxygen release capacity and good Ce3+/Ce4+Switching capability, can be with area load
Component produces stronger interaction, so as to promote its catalytic performance to be obviously improved.But, CeO2Pure carrier
Can there is the deficiencies such as specific surface area is small, heat endurance is poor, high temperature is easily sintered, this is limited to a certain extent
It is widely applied.People have found under study for action, by CeO2Lattice in mix exogenous metal ions
Forming cerium-based composite oxides can effectively overcome disadvantages mentioned above.For example, (Shu, the Y. such as Quan；Sun,H.；
Quan,X.；Chen,S.J.Phys.Chem.C 2012,
116,25319.) it is prepared for using infusion process a series of through FeOxModified CeO2/TiO2Catalyst is used for
NH3- SCR reacts, and research finds, FeOxModified cause catalyst surface Ce3+Increase with absorption oxygen content,
Advantageously form more NH4 +And NO2And promote CeO2In the dispersion of carrier surface, therefore FeOx's
The CeO that addition has been obviously improved2/TiO2The nitrogen oxides abjection ability of catalyst.There are research (Liu, Z.M.；
Zhu,J.Z.；Zhang,S.X.；Ma,L.L.；Woo, S.I.Catal.Commun.2014,46,90.) show,
MoO3Be added with beneficial to NH3Absorption, can effectively suppress H2O and SO2Absorption and sulfate
Formed, and then the water resistant sulfur resistance of catalyst can be obviously improved, show excellent catalytic performance.
In summary, cerium oxide base composite oxides can effectively overcome the pure carrier specific surface area of cerium oxide it is small,
The shortcomings of heat endurance is poor, high temperature is easily sintered, and then in NH3- SCR reaction in have widely should
With.Therefore, process is simple how is prepared, it is with low cost, to the non-vanadium of high activity of environment nontoxic pollution-free
Base catalyst is the key link for reducing nitrogen oxides total amount.
The content of the invention
The purpose of the present invention and effective effect are on the one hand to overcome commercialization catalytic component based on vanadium low temperature NO at presentx
Elimination factor is poor, relatively low N under high temperature2Selectivity and V2O5Virose deficiency of tool itself；On the other hand,
The shortcomings of pure carrier specific surface area of cerium oxide is small, heat endurance is poor, high temperature is easily sintered can be overcome.
Above-mentioned technical purpose of the invention is achieved through the following technical solutions：
A kind of transition metal composite oxide catalytic agent provided by the present invention, by main active component A and has
Auxiliary agent B two parts composition of cooperative effect, wherein, main active component A refers to cerium oxide, or cerium oxide
With the composite oxides of at least one of both tungsten oxide and molybdenum oxide, the auxiliary agent B with cooperative effect
It is the composite oxides of a kind of hollow-core construction transition metal M and ruthenium, and, the auxiliary agent B with hollow-core construction
It is evenly coated at main active components A surface.
M element and the mol ratio of cerium are 0.005~0.1, preferably 0.01~0.08 in the auxiliary agent B, enter one
Step is preferably 0.02~0.055.
In the main active component A, the total mole number of tungsten and molybdenum is 0~0.6 with the mol ratio of cerium, preferably
0.02~0.45, more preferably 0.05~0.35.
Cerium oxide, tungsten oxide and molybdenum oxide in described main active components A can be nano particle, nanometer
Any one in rod, nanometer sheet, nano wire, micropore, mesoporous or sub-micro Porous materials or two kinds and two
Plant the composition of the above.
Described main active component A refers to cerium oxide, or both cerium oxide and tungsten oxide and molybdenum oxide
At least one of composite oxides, wherein, in both described cerium oxide and tungsten oxide and molybdenum oxide
At least one composite oxides, refer to the composite oxides of simple physical mixing, or refer to synthesize
The cerium oxide and oxygen of fabricated in situ are carried out in journey using chemical synthesis such as co-precipitation, sol-gel, hydro-thermal methods
Change the composite oxides of at least one of both tungsten and molybdenum oxide.
Described auxiliary agent B is the composite oxides of a kind of hollow-core construction transition metal M and ruthenium, hollow-core construction
A diameter of 8nm~25nm, hollow structure material is uniformly scattered in the surface of main active component A.
Described transition metal M is one kind or two or more in copper, nickel, cobalt, iron, zinc, titanium, manganese
Combination.
A kind of transition metal composite oxide catalytic agent that the present invention is provided, its preparation method comprises the following steps：
A be added to M presomas in oleyl amine by (), stirring and dissolving；Then heating reflux reaction；
B () continues heating reflux reaction to ruthenium presoma is added in the reacted solution of step (a)；
C () separates step (b) gained product, washing is scattered in organic solvent again, and adds main active components A, is separated after absorption,
Washing, dries；
D () calcines step (c) products therefrom, you can obtain the mistake that the auxiliary agent B of hollow-core construction is evenly coated at main active components A surface and is formed
Cross metal composite oxide catalyst.
The M presomas be cupric perchlorate, copper formate, copper chloride, copper citrate, Cupric salicylate, copper nitrate, copper bromide, copper acetate, copper stearate,
Copper oleate, acetylacetone copper, nickelous perchlorate, nickel formate, nickel chloride, citric acid nickel, nickel salicylates, nickel nitrate, nickelous bromide, nickel acetate,
Nickel stearate, oleic acid nickel, nickel acetylacetonate, manganese chloride, manganese nitrate, manganous bromide, manganese acetate, manganese acetylacetonate, cobalt chloride, cobalt nitrate,
Cobaltous bromide, cobalt acetate, acetylacetone cobalt, iron chloride, ferric nitrate, ferric bromide, ferric acetyl acetonade, zinc chloride, zinc nitrate, zinc bromide,
Zinc acetate, zinc stearate, zinc acetylacetonate, titanium chloride, Titanium Nitrate, titanium bromide, titanium stearate, in titanium acetylacetone a kind or 2 kinds with
On combination；Preferably copper chloride, copper nitrate, nickel chloride, manganese chloride, cobalt chloride, cobalt nitrate, iron chloride, ferric nitrate, zinc chloride,
Zinc nitrate, titanium chloride, one kind or two or more combination in Titanium Nitrate；Particularly preferably copper chloride, manganese chloride, iron chloride, nickel chloride,
One kind or two or more combination in cobalt chloride；
Preferably, concentration of the M presomas in oleyl amine be 8mmol/L~110mmol/L, preferably 18mmol/L~55mmol/L, further preferably
It is 22~30mmol.
The temperature being heated to reflux in the step (a) is 85~250 DEG C, more preferably preferably 120~220 DEG C, 160~190 DEG C；It is described to be heated to reflux
The time of reaction is 0.5~30h, more preferably preferably 1.5~20h, 2.5~10h.
Further, step (b) the ruthenium presoma be ruthenium trichloride, (isopropyl toluene) [(S, S)-Ts-DPEN] ruthenic chloride, acetylacetone,2,4-pentanedione ruthenium,
The ammonium of tri-chlorination six closes the one kind or two or more combination in ruthenium, nitrosyl nitrate ruthenium；
Preferably, the M presomas and the mol ratio of ruthenium presoma are 1~5, preferably 4~2, more preferably 2.7~2.2.
Further, the temperature that the step (b) is heated at reflux reaction is 150~280 DEG C, preferably 175~265 DEG C；The heating reflux reaction when
Between be 0.8~30h, more preferably preferably 1.5~20h, 2.5~10h.
The time of the absorption is more than 0.5h, more preferably preferably 1~20h, 2h~8h.
Washing after step (b) gained product is separated in described step (c) uses a kind in methyl alcohol, ethanol, propyl alcohol, acetone, n-butanol
Or mixture of more than two kinds is carried out；Preferably methyl alcohol and/or ethanol；More preferably ethanol；
Preferably, the washing after adsorbing and separate is carried out using the one kind or two or more mixing in methyl alcohol, ethanol, water；
Preferably, the washing is more than 3 times, preferably 5 times；
Preferably, the organic solvent is toluene, dimethylbenzene, chlorobenzene, dichloro-benzenes, carbon tetrachloride, hexamethylene, hexane, chloropropane, hexane, heptane
In one kind or two or more mixing；
Preferably, it is described to be separated into centrifugation.
Further, step (d) calcining is carried out in air, oxygen or other oxidizing atmospheres；
Preferably, the temperature of the calcining is 200 DEG C~550 DEG C, more preferably preferably 250~450 DEG C, 300~400 DEG C；The calcining when
Between be 0.5~12h, more preferably preferably 1.5~8h, 2.5~6h.
A kind of transition metal composite oxide catalytic agent provided by the present invention, can select in nitrogen oxides
Property catalysis reduction field, such as, apply in exhaust gas from diesel vehicle, coal-burning power plant, oil plant and smeltery's flue gas
The fields such as the catalytic purification Deng nitrogen oxides.
Above-mentioned any one transition metal composite oxide catalytic agent provided by the present invention, at 160~430 DEG C
In the range of, transformation efficiency of the oxides of nitrogen is more than 92%, is 100% between 190~380 DEG C；At 160~430 DEG C
In the range of, the selectivity of nitrogen is more than 91%, and in the range of 145~430 DEG C, the selectivity of nitrogen is more than 96%,
In the range of 145~350 DEG C, the selectivity of nitrogen is 100%.
Specific embodiment
Embodiment 1
A certain amount of nickel chloride is accurately weighed, is added in appropriate oleyl amine so that nickel chloride is dense in oleyl amine
It is 25mmol/L to spend, heating stirring, nickel chloride is fully dissolved, and then under 180 DEG C of oil baths, is heated back
Stream 5h；To adding ruthenic chloride in above-mentioned reacted solution so that nickel is 2.5 with the mol ratio of ruthenium, at 180 DEG C
Under continue to be heated to reflux 4h；After question response terminates, centrifugation is washed 3 times with toluene and methyl alcohol mixed solution,
It is then dispersed in toluene, adds proper amount of nano cerium oxide so that nickel is 0.03 with the mol ratio of cerium, absorption
4h, is then centrifuged for, and is washed with ethanol 3 times, dries；Finally by dried product in atmosphere in 350 DEG C
Under the conditions of heat 4h, you can obtain being evenly coated at nano-cerium oxide table by Hollow Nickel ruthenium nano composite oxide
The transition metal composite oxide catalytic agent that face is formed.
Embodiment 2
A certain amount of titanium acetylacetone is accurately weighed, is added in appropriate oleyl amine so that titanium acetylacetone is in oil
Concentration in amine is 8mmol/L, and heating stirring makes titanium acetylacetone fully dissolve, then in 85 DEG C of oil baths
Under, it is heated to reflux 30h；To addition nitrosyl nitrate ruthenium in above-mentioned reacted solution so that titanium and ruthenium
Mol ratio is 5, continues to be heated to reflux 0.8h at 280 DEG C；After question response terminates, centrifugation, with toluene and first
Mixed alkoxide solution is washed 3 times, is then dispersed in toluene, adds the original of proper amount of nano cerium oxide and molybdenum oxide
Position compound (molybdenum is 0.02 with the mol ratio of cerium) so that titanium is 0.005 with the mol ratio of cerium, adsorbs 1h,
It is then centrifuged for, is washed with ethanol 3 times, dries；Finally by dried product in atmosphere in 200 DEG C of conditions
Lower heating 10h, you can obtain being evenly coated at nano-cerium oxide and oxidation by hollow titanium ruthenium nano composite oxide
The transition metal composite oxide catalytic agent that molybdenum composite surface is formed.
Embodiment 3
A certain amount of acetylacetone copper is accurately weighed, is added in appropriate oleyl amine so that acetylacetone copper is in oil
Concentration in amine is 110mmol/L, and heating stirring makes acetylacetone copper fully dissolve, then in 250 DEG C of oil
Under bath, 0.5h is heated to reflux；To adding ruthenic chloride in above-mentioned reacted solution so that titanium and ruthenium mole
Than being 1, continue to be heated to reflux 20h at 175 DEG C；After question response terminates, centrifugation is mixed with toluene and methyl alcohol
Close solution to wash 3 times, be then dispersed in toluene, add the mixing of appropriate sub-micro hole cerium oxide and tungsten oxide
Thing (tungsten is 0.6 with the mol ratio of cerium) so that copper is 0.01 with the mol ratio of cerium, adsorbs 20h, is then centrifuged for,
Washed with ethanol 3 times, dried；Dried product is finally heated into 0.5h under the conditions of 550 DEG C in atmosphere,
Can obtain and nano-cerium oxide and tungsten oxide mixture table are evenly coated at by hollow copper ruthenium nano composite oxide
The transition metal composite oxide catalytic agent that face is formed.
Embodiment 4
A certain amount of cobalt acetate and copper nitrate are accurately weighed, is added in appropriate oleyl amine so that cobalt acetate and nitre
Total concentration of the sour copper in oleyl amine is 55mmol/L, and heating stirring makes cobalt acetate and copper nitrate fully dissolve,
Then under 220 DEG C of oil baths, it is heated to reflux 1.5h；To adding ruthenic chloride in above-mentioned reacted solution so that
The total mole number of cobalt and copper is 4 with the mol ratio of ruthenium, continues to be heated to reflux 1.5h at 245 DEG C；Question response knot
Shu Hou, centrifugation, is washed 3 times with toluene and methyl alcohol mixed solution, is then dispersed in toluene, is added appropriate
Nano-cerium oxide so that the total mole number of cobalt and copper is 0.1 with the mol ratio of cerium, adsorbs 16h, is then centrifuged for,
Washed with ethanol 3 times, dried；Dried product is finally heated into 1.5h under the conditions of 450 DEG C in atmosphere,
Can obtain and the transition that nano-cerium oxide surface is formed is evenly coated at by hollow cobalt copper ruthenium nano composite oxide
Metal composite oxide catalyst.
Embodiment 5
A certain amount of zinc stearate is accurately weighed, is added in appropriate oleyl amine so that zinc stearate is in oleyl amine
Total concentration be 40mmol/L, heating stirring makes zinc stearate fully dissolve, then under 190 DEG C of oil baths,
It is heated to reflux 2.5h；To adding ruthenic chloride in above-mentioned reacted solution so that zinc is 3 with the mol ratio of ruthenium,
Continue to be heated to reflux 2.5h at 265 DEG C；After question response terminates, centrifugation is washed with toluene and methyl alcohol mixed solution
Wash 3 times, be then dispersed in toluene, add proper amount of nano cerium oxide so that zinc is 0.055 with the mol ratio of cerium,
Absorption 12h, is then centrifuged for, and is washed with ethanol 3 times, dries；Finally by dried product in atmosphere in
2.5h is heated under the conditions of 500 DEG C, you can obtain being evenly coated at nano oxygen by hollow zinc ruthenium nano composite oxide
Change the transition metal composite oxide catalytic agent that cerium surface is formed.
Embodiment 6
A certain amount of ferric nitrate is accurately weighed, is added in appropriate oleyl amine so that ferric nitrate is total in oleyl amine
Concentration is 30mmol/L, and heating stirring makes ferric nitrate fully dissolve, then under 100 DEG C of oil baths, heating
Backflow 20h；To adding ruthenic chloride in above-mentioned reacted solution so that iron is 2 with the mol ratio of ruthenium, at 220 DEG C
Under continue to be heated to reflux 6h；After question response terminates, centrifugation is washed 3 times with toluene and methyl alcohol mixed solution,
It is then dispersed in toluene, adds proper amount of nano cerium oxide so that iron is 0.02 with the mol ratio of cerium, absorption
8h, is then centrifuged for, and is washed with ethanol 3 times, dries；Finally by dried product in atmosphere in 400 DEG C
Under the conditions of heat 6h, you can obtain being evenly coated at nano-cerium oxide table by cored iron ruthenium nano composite oxide
The transition metal composite oxide catalytic agent that face is formed.
Embodiment 7
A certain amount of nickel acetylacetonate is accurately weighed, is added in appropriate oleyl amine so that nickel acetylacetonate is in oil
Total concentration in amine is 22mmol/L, and heating stirring makes nickel acetylacetonate fully dissolve, then at 160 DEG C
Under oil bath, 10h is heated to reflux；To addition acetylacetone,2,4-pentanedione ruthenium in above-mentioned reacted solution so that nickel and ruthenium
Mol ratio is 2.5, continues to be heated to reflux 30h at 150 DEG C；After question response terminates, centrifugation, with toluene and
Methyl alcohol mixed solution is washed 3 times, is then dispersed in toluene, adds the In-situ reaction of cerium oxide and tungsten oxide
Thing (tungsten is 0.25 with the mol ratio of cerium) so that nickel is 0.08 with the mol ratio of cerium, adsorbs 2h, is then centrifuged for,
Washed with ethanol 3 times, dried；Dried product is finally heated into 8h under the conditions of 300 DEG C in atmosphere,
Can obtain and nano-cerium oxide is evenly coated at by Hollow Nickel ruthenium nano composite oxide and tungsten oxide nanometer is combined
The transition metal composite oxide catalytic agent that thing surface is formed.
Embodiment 8
A certain amount of manganese chloride is accurately weighed, is added in appropriate oleyl amine so that manganese chloride is total in oleyl amine
Concentration is 18mmol/L, and heating stirring makes ferric nitrate fully dissolve, then under 120 DEG C of oil baths, heating
Backflow 15h；To addition acetylacetone,2,4-pentanedione ruthenium in above-mentioned reacted solution so that manganese is 2.7 with the mol ratio of ruthenium,
Continue to be heated to reflux 10h at 200 DEG C；After question response terminates, centrifugation is washed with toluene and methyl alcohol mixed solution
Wash 3 times, be then dispersed in toluene, add proper amount of nano cerium oxide so that manganese is 0.04 with the mol ratio of cerium,
Absorption 5h, is then centrifuged for, and is washed with ethanol 3 times, dries；Finally by dried product in atmosphere in
12h is heated under the conditions of 250 DEG C, you can obtain being evenly coated at nano oxygen by hollow manganese ruthenium nano composite oxide
Change the transition metal composite oxide catalytic agent that cerium surface is formed.
Comparative example 1
With identical nano-cerium oxide in embodiment 1 directly as catalyst, without using any oxygen such as nickel rutheniums
Compound carries out surface modification.
Comparative example 2
With identical nano-cerium oxide in embodiment 1, it is not to use the method in embodiment 1 that different places are
What the nickel ruthenium composite oxides of the hollow-core construction of preparation were modified nano-cerium oxide, but use phase on year-on-year basis
The common nickel ruthenium composite oxides of example carry out the nano combined oxygen of cerium base obtained after surface modification to nano-cerium oxide
Compound catalyst.
Comparative example 3
With identical nano-cerium oxide in embodiment 2 and molybdenum oxide compound directly as catalyst, do not add
Plus any oxide such as titanium ruthenium carries out surface modification.
Comparative example 4
With identical nano-cerium oxide in embodiment 2 and molybdenum oxide compound, different places are not to be using real
The titanium ruthenium composite oxides for applying hollow-core construction prepared by the method in example 2 are compound to nano-cerium oxide and molybdenum oxide
What thing was modified, but the common titanium ruthenium composite oxides of same ratio are used to nano-cerium oxide and oxidation
Molybdenum compound carries out the cerium base nano composite oxide catalyst obtained after surface modification.
Comparative example 5
With identical nano-cerium oxide in embodiment 3 and tungsten oxide mixture directly as catalyst, do not add
Plus any oxide such as copper ruthenium carries out surface modification.
Comparative example 6
With identical nano-cerium oxide in embodiment 3 and tungsten oxide mixture, different places are not to be using real
The copper ruthenium composite oxides for applying hollow-core construction prepared by the method in example 1 mix to nano-cerium oxide and tungsten oxide
What thing was modified, but the ordinary copper ruthenium composite oxides of same ratio are used to nano-cerium oxide and oxidation
Tungsten mixture carries out the cerium base nano composite oxide catalyst obtained after surface modification.
Comparative example 7
It is any without addition cobalt copper ruthenium etc. with identical nano-cerium oxide in embodiment 4 directly as catalyst
Oxide carries out surface modification.
Comparative example 8
With identical nano-cerium oxide in embodiment 4, it is not to use the method in embodiment 4 that different places are
What the cobalt copper ruthenium composite oxides of the hollow-core construction of preparation were modified nano-cerium oxide, but use identical
The cerium base nanometer that the common cobalt copper ruthenium composite oxides of ratio carry out being obtained after surface modification to nano-cerium oxide is multiple
Close oxide catalyst.
Comparative example 9
With identical nano-cerium oxide in embodiment 5 directly as catalyst, without using any oxygen such as zinc rutheniums
Compound carries out surface modification.
Comparative example 10
With identical nano-cerium oxide in embodiment 5, it is not to use the method in embodiment 5 that different places are
What the zinc ruthenium composite oxides of the hollow-core construction of preparation were modified nano-cerium oxide, but use phase on year-on-year basis
The common zinc ruthenium composite oxides of example carry out the nano combined oxygen of cerium base obtained after surface modification to nano-cerium oxide
Compound catalyst.
Comparative example 11
With identical nano-cerium oxide in embodiment 5 directly as catalyst, without using any oxygen such as zinc rutheniums
Compound carries out surface modification.
Comparative example 12
With identical nano-cerium oxide in embodiment 6, it is not to use the method in embodiment 6 that different places are
What the iron ruthenium composite oxides of the hollow-core construction of preparation were modified nano-cerium oxide, but use phase on year-on-year basis
The common iron ruthenium composite oxides of example carry out the nano combined oxygen of cerium base obtained after surface modification to nano-cerium oxide
Compound catalyst.
Comparative example 13
With identical nano-cerium oxide in embodiment 7 and tungsten oxide compound directly as catalyst, do not add
Plus any oxide such as nickel ruthenium carries out surface modification.
Comparative example 14
With identical nano-cerium oxide in embodiment 7 and tungsten oxide compound, different places are not to be using real
The nickel ruthenium composite oxides for applying hollow-core construction prepared by the method in example 7 are compound to nano-cerium oxide and tungsten oxide
What thing was modified, but the common nickel ruthenium composite oxides of same ratio are used to nano-cerium oxide and oxidation
Tungsten compound carries out the cerium base nano composite oxide catalyst obtained after surface modification.
Comparative example 15
With identical nano-cerium oxide in embodiment 8 directly as catalyst, without using any oxygen such as manganese rutheniums
Compound carries out surface modification.
Comparative example 16
With identical nano-cerium oxide in embodiment 8, it is not to use the method in embodiment 8 that different places are
What the manganese ruthenium composite oxides of the hollow-core construction of preparation were modified nano-cerium oxide, but use phase on year-on-year basis
The common manganese ruthenium composite oxides of example carry out the nano combined oxygen of cerium base obtained after surface modification to nano-cerium oxide
Compound catalyst.
Any one cerium-based composite oxides catalysis in above-described embodiment provided by the present invention and comparative example
Agent, its activity characterization condition is：Under test gas atmosphere is 600ppmNOx, 600ppmNH3, 5%O2, N2
It is Balance Air, the total flow of gas is 500ml/min, total space-time is 50000/h, reaction temperature is 145~
550℃.Characterization result is as shown in Table 1 and Table 2.
The catalyst of table 1 is to NOxConversion ratio
The catalyst of table 2 is to N2Selectivity
Claims (17)
1. a kind of transition metal composite catalyst, it is characterised in that the transition metal composite oxide catalytic agent is by main activearm
Point A and the composition of the auxiliary agent B two parts with cooperative effect, wherein, main active component A refers to cerium oxide, or cerium oxide and
The composite oxides of at least one of both tungsten oxide and molybdenum oxide, the auxiliary agent B with cooperative effect is a kind of hollow-core construction
The composite oxides of transition metal M and ruthenium, and, the auxiliary agent B with hollow-core construction is evenly coated at main active components A surface.
2. transition metal composite oxide catalytic agent according to claim 1, it is characterised in that M units in the auxiliary agent B
Element is 0.005~0.1, preferably 0.01~0.08, more preferably 0.02~0.055 with the mol ratio of cerium.
3. transition metal composite oxide catalytic agent according to claim 1, it is characterised in that the main active component A
In, the total mole number of tungsten and molybdenum is 0~0.6, preferably 0.02~0.45, more preferably 0.05~0.35 with the mol ratio of cerium.
4. transition metal composite oxide catalytic agent according to claim 1, it is characterised in that described main active component
Cerium oxide, tungsten oxide and molybdenum oxide in A can be nano particle, nanometer rods, nanometer sheet, nano wire, micropore, it is mesoporous or
Any one in person's sub-micro Porous materials or two kinds and two or more compositions.
5. transition metal composite oxide catalytic agent according to claim 1, it is characterised in that described main active component
A refers to cerium oxide, or the composite oxides at least one of both cerium oxide and tungsten oxide and molybdenum oxide, wherein, institute
The composite oxides of at least one of both cerium oxide and tungsten oxide and molybdenum oxide stated, refer to the compound of simple physical mixing
Oxide, or refer to that fabricated in situ is carried out using chemical synthesis such as co-precipitation, sol-gel, hydro-thermal methods in building-up process
Cerium oxide and tungsten oxide and molybdenum oxide both at least one of composite oxides.
6. transition metal composite oxide catalytic agent according to claim 1, it is characterised in that described auxiliary agent B is
The composite oxides of hollow-core construction transition metal M and ruthenium are planted, a diameter of 8nm~25nm of hollow-core construction, hollow structure material is uniform
The surface for being scattered in main active component A.
7. transition metal composite oxide catalytic agent according to claim 1, it is characterised in that described transition metal M
One kind or two or more combination in for copper, nickel, cobalt, iron, zinc, titanium, manganese.
8. transition metal composite oxide catalytic agent according to claims 1 to 7, its preparation method comprises the following steps：
A be added to M presomas in oleyl amine by (), stirring and dissolving；Then heating reflux reaction；
B () continues heating reflux reaction to ruthenium presoma is added in the reacted solution of step (a)；
C () separates step (b) gained product, washing is scattered in organic solvent again, and adds main active components A,
Separated after absorption, washing is dried；
D () calcines step (c) products therefrom, you can the auxiliary agent B for obtaining hollow-core construction is evenly coated at main active components A table
Face and the transition metal composite oxide catalytic agent that is formed.
9. preparation method according to claim 8, it is characterised in that step (a) the M presomas are cupric perchlorate, formic acid
Copper, copper chloride, copper citrate, Cupric salicylate, copper nitrate, copper bromide, copper acetate, copper stearate, copper oleate, second
Acyl acetone copper, nickelous perchlorate, nickel formate, nickel chloride, citric acid nickel, nickel salicylates, nickel nitrate, nickelous bromide, acetic acid
Nickel, nickel stearate, oleic acid nickel, nickel acetylacetonate, manganese chloride, manganese nitrate, manganous bromide, manganese acetate, manganese acetylacetonate,
Cobalt chloride, cobalt nitrate, cobaltous bromide, cobalt acetate, acetylacetone cobalt, iron chloride, ferric nitrate, ferric bromide, acetylacetone,2,4-pentanedione
Iron, zinc chloride, zinc nitrate, zinc bromide, zinc acetate, zinc stearate, zinc acetylacetonate, titanium chloride, Titanium Nitrate, bromine
Change titanium, titanium stearate, one kind or two or more combination in titanium acetylacetone；Preferably copper chloride, copper nitrate, chlorination
Nickel, manganese chloride, cobalt chloride, cobalt nitrate, iron chloride, ferric nitrate, zinc chloride, zinc nitrate, titanium chloride, 1 in Titanium Nitrate
Plant or combination of more than two kinds；Particularly preferably copper chloride, manganese chloride, iron chloride, nickel chloride, a kind or 2 in cobalt chloride
Plant the combination of the above；
Preferably, concentration of the M presomas in oleyl amine be 8mmol/L~110mmol/L, preferably 18mmol/L~55mmol/L,
More preferably 22~30mmol.
10. preparation method according to claim 8 or claim 9, it is characterised in that claim 8 step (a) is described to be heated to reflux
Temperature is 85~250 DEG C, more preferably preferably 120~220 DEG C, 160~190 DEG C；The heating reflux reaction when
Between be 0.5~30h, more preferably preferably 1.5~20h, 2.5~10h.
11. preparation method according to claim any one of 8-10, it is characterised in that claim 8 step (b) ruthenium
Presoma is ruthenium trichloride, (isopropyl toluene) [(S, S)-Ts-DPEN] ruthenic chloride, acetylacetone,2,4-pentanedione ruthenium, tri-chlorination six
Ammonium closes the one kind or two or more combination in ruthenium, nitrosyl nitrate ruthenium；
Preferably, the M presomas and the mol ratio of ruthenium presoma are 1~5, preferably 4~2, more preferably 2.7~2.2.
12. preparation method according to claim any one of 8-11, it is characterised in that claim 8 step (b) is described to return
The temperature for flowing heating response is 150~280 DEG C, preferably 175~265 DEG C；The time of the heating reflux reaction is 0.8~30h,
Preferably 1.5~20h, more preferably 2.5~10h.
13. preparation method according to claim any one of 8-12, it is characterised in that inhaled described in claim 8 step (c)
The attached time is more than 0.5h, more preferably preferably 1~20h, 2h~8h.
14. preparation method according to claim any one of 8-13, it is characterised in that by step in claim 8 step (c)
Washing b () gained product is separated after uses a kind or 2 kinds in methyl alcohol, ethanol, propyl alcohol, acetone, n-butanol
Mixture above is carried out；Preferably methyl alcohol and/or ethanol；More preferably ethanol；
Preferably, the washing after adsorbing and separate is carried out using the one kind or two or more mixing in methyl alcohol, ethanol, water；
Preferably, the washing is more than 3 times, preferably 5 times；
Preferably, the organic solvent be toluene, dimethylbenzene, chlorobenzene, dichloro-benzenes, carbon tetrachloride, hexamethylene, hexane, chloropropane,
One kind or two or more mixing in hexane, heptane；
Preferably, it is described to be separated into centrifugation.
15. preparation method according to claim any one of 8-14, it is characterised in that claim 8 step (d) calcining
Carried out in air, oxygen or other oxidizing atmospheres；
Preferably, the temperature of the calcining is 200 DEG C~550 DEG C, more preferably preferably 250~450 DEG C, 300~400 DEG C；
The time of the calcining is 0.5~12h, more preferably preferably 1.5~8h, 2.5~6h.
16. any one transition metal composite oxide catalytic agent, its preparation method and use according to claim 1~15
On the way, it is characterised in that described transition metal composite oxide catalytic agent can be catalyzed reduction field in nitrous oxides selectivity,
Such as, apply in fields such as the catalytic purifications of nitrogen oxides such as exhaust gas from diesel vehicle, coal-burning power plant, oil plant and smeltery's flue gas.
17. any one transition metal composite oxide catalytic agent, its preparation method and use according to claim 1~15
On the way, it is characterised in that in the range of 160~430 DEG C, transformation efficiency of the oxides of nitrogen is more than 92%, is 100% between 190~380 DEG C；
In the range of 160~430 DEG C, the selectivity of nitrogen is more than 91%, and in the range of 145~430 DEG C, the selectivity of nitrogen is more than 96%,
In the range of 145~350 DEG C, the selectivity of nitrogen is 100%.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005021137A1 (en) * | 2003-09-03 | 2005-03-10 | Hte Aktiengeselschaft | Catalyst for removing pollutants from exhaust gases from lean-burn engines, with ruthenium as active metal |
| CN103172030A (en) * | 2013-03-22 | 2013-06-26 | 清华大学深圳研究生院 | Oxide powder and preparation method thereof as well as catalyst and carrier thereof |
| CN103433034A (en) * | 2013-09-13 | 2013-12-11 | 国电环境保护研究院 | Low-temperature SCR (Selective Catalytic Reduction) catalyst based on active coke loaded manganese-cerium composite oxide and preparation method of low-temperature SCR catalyst |
| CN103480371A (en) * | 2013-09-22 | 2014-01-01 | 中国神华能源股份有限公司 | Denitration and demercuration catalyst as well as preparing method and application thereof |
| CN104909352A (en) * | 2015-06-02 | 2015-09-16 | 中国科学院过程工程研究所 | Hollow-structure transition metal/ruthenium composite oxide nano material and preparation method thereof |
-
2015
- 2015-12-30 CN CN201511018830.8A patent/CN106925265B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005021137A1 (en) * | 2003-09-03 | 2005-03-10 | Hte Aktiengeselschaft | Catalyst for removing pollutants from exhaust gases from lean-burn engines, with ruthenium as active metal |
| CN103172030A (en) * | 2013-03-22 | 2013-06-26 | 清华大学深圳研究生院 | Oxide powder and preparation method thereof as well as catalyst and carrier thereof |
| CN103433034A (en) * | 2013-09-13 | 2013-12-11 | 国电环境保护研究院 | Low-temperature SCR (Selective Catalytic Reduction) catalyst based on active coke loaded manganese-cerium composite oxide and preparation method of low-temperature SCR catalyst |
| CN103480371A (en) * | 2013-09-22 | 2014-01-01 | 中国神华能源股份有限公司 | Denitration and demercuration catalyst as well as preparing method and application thereof |
| CN104909352A (en) * | 2015-06-02 | 2015-09-16 | 中国科学院过程工程研究所 | Hollow-structure transition metal/ruthenium composite oxide nano material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| WANMIAO CHEN, ET AL.: "Mechanism of the Selective Catalytic Oxidation of Slip Ammonia over Ru-Modified Ce-Zr Complexes Determined by in Situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy", 《ENVIRON. SCI. TECHNOL.》 * |
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