CN115532273B - Catalyst, preparation method and application thereof - Google Patents
Catalyst, preparation method and application thereof Download PDFInfo
- Publication number
- CN115532273B CN115532273B CN202211267858.5A CN202211267858A CN115532273B CN 115532273 B CN115532273 B CN 115532273B CN 202211267858 A CN202211267858 A CN 202211267858A CN 115532273 B CN115532273 B CN 115532273B
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- China
- Prior art keywords
- catalyst
- transition metal
- ceo
- precursor
- solvent
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 68
- 150000003624 transition metals Chemical class 0.000 claims abstract description 41
- 239000011148 porous material Substances 0.000 claims abstract description 22
- 230000003197 catalytic effect Effects 0.000 claims abstract description 20
- 239000012855 volatile organic compound Substances 0.000 claims abstract description 19
- 239000002159 nanocrystal Substances 0.000 claims abstract description 12
- 230000003647 oxidation Effects 0.000 claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- 239000013078 crystal Substances 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims description 36
- 239000012695 Ce precursor Substances 0.000 claims description 34
- 239000002904 solvent Substances 0.000 claims description 34
- 239000008139 complexing agent Substances 0.000 claims description 31
- 239000011259 mixed solution Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 24
- 238000001354 calcination Methods 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- 230000032683 aging Effects 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- 229960002798 cetrimide Drugs 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 238000009826 distribution Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 21
- 238000003756 stirring Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 10
- 229910052684 Cerium Inorganic materials 0.000 description 9
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 9
- 239000002131 composite material Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229910000420 cerium oxide Inorganic materials 0.000 description 7
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000005204 segregation Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 3
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229960004106 citric acid Drugs 0.000 description 3
- 229960002303 citric acid monohydrate Drugs 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 238000007084 catalytic combustion reaction Methods 0.000 description 2
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 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 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 150000000703 Cerium Chemical class 0.000 description 1
- 229910021583 Cobalt(III) fluoride Inorganic materials 0.000 description 1
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910021575 Iron(II) bromide Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910021569 Manganese fluoride Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ZGMCLEXFYGHRTK-UHFFFAOYSA-N [Fe].[Ce] Chemical compound [Fe].[Ce] ZGMCLEXFYGHRTK-UHFFFAOYSA-N 0.000 description 1
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 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
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- PGJHGXFYDZHMAV-UHFFFAOYSA-K azanium;cerium(3+);disulfate Chemical compound [NH4+].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O PGJHGXFYDZHMAV-UHFFFAOYSA-K 0.000 description 1
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229960001759 cerium oxalate Drugs 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- ZMZNLKYXLARXFY-UHFFFAOYSA-H cerium(3+);oxalate Chemical compound [Ce+3].[Ce+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZMZNLKYXLARXFY-UHFFFAOYSA-H 0.000 description 1
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 1
- QCCDYNYSHILRDG-UHFFFAOYSA-K cerium(3+);trifluoride Chemical compound [F-].[F-].[F-].[Ce+3] QCCDYNYSHILRDG-UHFFFAOYSA-K 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
- MOOUSOJAOQPDEH-UHFFFAOYSA-K cerium(iii) bromide Chemical compound [Br-].[Br-].[Br-].[Ce+3] MOOUSOJAOQPDEH-UHFFFAOYSA-K 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 description 1
- YCYBZKSMUPTWEE-UHFFFAOYSA-L cobalt(ii) fluoride Chemical compound F[Co]F YCYBZKSMUPTWEE-UHFFFAOYSA-L 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 description 1
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- CTNMMTCXUUFYAP-UHFFFAOYSA-L difluoromanganese Chemical compound F[Mn]F CTNMMTCXUUFYAP-UHFFFAOYSA-L 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 1
- 229940046149 ferrous bromide Drugs 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 description 1
- FZGIHSNZYGFUGM-UHFFFAOYSA-L iron(ii) fluoride Chemical compound [F-].[F-].[Fe+2] FZGIHSNZYGFUGM-UHFFFAOYSA-L 0.000 description 1
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 description 1
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- DBJLJFTWODWSOF-UHFFFAOYSA-L nickel(ii) fluoride Chemical compound F[Ni]F DBJLJFTWODWSOF-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- SWURHZJFFJEBEE-UHFFFAOYSA-J tetrafluorocerium Chemical compound F[Ce](F)(F)F SWURHZJFFJEBEE-UHFFFAOYSA-J 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/864—Removing carbon monoxide or hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
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- B01J35/647—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention relates to a catalyst, a preparation method and application thereof. The catalyst is prepared from CeO 2 Nanocrystalline is piled up, wherein, the CeO 2 The lattice of the nanocrystalline is doped with transition metal, and the catalyst has a crystal structure composed of CeO 2 The nano crystals are piled to form a plurality of pore canal structures, and the average pore diameter of the pore canal structures is 2-20 nm. The catalyst provided by the invention has more uniform doping element distribution, more active sites, more excellent catalytic performance and better structural stability, and can be used for catalytic oxidation of volatile organic compounds. Furthermore, the preparation method of the catalyst is simple and feasible, raw materials are easy to obtain, and the catalyst is suitable for mass production.
Description
Technical Field
The invention relates to a catalyst and a preparation method and application thereof, in particular to a catalyst for catalytic oxidation of volatile organic compounds and a preparation method and application thereof, belonging to the field of catalysts.
Background
The volatile organic compounds (Volatile organic compounds, VOCs) are organic compounds with saturated vapor pressure higher than 133.32Pa and boiling point between 50 and 250 ℃, have atmospheric photochemical reaction activity, can generate photochemical smog and secondary organic aerosol, are O 3 And PM 2.5 The common precursor is the key for treating the atmospheric pollution.
VOCs emission control technology is mainly divided into a recovery method and a destruction method. The recovery method mainly aims at a few emission sources with recovery value and higher concentration. The destruction method has wider application range, and mainly aims at the emission sources which are more common and lack of recovery value, and the VOCs are converted into carbon dioxide and water in the modes of combustion, catalytic oxidation, biodegradation and the like to realize harmless treatment. The catalytic oxidation method has good stability, can obviously reduce the reaction temperature and byproducts, thereby improving the safety and reducing the operation cost, and has the most extensive application prospect. The VOCs catalytic combustion catalyst used in the industry at present is mainly a noble metal catalyst, has high cost and is easy to be deactivated due to noble metal loss, sintering, poisoning and the like. In addition, the national precious metal reserves are insufficient, and the strategic safety of industrial production and people living can be seriously endangered by excessively depending on the precious metal catalyst.
The cerium-based catalyst has excellent oxidation-reduction property and oxygen storage and release capability, the price of light rare earth elements is low, and the cerium-based catalyst has good prospect of substituting noble metals to realize industrial application, but the cerium-based catalyst generally has the problems of poor dispersibility of doping elements, low active site content, insufficient activity and the like.
Citation 1 discloses an iron-cerium composite oxide catalyst for VOCs treatment and a preparation method thereof. The Fe-Ce composite oxide catalyst consists of rare earth goldComposite oxide Ce of cerium (Ce) and transition metal iron (Fe) x Fe y O z A catalyst in the form of a solid powder; where x=2 to 40, y=2 to 4, and z=7 to 86. However, in the composite oxide, transition metal iron cannot be uniformly doped, so that obvious tensile lattice strain does not occur, and reactive sites such as oxygen vacancies are insufficient, so that the catalytic activity is low.
Reference 2 discloses a cerium-zirconium-based composite oxide in which elements are distributed in a gradient manner, the composite oxide containing cerium element and zirconium element, the cerium element and zirconium element being distributed in a gradient manner from inside to outside in crystal grains, and a method for producing the same. The cerium-zirconium-based composite oxide with gradient element distribution is prepared by a step-by-step precipitation method, firstly, zirconium-rich components are precipitated firstly, and can form a high-heat stable crystal structure and a grain stacking structure, so that segregation of zirconium on the surface after high-temperature treatment is slowed down, and element migration among grains is reduced; secondly, the cerium-rich component is sunk later, so that the cerium content of the surface layer of the crystal grain is improved, the utilization rate of cerium element is improved, and the oxygen storage amount and the oxygen storage and release rate are improved. However, in the composite oxide, the intrinsic activity of the transition metal zirconium is poor, the doping dispersibility is low, the active site content is low, and the activity is insufficient, so that the catalytic activity is low.
Therefore, improving the dispersibility of doping elements in the catalyst, increasing the content of active sites and improving the catalytic combustion performance of VOCs is a technical problem to be solved urgently.
Citation literature:
citation 1: CN 113398939A
Citation 2: CN 112076740A
Disclosure of Invention
Problems to be solved by the invention
In view of the technical problems existing in the prior art, for example: the invention provides a catalyst, which has the advantages of poor dispersibility of doping elements, low content of active sites, insufficient activity and the like. The catalyst provided by the invention has more uniform doping element distribution, more active sites, more excellent catalytic performance and better structural stability, and can be used for catalytic oxidation of volatile organic compounds.
Furthermore, the invention also provides a preparation method of the catalyst, which is simple and easy to implement, raw materials are easy to obtain, and the catalyst is suitable for mass production.
Solution for solving the problem
[1]A catalyst, wherein the catalyst is composed of CeO 2 The nano-crystal is formed by stacking, wherein,
the CeO 2 The lattice of the nanocrystal is doped with a transition metal, and,
the catalyst has a catalyst composed of CeO 2 The nano crystals are piled to form a plurality of pore canal structures, and the average pore diameter of the pore canal structures is 2-20 nm.
[2]According to [1] above]The catalyst, wherein, the CeO is singly 2 The average diameter of the nanocrystalline is 2-30 nm; and/or the mol ratio of the transition metal element to the Ce element in the catalyst is 1:99-30:70.
[3] The catalyst according to the above [1] or [2], wherein the catalyst is represented by:
TM n％ -CeO 2
wherein TM represents a transition metal element, n% represents the mole percentage of the transition metal element to the total metal elements in the catalyst, and the value of n is 1-30;
preferably, the transition metal element includes one or a combination of two or more of Fe, mn, co, cu, ni, zn, V, cr, ti, pd, ag, cd.
[4] A method for producing the catalyst according to any one of the above [1] to [3], wherein the method comprises the steps of:
mixing a cerium precursor, a transition metal precursor and a complexing agent in a solvent to obtain a mixed solution;
volatilizing the solvent in the mixed solution to form a gel product;
igniting and aging the gel product to obtain burnout powder;
and calcining the burnout powder to obtain the catalyst.
[5] The production method according to the above [4], wherein the mass ratio of the cerium precursor to the transition metal precursor is 5:1 to 200:1; and/or the ratio of the mass of the complexing agent to the total mass of the cerium precursor and the transition metal precursor is 1:10-2:1.
[6] The preparation method according to the above [4] or [5], wherein the mass concentration of the complexing agent in the mixed solution is 0.5 to 250mg/mL; and/or, in the mixed solution, the total mass concentration of the cerium precursor and the transition metal precursor is 0.5-250 mg/mL.
[7] The process according to the above [4] to [6], wherein the complexing agent comprises one or a combination of two or more of citric acid, EDTA, polyoxyethylene polyoxypropylene ether block copolymer, cetrimide.
[8] The production method according to the above [4] to [7], wherein the solvent in the mixed solution is volatilized by heating; preferably, the heating temperature is 40-120 ℃, and the heating time is 0.5-48 h; and/or
Igniting the gel product by heating; preferably, the ignition temperature is 130-250 ℃, and the aging time is 0.5-48 h.
[9] The production method according to the above [4] to [8], wherein the calcination is calcination under the condition of an oxygen content of 1 to 100%; the calcination temperature is 200-800 ℃, and the calcination time is 0.5-12 h.
[10] The use of the catalyst according to any one of [1] to [3] above for catalytic oxidation of volatile organic compounds.
ADVANTAGEOUS EFFECTS OF INVENTION
The catalyst provided by the invention has more uniform doping element distribution, more active sites, more excellent catalytic performance and better structural stability, and can be used for catalytic oxidation of volatile organic compounds.
Furthermore, the preparation method of the catalyst is simple and feasible, raw materials are easy to obtain, and the catalyst is suitable for mass production.
Drawings
FIG. 1 shows the conversion of toluene to temperature for the catalytic oxidation of the catalysts of examples 1-3 and comparative example 1 of the present invention.
FIG. 2 shows Co according to example 2 of the present invention 10％ -CeO 2 Microstructure test results of the catalyst;
wherein a in FIG. 2 shows Co 10％ -CeO 2 An X-ray diffraction spectrum of the catalyst;
b in FIG. 2 shows Co 10％ -CeO 2 X-ray absorption fine structure spectrum of the catalyst;
c in FIG. 2 shows Co 10％ -CeO 2 A transmission electron microscope image of the catalyst;
d in FIG. 2 shows Co 10％ -CeO 2 Spherical aberration correcting scanning transmission electron microscope image of the catalyst.
Detailed Description
Various exemplary embodiments, features and aspects of the invention are described in detail below. The word "exemplary" is used herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
Furthermore, in the following detailed description, numerous specific details are set forth in order to provide a better illustration of the invention. It will be understood by those skilled in the art that the present invention may be practiced without some of these specific details. In other instances, well known methods, procedures, means, equipment and steps have not been described in detail so as not to obscure the present invention.
Unless otherwise indicated, all units used in this specification are units of international standard, and numerical values, ranges of values, etc. appearing in the present invention are understood to include systematic errors unavoidable in industrial production.
In the present specification, "%" means mass% unless otherwise specified.
In the present specification, the meaning of "can" includes both the meaning of performing a certain process and the meaning of not performing a certain process.
Reference throughout this specification to "some specific/preferred embodiments," "other specific/preferred embodiments," "an embodiment," and so forth, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the elements may be combined in any suitable manner in the various embodiments.
In the present specification, the numerical range indicated by the term "numerical value a to numerical value B" means a range including the end point numerical value A, B.
< first aspect >
The first aspect of the present invention provides a catalyst comprising CeO 2 The nano-crystal is formed by stacking, wherein,
the CeO 2 The lattice of the nanocrystal is doped with a transition metal, and,
the catalyst has a catalyst composed of CeO 2 The nano crystals are piled to form a plurality of pore canal structures, and the average pore diameter of the pore canal structures is 2-20 nm.
The transition metal element in the catalyst disclosed by the invention is uniformly doped in atomic scale, has excellent catalytic activity, is similar to that of a noble metal catalyst, has good stability, and is low in cost.
In the present invention, the transition metal is represented by CeO 2 The crystal lattice of the nanocrystalline is uniformly doped at the atomic level, and segregation and agglomeration phenomena can not occur; the inventor discovers that the transition metal doping can induce the cerium oxide to form reactive sites such as oxygen vacancies and the like, and can also improve the redox performance and oxygen storage and release capacity of the cerium oxide as an electronic auxiliary agent, but the segregation and agglomeration of the cerium oxide can lead to weakening of the effects.
CeO of the present invention 2 The grain size of the nanocrystalline is uniform, ceO 2 The nanocrystals can form a plurality of pore structures through disordered stacking. The uniform grain size can ensure the uniformity of the catalyst, promote the further coating and utilization performance, and multiple pore canal junctionsThe structure is favorable for the adsorption process of pollutants such as volatile organic compounds and the like, and is the basis for improving the catalytic oxidation performance.
The inventor discovers that the average pore diameter of the pore channel structure is too small, which is unfavorable for the diffusion of reactants, the average pore diameter of the pore channel structure is too large, the specific surface area is reduced, and the exposure number of active sites is reduced, which is unfavorable for the reaction. Thus, in the present invention, the average pore diameter of the pore structure is preferably 2 to 20nm, for example: 5nm, 8nm, 10nm, 12nm, 15nm, 18nm, etc.
In some specific embodiments, a single one of the CeO' s 2 The average diameter of the nanocrystals is 2 to 30nm, for example: 5nm, 8nm, 10nm, 12nm, 15nm, 18nm, 20nm, 22nm, 25nm, 28nm, etc. If a single CeO 2 The diameter of the nanocrystalline is too small, so that the nanocrystalline is difficult to synthesize and easy to sinter; if a single CeO 2 The diameter of the nanocrystalline is too large, the specific surface area of the catalyst can be obviously reduced, and the exposure number of active sites is reduced, which is unfavorable for the reaction. Preferably, the average diameter of the individual nanocrystals is from 4 to 10nm.
In other specific embodiments, the molar ratio of transition metal element to Ce element in the catalyst is from 1:99 to 30:70, for example: 2:98, 5:95, 8:92, 10:90, 12:88, 15:85, 18:82, 20:80, 22:78, 25:75, 28:72, etc. If the content of the transition metal element is too low, the activity is not sufficiently promoted, and if the content of the transition metal element is too high, segregation is caused.
Further, in the present invention, the catalyst is represented as:
TM n％ -CeO 2
wherein TM represents a transition metal element, n% represents a mole percentage of the transition metal element to the total metal elements in the catalyst, and the value of n is 1 to 30, for example: 2. 5, 8, 10, 12, 15, 18, 20, 22, 25, 28, etc.;
preferably, the transition metal element includes one or a combination of two or more of Fe, mn, co, cu, ni, zn, V, cr, ti, pd, ag, cd.
<Second aspect>
A second aspect of the present invention provides a method for preparing a catalyst according to the first aspect of the present invention, comprising the steps of:
mixing a cerium precursor, a transition metal precursor and a complexing agent in a solvent to obtain a mixed solution;
volatilizing the solvent in the mixed solution to form a gel product;
igniting and aging the gel product to obtain burnout powder;
and calcining the burnout powder to obtain the catalyst.
The preparation method is simple, is suitable for large-scale production, and has commercial prospect.
Mixing
The invention obtains a mixed solution by mixing a cerium precursor, a transition metal precursor and a complexing agent in a solvent.
In some specific embodiments, the cerium precursor to the transition metal precursor mass ratio is from 5:1 to 200:1, for example: 10:1, 20:1, 50:1, 80:1, 100:1, 120:1, 150:1, 180:1, etc.; the inventor discovers that when the mass ratio of the cerium precursor to the transition metal precursor is 5:1-200:1, the content of the transition metal element in the catalyst can be regulated and controlled. Too high a mass ratio of cerium precursor to transition metal precursor may result in too small doping amount of transition metal element and poor performance, and too low a mass ratio of cerium precursor to transition metal precursor may result in uneven doping of transition metal element and phase change.
Further, in the mixed solution, the total mass concentration of the cerium precursor and the transition metal precursor is 0.5 to 250mg/mL, for example: 1mg/mL, 10mg/mL, 20mg/mL, 50mg/mL, 80mg/mL, 100mg/mL, 120mg/mL, 150mg/mL, 180mg/mL, 200mg/mL, 220mg/mL, 250mg/mL, 280mg/mL, etc. The total mass concentration of the cerium precursor and the transition metal precursor can regulate and control the synthesis amount of the catalyst, and if the total mass concentration of the cerium precursor and the transition metal precursor is too high, the cerium precursor and the transition metal element precursor can not be completely dissolved, and if the total mass concentration of the cerium precursor and the transition metal precursor is too low, the solvent waste can be caused.
In other specific embodiments, the ratio of the mass of the complexing agent to the total mass of the cerium precursor and the transition metal precursor is from 1:10 to 2:1, for example: 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, 1:1, etc. The inventors found that when the ratio of the mass of the complexing agent to the total mass of the cerium precursor and the transition metal precursor is 1:10-2:1, the content of the complexing agent in the synthesis process can be regulated, if the ratio of the mass of the complexing agent to the total mass of the cerium precursor and the transition metal precursor is too high, the complexing agent is wasted and impurities are deposited, and if the ratio of the mass of the complexing agent to the total mass of the cerium precursor and the transition metal precursor is too low, the complex of the transition metal element is poor and the doping is uneven.
Further, in the mixed solution, the mass concentration of the complexing agent is 0.5-250 mg/mL, for example: 1mg/mL, 10mg/mL, 20mg/mL, 50mg/mL, 80mg/mL, 100mg/mL, 120mg/mL, 150mg/mL, 180mg/mL, 200mg/mL, 220mg/mL, 250mg/mL, 280mg/mL, etc. If the mass concentration of the complexing agent is too high, the complexing agent may not be completely dissolved, and if the total mass concentration is too low, the solvent is wasted.
Further, in the present invention, the cerium precursor may generally be any viable cerium salt in the present invention. For example: cerium nitrate, cerium chloride, cerium trifluoride, cerium tetrafluoride, ammonium cerium nitrate, cerium sulfate, cerium acetate, cerium oxalate, cerium bromide, ammonium cerium sulfate, or the like.
For transition metal precursors, it is generally possible to use any of the transition metal-containing salts of the present invention. Taking manganese salt, ferric salt, cobalt salt, nickel salt and copper salt as examples, the transition metal precursor may be one or more of manganese nitrate, manganese chloride, manganese fluoride, manganese sulfate, manganese acetate, manganese oxalate, manganese bromide, ferric nitrate, ferrous nitrate, ferric chloride, ferrous chloride, ferric fluoride, ferrous fluoride, ferric sulfate, ferrous sulfate, ferric acetate, ferrous acetate, ferric oxalate, ferric bromide, ferrous bromide, cobalt nitrate, cobalt chloride, cobalt fluoride, cobalt sulfate, cobalt acetate, cobalt oxalate, cobalt bromide, nickel nitrate, nickel chloride, nickel fluoride, nickel sulfate, nickel acetate, nickel oxalate, nickel bromide, copper nitrate, copper chloride, copper fluoride, copper sulfate, copper acetate, copper oxalate and copper bromide.
The complexing agent is not particularly limited as long as it is a complexing agent capable of forming a gel. Specifically, the complexing agent comprises one or a combination of more than two of citric acid, EDTA and cetrimide. Wherein the citric acid may comprise citric acid monohydrate.
The solvent is not particularly limited, and may be any solvent available in the art. Specifically, in the present invention, the solvent may be selected from an organic solvent or water. The organic solvent may be a polar solvent such as an alcohol solvent, a ketone solvent, an ester solvent, a nitrile solvent, etc., and the solvent is at least one of water, ethanol, methanol, or acetone from the viewpoint of subsequent treatment. In some embodiments of the present invention, the solvent may also be a mixture of the above polar solvent and water, and when the solvent is used as a mixed solvent, the water is preferably contained in the solvent in a mass fraction of 70% or more based on the total mass of the solvent.
In some specific embodiments, the mixing comprises:
mixing a cerium precursor and a transition metal precursor in a solvent to obtain a first clear solution;
mixing the complexing agent in a solvent to obtain a second clarified solution;
and mixing the first clarified solution with the second clarified solution to obtain a mixed solution.
According to the invention, the cerium precursor and the transition metal element precursor can be fully contacted by firstly obtaining the first clear solution, and the cerium oxide nanocrystalline catalyst with uniform transition metal element doping can be stably obtained in the subsequent steps.
Specifically, in the first clarified solution of the present invention, the total mass concentration of the cerium precursor and the transition metal precursor is 1 to 500mg/mL, for example: 10mg/mL, 50mg/mL, 100mg/mL, 150mg/mL, 200mg/mL, 250mg/mL, 300mg/mL, 350mg/mL, 400mg/mL, 450mg/mL, etc. When the total mass concentration of the cerium precursor and the transition metal precursor is 1-500 mg/mL, a suitable content of the cerium precursor and the transition metal precursor can be obtained.
Further, in obtaining the first clarified solution, there is no particular limitation on the means for mixing, and preferably, the mixing may be performed under stirring. The stirring time is not particularly limited, and may be set as required as long as the first clear solution is obtained.
The invention can fully combine the complexing agent and the solvent by obtaining the second clear solution, and stably complex cerium precursor and transition metal element precursor ions in the subsequent steps.
Specifically, in the first clarified solution of the present invention, the complexing agent has a mass concentration of 1 to 500mg/mL, for example: 10mg/mL, 50mg/mL, 100mg/mL, 150mg/mL, 200mg/mL, 250mg/mL, 300mg/mL, 350mg/mL, 400mg/mL, 450mg/mL, etc. When the mass concentration of the complexing agent is 1-500 mg/mL, the complexing agent with proper content can be obtained.
Further, in obtaining the second clarified solution, there is no particular limitation on the means for mixing, and preferably, the mixing may be performed under stirring. The stirring time is not particularly limited, and the present invention may be set as required as long as the second clear solution is obtained.
And finally, mixing the first clarified solution with the second clarified solution to obtain a mixed solution. In obtaining the mixed solution, there is no particular limitation on the means of mixing, and it is preferable that the mixing be performed under stirring. The stirring time is not particularly limited, and the present invention may be set as required as long as a mixed solution is obtained.
Specifically, when the first clarified solution and the second clarified solution are mixed, the stirring time may be 0.5 to 48 hours, for example: 1h, 5h, 10h, 15h, 20h, 25h, 30h, 35h, 40h, 45h, etc. When the stirring time is 0.5-48 h, the complexing agent, the cerium precursor and the transition metal precursor can be fully complexed, so that the catalyst with uniformly doped transition metal elements in atomic level can be stably obtained in the subsequent step. If the stirring time is too short, the complexation is incomplete, and if the stirring time is too long, the solvent volatilizes and energy is wasted.
Solvent evaporation
The invention forms a gel product by volatilizing the solvent in the mixed solution.
In some specific embodiments, the solvent in the mixed solution may be volatilized by heating. Preferably, the temperature of the heating is 40 to 120 ℃, for example: 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃ and the like, wherein the heating time is 0.5 to 48 hours, for example: 1h, 5h, 10h, 15h, 20h, 25h, 30h, 35h, 40h, 45h, etc. When the heating temperature is 40-120 ℃ and the heating time is 0.5-48 h, proper evaporation of the solvent and gel formation can be ensured, and a catalyst with transition metal elements uniformly doped in an atomic level can be stably obtained in the subsequent steps.
Ignition of
The invention obtains the burnout powder by igniting and aging the gel product.
In some specific embodiments, the gel product is ignited by means of an elevated temperature; preferably, the ignition temperature is 130-250 ℃, for example: 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃ and the like; the aging time is 0.5 to 48 hours, for example: 1h, 5h, 10h, 15h, 20h, 25h, 30h, 35h, 40h, 45h, etc. When the ignition temperature is 130-250 ℃ and the aging time is 0.5-48 hours, the gel can be ensured to be rapidly ignited, the cerium precursor, the transition metal element precursor and the complexing agent are fully decomposed, and finally the aging is stable, so that the cerium oxide nanocrystalline can be stably obtained in the subsequent step, if the ignition temperature is too low, the ignition cannot be performed, and if the ignition temperature is too high, energy is wasted and potential safety hazards are brought. If the aging time is too short, the obtained catalyst structure is unstable, and if the aging time is too long, the production time and energy are wasted.
Calcination
The catalyst is obtained by calcining the obtained burnout powder. Specifically, the calcination temperature is 200 to 800 ℃, for example: 250 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, etc.; the calcination time is 0.5 to 12 hours, for example: 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, etc. When the calcination temperature is 200-800 ℃ and the calcination time is 0.5-12 h, the catalyst can be ensured to be fully activated and the sintering deactivation caused by overlong time or overhigh temperature can not occur.
The calcination apparatus is not particularly limited, and for example, a tube furnace, a muffle furnace, or the like can be used.
The present invention is not particularly limited in other conditions of calcination, for example: can be carried out under oxygen-containing conditions, preferably at an oxygen content of 1 to 100%, for example: calcination is performed under conditions of 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% of oxygen content, etc.
< third aspect >
A third aspect of the present invention provides the use of a catalyst according to the first or second aspect of the present invention for the catalytic oxidation of volatile organic compounds. The catalyst of the invention can be widely applied to emission control of volatile organic waste gas in key industries such as petrochemical industry, spray coating manufacturing, package printing, leather manufacturing, textile printing and dyeing and the like.
In particular, the volatile organic compound may be one or more of aliphatic hydrocarbons, aromatic hydrocarbons, aldehydes, esters, ketones, acids or their halides, preferably including toluene.
Further, the catalyst of the present invention is used at a temperature of 100 to 600 ℃, for example: 150 ℃, 200 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, etc.
Examples
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
Step one: 12.38g of Ce (NO) were weighed out 3 ) 3 ·6H 2 O and 0.44g of Co (NO) 3 ) 2 ·6H 2 O, weighing 50mL of deionized water, dissolving the weighed cerium precursor and the transition metal element precursor solvent in the deionized water, and stirring for 1h to obtain a clear solution;
step two: weighing 6.30g of citric acid monohydrate, weighing 100mL of deionized water, dissolving the weighed citric acid monohydrate in the deionized water, and stirring for 1h to obtain a clear solution;
step three: adding the clarified solution obtained in the step one into the clarified solution obtained in the step two, and stirring for 4 hours to obtain a mixed solution;
step four: heating the mixed solution obtained in the step three at 80 ℃ for 3 hours to obtain gel, and evaporating deionized water to form a gel product;
step five: heating and igniting the gel obtained in the step four at 200 ℃ and aging for 12 hours to obtain burnout powder;
step six: calcining the burnout powder obtained in the fifth step at 600 ℃ for 4 hours under the air (oxygen content of 21%) to obtain the Co for catalyzing and oxidizing the volatile organic compounds 5％ -CeO 2 A catalyst.
Example 2
Using the same procedure as in example 1, only Ce (NO 3 ) 3 ·6H 2 O was changed to 11.72g, co (NO 3 ) 2 ·6H 2 O was changed to 0.87g to obtain Co 10％ -CeO 2 A catalyst.
Example 3
Using the same procedure as in example 1, only Ce (NO 3 ) 3 ·6H 2 O was changed to 11.07g, co (NO) 3 ) 2 ·6H 2 O was changed to 1.31g to obtain Co 15％ -CeO 2 A catalyst.
Comparative example
Transition metal undoped ceria (CeO) 2 ) Preparation of the catalyst
Using the same procedure as in example 1, only Ce (NO 3 ) 3 ·6H 2 O becomes 13.03g, co (NO) 3 ) 2 ·6H 2 O to obtain CeO 2 A catalyst.
Performance testing
1. Catalytic oxidation Performance test
Test conditions: the catalyst powders obtained in examples 1-3 and comparative example were tabletted, crushed and sieved, 40-60 mesh catalyst particles were selected for evaluation of catalytic oxidation activity of VOCs, toluene was selected by treating exhaust gas with 0.1g of catalyst, total flow rate of exhaust gas was 100mL/min, space velocity GHSV 60,000 mL/(gh), exhaust gas concentration was 1000ppm toluene, O 2 21vol.％，N 2 79vol.% and the results are shown in figure 1.
From the test results, the toluene catalytic oxidation activity of the catalysts of examples 1-3 of the present invention increases rapidly with increasing temperature, and the toluene conversion at each operating temperature of 245-300 ℃ is significantly better than that of the comparative examples, with significantly lower activation temperature and toluene 90% conversion temperature.
2. Microstructure testing
FIG. 2 shows Co according to example 2 of the present invention 10％ -CeO 2 Microstructure test results of the catalyst. Wherein a in FIG. 2 shows Co 10％ -CeO 2 An X-ray diffraction spectrum of the catalyst; b in FIG. 2 shows Co 10％ -CeO 2 X-ray absorption fine structure spectrum of the catalyst;c in FIG. 2 shows Co 10％ -CeO 2 A transmission electron microscope image of the catalyst; d in FIG. 2 shows Co 10％ -CeO 2 Spherical aberration correcting scanning transmission electron microscope image of the catalyst.
As can be seen from FIG. 2, co of example 2 of the present invention 10％ -CeO 2 The catalyst retains the phase and lattice structure of the ceria; co (Co) 10％ -CeO 2 No segregated or agglomerated cobalt element was observed for the catalyst. And Co is 10％ -CeO 2 The cobalt element in the catalyst is uniformly doped in an atomic level in the crystal lattice of the cerium oxide; in addition, it can be seen that Co 10％ -CeO 2 Is a porous material, and has an average pore diameter of about 3-4 nm; co (Co) 10％ -CeO 2 The cobalt-doped cerium dioxide nanocrystalline composite material is formed by stacking cobalt-doped cerium dioxide nanocrystalline, wherein the average diameter of single nanocrystalline is about 5-7 nm, and the size is uniform; co (Co) 10％ -CeO 2 As the cobalt element is evenly doped in atomic level to generate tensile lattice strain, the cerium oxide lattice has a defect structure such as distortion, stacking fault and the like, which is favorable for generating reactive sites such as oxygen vacancies and the like.
In addition, the applicant also conducted microstructure test analysis on examples 1 and 3, and the results were substantially identical to the microstructure of example 2.
The above examples of the present invention are merely illustrative of the present invention and are not intended to limit the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (12)
1. A catalyst, characterized in that the catalyst is composed of CeO 2 The nano-crystal is formed by stacking, wherein,
the CeO 2 The crystal lattice of the nanocrystalline is doped with transition metal which is doped in atomic level; and, in addition, the processing unit,
the catalyst has a catalyst composed of CeO 2 A plurality of pore canal structures are formed by stacking the nanocrystals, the average pore diameter of the pore canal structures is 2-20 nm,
wherein the stacking is a disordered stacking; the mol ratio of transition metal element to Ce element in the catalyst is 1:99-30:70;
the preparation method of the catalyst comprises the following steps:
mixing a cerium precursor, a transition metal precursor and a complexing agent in a solvent to obtain a mixed solution;
volatilizing the solvent in the mixed solution to form a gel product;
igniting and aging the gel product to obtain burnout powder;
calcining the burnout powder to obtain a catalyst;
wherein the complexing agent comprises one or more than two of citric acid, EDTA and cetrimide; the solvent is water.
2. The catalyst according to claim 1, wherein the CeO is singly of said CeO 2 The average diameter of the nanocrystalline is 2-30 nm.
3. The catalyst according to claim 1 or 2, characterized in that it is expressed as:
TM n％ -CeO 2
wherein TM represents a transition metal element, n% represents the mole percentage of the transition metal element to the total metal elements in the catalyst, and the value of n is 1-30.
4. A catalyst according to claim 3, wherein the transition metal element comprises one or a combination of two or more of Fe, mn, co, cu, ni, zn, cr, ti, pd, ag, cd.
5. A method for preparing the catalyst according to any one of claims 1 to 4, comprising the steps of:
mixing a cerium precursor, a transition metal precursor and a complexing agent in a solvent to obtain a mixed solution;
volatilizing the solvent in the mixed solution to form a gel product;
igniting and aging the gel product to obtain burnout powder;
calcining the burnout powder to obtain a catalyst;
wherein the complexing agent comprises one or more than two of citric acid, EDTA and cetrimide; the solvent is water.
6. The method according to claim 5, wherein the mass ratio of the cerium precursor to the transition metal precursor is 5:1 to 200:1; and/or the ratio of the mass of the complexing agent to the total mass of the cerium precursor and the transition metal precursor is 1:10-2:1.
7. The preparation method according to claim 5 or 6, wherein the mass concentration of the complexing agent in the mixed solution is 0.5-250 mg/mL; and/or, in the mixed solution, the total mass concentration of the cerium precursor and the transition metal precursor is 0.5-250 mg/mL.
8. The method according to claim 5 or 6, wherein the solvent in the mixed solution is volatilized by heating; and/or
The gel product is ignited by means of an elevated temperature.
9. The method according to claim 8, wherein the heating temperature is 40 to 120 ℃ and the heating time is 0.5 to 48 hours.
10. The method of claim 8, wherein the ignition temperature is 130-250 ℃ and the aging time is 0.5-48 hours.
11. The method according to claim 5 or 6, wherein the calcination is calcination under an oxygen content of 1 to 100%; the calcination temperature is 200-800 ℃, and the calcination time is 0.5-12 h.
12. Use of a catalyst according to any one of claims 1-4 for the catalytic oxidation of volatile organic compounds.
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