CN115532273A - Catalyst, preparation method and application thereof - Google Patents
Catalyst, preparation method and application thereof Download PDFInfo
- Publication number
- CN115532273A CN115532273A CN202211267858.5A CN202211267858A CN115532273A CN 115532273 A CN115532273 A CN 115532273A CN 202211267858 A CN202211267858 A CN 202211267858A CN 115532273 A CN115532273 A CN 115532273A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- transition metal
- ceo
- precursor
- cerium
- 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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- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 69
- 150000003624 transition metals Chemical class 0.000 claims abstract description 47
- 230000003197 catalytic effect Effects 0.000 claims abstract description 21
- 239000002159 nanocrystal Substances 0.000 claims abstract description 21
- 239000011148 porous material Substances 0.000 claims abstract description 21
- 239000012855 volatile organic compound Substances 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 230000003647 oxidation Effects 0.000 claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- 239000013078 crystal Substances 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims description 35
- 239000012695 Ce precursor Substances 0.000 claims description 33
- 239000002904 solvent Substances 0.000 claims description 33
- 239000008139 complexing agent Substances 0.000 claims description 30
- 239000011259 mixed solution Substances 0.000 claims description 23
- 238000001354 calcination Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 15
- 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
- 230000032683 aging Effects 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 229920001400 block copolymer Polymers 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 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 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- 229960002798 cetrimide Drugs 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 238000009826 distribution Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 21
- 229910000420 cerium oxide Inorganic materials 0.000 description 15
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 15
- 238000003756 stirring Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical group C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 9
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 9
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 9
- 229920001983 poloxamer Polymers 0.000 description 9
- 229960000502 poloxamer Drugs 0.000 description 9
- 229910052684 Cerium Inorganic materials 0.000 description 8
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910052726 zirconium Inorganic materials 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 239000007789 gas Substances 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
- 238000003860 storage Methods 0.000 description 4
- 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
- 230000009286 beneficial effect Effects 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
- 230000008020 evaporation Effects 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
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- ZGMCLEXFYGHRTK-UHFFFAOYSA-N [Fe].[Ce] Chemical compound [Fe].[Ce] ZGMCLEXFYGHRTK-UHFFFAOYSA-N 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
- 238000012937 correction Methods 0.000 description 2
- 230000006378 damage 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
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 238000011056 performance test Methods 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
- 238000000851 scanning transmission electron micrograph Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005303 weighing Methods 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
- 238000009825 accumulation Methods 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
- 230000004913 activation Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 238000003915 air pollution Methods 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
- 159000000032 aromatic acids Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 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
- 238000006065 biodegradation reaction Methods 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
- AZRCLCUGADNYQP-UHFFFAOYSA-H cerium(3+) trisulfite Chemical compound [Ce+3].[Ce+3].[O-]S([O-])=O.[O-]S([O-])=O.[O-]S([O-])=O AZRCLCUGADNYQP-UHFFFAOYSA-H 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
- 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
- 230000000536 complexating effect Effects 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
- 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
- 239000006185 dispersion Substances 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
- 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
- 229940062993 ferrous oxalate Drugs 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000000446 fuel 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
- 230000002779 inactivation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002505 iron 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
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-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
- 239000000463 material Substances 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
- 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
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 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
- 238000001556 precipitation Methods 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 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
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- 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 made of CeO 2 Nano crystal is stacked, wherein, the CeO 2 The crystal lattice of the nanocrystal is doped with a transition metal, and the catalyst has a structure made of CeO 2 And a plurality of pore channel structures are formed by stacking the nano crystals, and the average pore diameter of the pore channel structures is 2-20 nm. The catalyst disclosed by the invention has the advantages of 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. Further, the catalysis of the present inventionThe preparation method of the agent is simple and easy to implement, the raw materials are easy to obtain, and the agent is suitable for mass production.
Description
Technical Field
The invention relates to a catalyst, a preparation method and application thereof, in particular to a catalyst for catalytic oxidation of volatile organic compounds, a preparation method and application thereof, and belongs to the field of catalysts.
Background
Volatile Organic Compounds (VOCs) are organic compounds with saturated vapor pressure higher than 133.32Pa and boiling point between 50-250 deg.C, have atmospheric photochemical reactivity, can produce photochemical smog and secondary organic aerosol, and are O 3 And PM 2.5 The common precursor is the key of air pollution treatment.
The 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 high concentration. The destruction method has wider application range, mainly aims at more common emission sources lacking in recovery value, and converts VOCs into carbon dioxide and water through combustion, catalytic oxidation, biodegradation and other modes 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 widest application prospect. The VOCs catalytic combustion catalyst applied in the industry at present is mainly a noble metal catalyst, has high cost and is easy to inactivate due to loss, sintering, poisoning and the like of noble metals. In addition, the precious metal reserves in our country are insufficient, and the strategic safety of industrial production and people's life can be seriously harmed by over-relying on the precious metal catalyst.
The cerium-based catalyst has excellent oxidation-reduction property and oxygen storage and release capacity, the light rare earth element has low price and good prospect of replacing noble metal to realize industrial application, but the problems of poor dispersion of doping elements, low content of active sites, insufficient activity and the like generally exist in the conventional cerium-based catalyst.
Therefore, the technical problems to be solved are to improve the dispersibility of doping elements in the catalyst, increase the content of active sites and improve the catalytic combustion performance of VOCs.
The cited documents are:
citation 1: CN 113398939A
Cited document 2: CN 112076740A
Disclosure of Invention
Problems to be solved by the invention
In view of the technical problems 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 disclosed by the invention has the advantages of 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 feasible, has easily obtained raw materials and is suitable for mass production.
Means for solving the problems
[1]The catalyst is prepared from CeO 2 The nano-crystals are piled up, wherein,
the CeO 2 The crystal lattice of the nanocrystal is doped with a transition metal, and,
the catalyst has a composition of CeO 2 And a plurality of pore channel structures are formed by stacking the nano crystals, and the average pore diameter of the pore channel structures is 2-20 nm.
[2]According to the above [1]The catalyst, wherein the CeO is singly present 2 The average diameter of the nanocrystalline is 2-30 nm; and/or the molar ratio of the transition metal element to the Ce element in the catalyst is 1.
[3] The catalyst according to the above [1] or [2], wherein the catalyst is represented by:
TM n％ -CeO 2
wherein TM represents transition metal element, n% represents the mole percentage content of the transition metal element in the total metal elements in the catalyst, and the value of n is 1-30;
preferably, the transition metal element comprises one or a combination of more than two of Fe, mn, co, cu, ni, zn, V, cr, ti, pd, ag and Cd.
[4] A process for producing a catalyst according to any one of the above [1] to [3], which 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 a mass ratio of the cerium precursor to the transition metal precursor is 5:1 to 200; 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 to 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 production method according to any one of [4] to [6], wherein the complexing agent includes one or a combination of two or more of citric acid, EDTA, a polyoxyethylene polyoxypropylene block copolymer, and cetrimide.
[8] The production methods 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 raising the temperature; preferably, the ignition temperature is 130-250 ℃, and the aging time is 0.5-48 h.
[9] The production process according to the above [4] to [8], wherein the calcination is a calcination under an oxygen content of 1 to 100%; the calcining temperature is 200-800 ℃, and the calcining time is 0.5-12 h.
[10] And a use of the catalyst according to any one of the above [1] to [3] for catalytic oxidation of volatile organic compounds.
ADVANTAGEOUS EFFECTS OF INVENTION
The catalyst disclosed by the invention has the advantages of 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, the raw materials are easy to obtain, and the catalyst is suitable for mass production.
Drawings
FIG. 1 shows a graph of the conversion of toluene by catalytic oxidation of catalysts of examples 1-3 of the present invention and comparative example 1 as a function of temperature.
FIG. 2 shows Co of 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 X-ray diffraction spectra 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 Transmission electron micrographs of the catalyst;
d in FIG. 2 shows Co 10％ -CeO 2 Spherical aberration correction scanning transmission electron micrographs of the catalyst.
Detailed Description
Various exemplary embodiments, features and aspects of the invention will be described in detail below. The word "exemplary" is used exclusively 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 understanding of the present 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, methods, means, devices and steps which are well known to those skilled in the art have not been described in detail so as not to obscure the invention.
All units used in the specification are international standard units unless otherwise stated, and numerical values and numerical ranges appearing in the present invention should be understood to include systematic errors inevitable in industrial production.
In the present specification, "%" denotes mass% unless otherwise specified.
In the present specification, the meaning of "may" includes both the meaning of performing a certain process and the meaning of not performing a certain process.
In the present specification, reference to "some particular/preferred embodiments," "other particular/preferred embodiments," "embodiments," and the like, 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 described elements may be combined in any suitable manner in the various embodiments.
In the present specification, the numerical range represented by "a value a to B value" means a range including the endpoint value A, B.
< first aspect >
A first aspect of the invention provides a catalyst consisting of CeO 2 The nano-crystals are piled up, wherein,
the CeO 2 The crystal lattice of the nanocrystal is doped with a transition metal, and,
the catalyst has a composition of CeO 2 And a plurality of pore channel structures are formed by stacking the nano crystals, and the average pore diameter of the pore channel structures is 2-20 nm.
The transition metal element in the catalyst disclosed by the invention is uniformly doped in an atomic level, has excellent catalytic activity, is similar to a noble metal catalyst, has good stability and is low in cost.
In the present invention, the transition metal is in CeO 2 The crystal lattice of the nano crystal is uniformly doped in an atomic level, and segregation and agglomeration phenomena cannot occur; the inventor finds that the transition metal doping can induce cerium dioxide to form reactive sites such as oxygen vacancies, and the transition metal doping can be used as an electron assistant to improve the oxidation-reduction property and oxygen storage and release capacity of the cerium dioxide, but the segregation and agglomeration of the transition metal doping can weaken the effect.
CeO of the invention 2 The grain size of the nanocrystal is uniform, ceO 2 Multiple pore channel structures can be formed among the nanocrystals through disordered stacking. The uniform grain size can ensure the homogeneity of the catalyst and promote the further coating utilizationThe porous structures are beneficial to the adsorption process of pollutants such as volatile organic compounds and the like, and the porous structures are the basis for improving the catalytic oxidation performance.
The inventor finds that the average pore diameter of the pore channel structure is too small, which is not beneficial to the diffusion of reactants, the average pore diameter of the pore channel structure is too large, the specific surface area is reduced, the exposure number of active sites is reduced, and the reaction is not beneficial. Therefore, 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, the CeO is present singly 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 single CeO 2 If the diameter of the nanocrystalline is too small, the nanocrystalline is difficult to synthesize and easy to sinter; if single CeO 2 The diameter of the nano crystal is too large, the specific surface area of the catalyst is likely to be obviously reduced, the exposure number of active sites is reduced, and the reaction is not facilitated. Preferably, the individual nanocrystals have an average diameter of 4 to 10nm.
In other specific embodiments, the molar ratio of transition metal element to Ce element in the catalyst is from 1: the following components 98, 5. If the content of the transition metal element is too low, the activity is not sufficiently improved, and if the content of the transition metal element is too high, segregation is caused.
Further, in the present invention, the catalyst is represented by:
TM n％ -CeO 2
wherein TM represents a transition metal element, n% represents the mole percent of the transition metal element based on the total metal elements in the catalyst, and the value of n is from 1 to 30, for example: 2. 5, 8, 10, 12, 15, 18, 20, 22, 25, 28, etc.;
preferably, the transition metal element comprises one or a combination of more than two of Fe, mn, co, cu, ni, zn, V, cr, ti, pd, ag and Cd.
<Second aspect of the invention>
A second aspect of the present invention provides a method for preparing the 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 a commercial prospect.
Mixing of
The cerium precursor, the transition metal precursor and the complexing agent are mixed in a solvent to obtain a mixed solution.
In some specific embodiments, the mass ratio of the cerium precursor to the transition metal precursor is 5:1 to 200, for example: 10; the inventors found that when the mass ratio of the cerium precursor to the transition metal precursor is 5:1 to 200. If the mass ratio of the cerium precursor to the transition metal precursor is too high, the doping amount of the transition metal element is too small, and the performance is not good, and if the mass ratio of the cerium precursor to the transition metal precursor is too low, the doping of the transition metal element is not uniform, and the phase of the transition metal element is changed.
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, and the like. The total mass concentration of the cerium precursor and the transition metal precursor can regulate and control the synthesis amount of the catalyst, if the total mass concentration of the cerium precursor and the transition metal precursor is too high, the cerium precursor and the transition metal precursor can be possibly not 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 to 2:1, for example: 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, 1:1, and the like. The inventor finds 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 1-2:1, 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 complexing 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 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, and the like. If the mass concentration of the complexing agent is too high, the complexing agent can not be completely dissolved, and if the mass concentration of the complexing agent is too low, the solvent is wasted.
Further, in the present invention, the cerium precursor may be generally any cerium salt that is feasible in the present invention. For example: cerium nitrate, cerium chloride, cerium trifluoride, cerium tetrafluoride, ammonium cerium nitrate, cerium sulfate, cerium sulfite, cerium acetate, cerium oxalate, cerium bromide, ammonium cerium sulfate, and the like.
For the transition metal precursor, any of the transition metal-containing salts that are feasible in the present invention can generally be used. Taking manganese salt, iron salt, cobalt salt, nickel salt and copper salt as examples, the transition metal precursor may be one or a combination of two 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, ferrous 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 in the present invention, and may be any complexing agent that can form a gel. Specifically, the complexing agent comprises one or a combination of more than two of citric acid, EDTA, polyoxyethylene polyoxypropylene ether block copolymer and cetrimide. Wherein the citric acid can comprise citric acid monohydrate, and the polyoxyethylene polyoxypropylene block copolymer can be poloxamer P85, poloxamer P94, poloxamer P104, poloxamer P105, poloxamer L121, poloxamer L122, poloxamer P123, poloxamer F127, poloxamer F68, etc.
As the solvent, the present invention 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, or the like, and the solvent may be at least one of water, ethanol, methanol, or acetone in view of the subsequent treatment. In some embodiments of the present invention, the solvent may also be a mixture of the above-mentioned polar solvent and water, and when the solvent is used as a mixed solvent, the mass fraction of water in the solvent is preferably 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 clarified solution;
mixing a complexing agent in a solvent to obtain a second clear solution;
and mixing the first clarified solution and the second clarified solution to obtain a mixed solution.
According to the invention, the first clarified solution is obtained firstly, so that the cerium precursor and the transition metal precursor can be fully contacted, and the cerium dioxide nanocrystalline catalyst with uniform transition metal 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, and the like. When the total mass concentration of the cerium precursor and the transition metal precursor is 1-500 mg/mL, the cerium precursor and the transition metal precursor with appropriate contents can be obtained.
Further, in obtaining the first clarified solution, there is no particular limitation on the apparatus for mixing, and preferably, the mixing may be performed under stirring during the mixing. The time of stirring is not particularly limited in the present invention, and may be set as needed as long as the first clarified solution is obtained.
According to the invention, the second clarified solution is obtained, so that the complexing agent and the solvent can be fully combined, and the cerium precursor and the transition metal precursor ions can be stably complexed in the subsequent steps.
Specifically, in the first clear solution of the present invention, the mass concentration of the complexing agent 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, and the like. 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, the means for mixing is not particularly limited, and preferably, the mixing may be performed under stirring during the mixing. The time for stirring is not particularly limited in the present invention, and may be set as needed as long as a 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 a device for mixing, and preferably, the mixing may be performed under stirring during the mixing. The time for stirring is not particularly limited, and may be set as needed 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 and the like. When the stirring time is 0.5-48 h, the complexing agent can be fully complexed with the cerium precursor and the transition metal precursor, and the subsequent steps can be ensured to stably obtain the catalyst with the transition metal elements uniformly doped in the atomic level. If the stirring time is too short, the complexation is incomplete, and if the stirring time is too long, the solvent is volatilized and energy is wasted.
Volatilization of solvent
The invention forms gel product by volatilizing the solvent in the mixed solution.
In some embodiments, the solvent in the mixed solution may be volatilized by heating. Preferably, the heating temperature is 40 to 120 ℃, for example: 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃ and the like, and the heating time is 0.5 to 48 hours, such as: 1h, 5h, 10h, 15h, 20h, 25h, 30h, 35h, 40h, 45h and the like. 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, the catalyst with the transition metal elements uniformly doped in an atomic level can be stably obtained in the subsequent steps, incomplete evaporation of the solvent can be caused if the heating time is too short and/or the temperature is too low, excessive evaporation of the solvent can not form gel if the heating time is too long and/or the temperature is too high, and premature ignition of the solution can be caused if the temperature is too high.
Igniting the fuel
The burnout powder is obtained by igniting and aging the gel product.
In some specific embodiments, the gel product is ignited by means of an elevated temperature; preferably, the temperature of the ignition is 130 to 250 ℃, for example: 150 deg.C, 160 deg.C, 170 deg.C, 180 deg.C, 190 deg.C, 200 deg.C, 210 deg.C, 220 deg.C, 230 deg.C, 240 deg.C, etc.; the aging time is 0.5 to 48 hours, for example: 1h, 5h, 10h, 15h, 20h, 25h, 30h, 35h, 40h, 45h and the like. When the ignition temperature is 130-250 ℃, the aging time is 0.5-48 h, the rapid ignition of the gel can be ensured, 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 dioxide nanocrystalline can be stably obtained in the subsequent steps, 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 caused. If the aging time is too short, the resulting catalyst structure may be unstable, and if the aging time is too long, production time and energy may be wasted.
Calcination of
The catalyst is obtained by calcining the obtained burnout powder. Specifically, the temperature of the calcination is 200 to 800 ℃, for example: 250 deg.C, 300 deg.C, 350 deg.C, 400 deg.C, 450 deg.C, 500 deg.C, 550 deg.C, 600 deg.C, 650 deg.C, 700 deg.C, 750 deg.C, etc.; the calcination time is 0.5 to 12 hours, for example: 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h and the like. When the calcining temperature is 200-800 ℃ and the calcining time is 0.5-12 h, the catalyst can be ensured to be fully activated and sintering inactivation cannot occur due to overlong time or overhigh temperature.
The apparatus for calcination is not particularly limited, and, for example, a tube furnace, a muffle furnace, or the like can be used.
Other conditions for the calcination in the present invention are not particularly limited, and examples thereof include: can be carried out under oxygen-containing conditions, and can preferably be carried out at an oxygen content of 1 to 100%, for example: the calcination is performed under conditions of 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% oxygen content, etc.
< third aspect >
A third aspect of the invention provides the use of a catalyst according to the first or second aspect of the invention in the catalytic oxidation of volatile organic compounds. The catalyst of the invention can be widely applied to the emission control of volatile organic compound waste gas in heavy-spot industries such as petrochemical industry, spraying manufacturing, packaging printing, leather manufacturing, textile printing and dyeing and the like.
Specifically, the volatile organic compound may be one or more of aliphatic hydrocarbon, aromatic hydrocarbon, aldehyde, ester, ketone, acid or their halide, preferably including toluene.
Further, the catalyst of the present invention is used at a temperature of 100 to 600 ℃, for example: 150 deg.C, 200 deg.C, 250 deg.C, 300 deg.C, 350 deg.C, 400 deg.C, 450 deg.C, 500 deg.C, 550 deg.C, etc.
Examples
Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are commercially available, and are not indicated by manufacturers.
Example 1
The method comprises the following steps: 12.38g of Ce (NO) are weighed out 3 ) 3 ·6H 2 O and 0.44g Co (NO) 3 ) 2 ·6H 2 Measuring 50mL of deionized water, dissolving the weighed cerium precursor and the transition metal 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 clear solution obtained in the step one into the clear 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 third step at 80 ℃ for 3h to obtain gel, and evaporating deionized water to form a gel product;
step five: heating the gel obtained in the step four at 200 ℃ for ignition and aging for 12h to obtain burnout powder;
step six: calcining the burnout powder obtained in the fifth step for 4 hours at 600 ℃ in air (with the oxygen content of 21 percent) to obtain the catalyst for catalytic oxidation volatilizationOrganic Co 5％ -CeO 2 A catalyst.
Example 2
Using the same procedure as in example 1, only Ce (NO) added 3 ) 3 ·6H 2 O to 11.72g, co (NO) added 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) added 3 ) 3 ·6H 2 O changed to 11.07g, co (NO) added 3 ) 2 ·6H 2 O was changed to 1.31g to obtain Co 15％ -CeO 2 A catalyst.
Comparative example
Cerium oxide (CeO) not doped with transition metal 2 ) Preparation of the catalyst
Using the same procedure as in example 1, only Ce (NO) added 3 ) 3 ·6H 2 O changed to 13.03g, and Co (NO) was not added any more 3 ) 2 ·6H 2 O to obtain CeO 2 A catalyst.
Performance test
1. Catalytic Oxidation Performance test
And (3) testing conditions are as follows: the catalyst powders obtained in the examples 1-3 and the comparative example are tableted, crushed and sieved, 40-60 meshes of catalyst particles are selected for evaluating the catalytic oxidation activity of VOCs, 0.1g of catalyst is adopted, toluene is selected for treating exhaust gas, the total flow of the exhaust gas is 100mL/min, the gas space velocity GHSV is 60, 000mL/(gh), the concentration of the exhaust gas is 1000ppm toluene, O 2 21vol.％，N 2 79vol.%, the results are shown in fig. 1.
From the test results, it can be seen that the catalytic oxidation activity of toluene of the catalysts of examples 1-3 of the present invention rapidly increases with increasing temperature, the toluene conversion at each operating temperature of 245-300 ℃ is significantly better than that of the comparative example, and the catalysts have significantly lower activation temperature and toluene 90% conversion temperature.
2. Microstructural testing
FIG. 2 showsCo of 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 X-ray diffraction spectra 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 Transmission electron micrograph of catalyst; d in FIG. 2 shows Co 10％ -CeO 2 Spherical aberration correction scanning transmission electron micrographs 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 cerium dioxide; co 10％ -CeO 2 No segregated or agglomerated cobalt element was observed for the catalyst. And Co 10％ -CeO 2 The cobalt element in the catalyst is uniformly doped in the crystal lattice of cerium dioxide in an atomic level; in addition, it can also be seen that Co 10％ -CeO 2 Is a porous material with an average pore diameter of about 3-4 nm; co 10％ -CeO 2 The cerium dioxide nano-crystal material is formed by stacking cobalt element doped cerium dioxide nano-crystals, the average diameter of a single nano-crystal is about 5-7 nm, and the size is uniform; co 10％ -CeO 2 Because the cobalt element is uniformly doped at atomic level to generate tensile lattice strain, the cerium dioxide crystal lattice has defect structures such as distortion, stacking fault and the like, and the generation of reactive sites such as oxygen vacancy and the like is facilitated.
In addition, the applicant also performed microstructure test analysis on examples 1 and 3, and the results thereof were substantially identical to the microstructure of example 2.
The above examples of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A catalyst, characterized in that the catalyst is prepared from CeO 2 The nano-crystals are piled up, wherein,
the CeO 2 The crystal lattice of the nanocrystal is doped with a transition metal, and,
the catalyst has a composition of CeO 2 And a plurality of pore channel structures are formed by accumulating the nano crystals, and the average pore diameter of the pore channel structures is 2-20 nm.
2. The catalyst according to claim 1, wherein the CeO is present singly 2 The average diameter of the nanocrystalline is 2-30 nm; and/or the molar ratio of the transition metal element to the Ce element in the catalyst is 1.
3. The catalyst according to claim 1 or 2, characterized in that it is represented by:
TM n％ -CeO 2
wherein TM represents transition metal element, n% represents the mole percentage content of the transition metal element in the total metal elements in the catalyst, and the value of n is 1-30;
preferably, the transition metal element comprises one or a combination of more than two of Fe, mn, co, cu, ni, zn, V, cr, ti, pd, ag and Cd.
4. A method for preparing a catalyst according to any one of claims 1 to 3, 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.
5. The preparation method according to claim 4, wherein the mass ratio of the cerium precursor to the transition metal precursor is 5:1-200; 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 to 2:1.
6. The preparation method according to claim 4 or 5, characterized in that 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.
7. The method according to any one of claims 4 to 6, wherein the complexing agent comprises one or a combination of two or more of citric acid, EDTA, a polyoxyethylene polyoxypropylene block copolymer, and cetrimide.
8. The production method according to any one of claims 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 raising the temperature; preferably, the ignition temperature is 130-250 ℃, and the aging time is 0.5-48 h.
9. The production method according to any one of claims 4 to 8, wherein the calcination is calcination under an oxygen content of 1 to 100%; the calcining temperature is 200-800 ℃, and the calcining time is 0.5-12 h.
10. Use of a catalyst according to any one of claims 1 to 3 for the catalytic oxidation of volatile organic compounds.
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