CN111185182A - Perovskite catalyst and preparation method and application thereof - Google Patents
Perovskite catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN111185182A CN111185182A CN202010149904.6A CN202010149904A CN111185182A CN 111185182 A CN111185182 A CN 111185182A CN 202010149904 A CN202010149904 A CN 202010149904A CN 111185182 A CN111185182 A CN 111185182A
- Authority
- CN
- China
- Prior art keywords
- perovskite
- catalyst
- perovskite catalyst
- microspheres
- preparation
- 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
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 9
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 7
- 150000002910 rare earth metals Chemical group 0.000 claims abstract description 7
- 150000003624 transition metals Chemical class 0.000 claims abstract description 7
- 150000001342 alkaline earth metals Chemical group 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 23
- 239000004005 microsphere Substances 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 17
- -1 amino silica microspheres Chemical compound 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 13
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 13
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 13
- 239000003929 acidic solution Substances 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 11
- 238000001179 sorption measurement Methods 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000004090 dissolution Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 5
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 20
- 230000000694 effects Effects 0.000 abstract description 20
- 229910052712 strontium Inorganic materials 0.000 abstract description 10
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 abstract description 10
- 230000002411 adverse Effects 0.000 abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
- 239000012855 volatile organic compound Substances 0.000 description 22
- 239000007787 solid Substances 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000001914 filtration Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 230000001590 oxidative effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 6
- 229910002187 La0.8Sr0.2CoO3 Inorganic materials 0.000 description 5
- 229960000583 acetic acid Drugs 0.000 description 5
- 238000007084 catalytic combustion reaction Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 229910052746 lanthanum Inorganic materials 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- 235000011054 acetic acid Nutrition 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 4
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 229910019828 La0.7Sr0.3CoO3 Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 150000004677 hydrates Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 229940006465 strontium cation Drugs 0.000 description 2
- PWYYWQHXAPXYMF-UHFFFAOYSA-N strontium(2+) Chemical compound [Sr+2] PWYYWQHXAPXYMF-UHFFFAOYSA-N 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910002254 LaCoO3 Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910003508 Sr0.3CoO3 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- OBFQBDOLCADBTP-UHFFFAOYSA-N aminosilicon Chemical compound [Si]N OBFQBDOLCADBTP-UHFFFAOYSA-N 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- YENOLDYITNSPMQ-UHFFFAOYSA-N carboxysilicon Chemical compound OC([Si])=O YENOLDYITNSPMQ-UHFFFAOYSA-N 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
- 229940005991 chloric acid Drugs 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 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
- 229920000642 polymer Polymers 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
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
-
- 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
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/651—50-500 nm
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention provides a perovskite catalyst and a preparation method and application thereof. The preparation method comprises the following steps: adsorbing the raw material solution by using a template agent to obtain a catalyst precursor; carrying out heat treatment on the catalyst precursor to obtain a doped perovskite type compound; at least partially dissolving the composite by which to at least partially remove the B element from the surface of the composite; wherein the doped perovskite-type complex has a composition A of the following formula (I)1‑xBxCO3(I) B represents doping in ACO3Metal element in perovskite structure, A element is selected from rare earth metal, B element is selected from alkaline earth metal, C is selected from transition metal, 0<x<1。The perovskite catalyst overcomes the adverse effect of the surface-enriched strontium element on the activity of the catalyst, and has high catalytic activity.
Description
Technical Field
The invention relates to purification treatment of volatile organic waste gas, in particular to a perovskite catalyst and a preparation method and application thereof, and particularly relates to a perovskite catalyst for efficiently catalyzing and oxidizing VOCs (volatile organic compounds), and preparation and application thereof, belonging to the technical field of environmental protection.
Background
Volatile Organic Compounds (VOCs) are one of the major atmospheric pollutants today and are extremely harmful to human health as well as to the environment. The volatile organic compounds mainly come from daily life such as building materials and decoration materials, and industries such as chemical engineering, boiler tail gas of power plants and the like. Most of volatile organic compounds (such as low carbon hydrocarbons, aromatic hydrocarbons, aldehydes and the like) have toxicity, foul smell, flammability and explosiveness, not only cause pollution to the ecological environment (such as photochemical smog, ozone layer damage, secondary organic aerosol and the like), but also seriously threaten human health. Because the pollution surface of the volatile organic compound is wide, the harm is large, the components are complex, the treatment difficulty is large, and the research on the control and treatment of the volatile organic compound has important significance for the sustainable development of human society.
Volatile organic compound emissions have been controlled by various means including activated carbon adsorption, biofiltration, thermal incineration, and catalytic combustion techniques. Of the many volatile organic compound removal technologies, catalytic combustion technology is the most viable mainstream technology. Has the advantages of high efficiency, no secondary pollution, wide application range, energy conservation and the like. At present, the research focus of the catalyst in the catalytic combustion technology mainly focuses on two main categories of noble metal and transition metal oxide. Noble metals are common low-temperature catalytic combustion catalysts and have high catalytic activity, but the problems of easy poisoning, resource scarcity, high cost and the like limit the large-scale popularization and application of the noble metals. The transition metal oxide contains various oxidation state metal ions and lattice defects (oxygen vacancies), and is favorable for volatile organic compounds and O2The adsorption and activation of the catalyst can lead the catalyst to show good activity in the catalytic combustion reaction of volatile organic compounds. And transition metal oxygenThe catalyst also has the advantages of low price, environmental protection, high thermal stability and the like, and has been increasingly paid more attention by academic circles and industrial circles.
The perovskite is a metal oxide formed by compounding transition metal and rare earth metal, and has proved to have better activity and high stability in the catalytic oxidation process of volatile organic compounds. Perovskite-type metal oxide (ABO)3) Due to their variability in composition and structure, they have different physicochemical properties (such as redox behavior, oxygen mobility, electronic and ionic conductivity), have been studied extensively over the past few decades, and have been used in various fields.
It is well known that the catalytic activity of perovskite-type metal oxides is related to their physicochemical properties, including morphology, specific surface area, pore structure and oxygen non-stoichiometry. In recent years, various methods of synthesizing perovskite metal oxides (soft-film plate method, hydrothermal method, combustion method, sol-gel method, coprecipitation method, molten salt method, etc.) have been successively reported to improve their physicochemical properties, thereby improving their catalytic activities. There are also researchers that can improve the catalytic activity of perovskites by doping the a site with other elements. However, the doped elements tend to concentrate on the surface of the perovskite, blocking the catalytically active B site elements, limiting further enhancement of perovskite activity.
Citation 1 discloses a high-activity perovskite hollow particle catalyst, and preparation and application thereof, wherein the catalyst has a nano-scale hollow particle structure and La1-xSrxFel-yMnyO3The compound oxide with perovskite type characteristic has the mole ratio of the sum of lanthanum cation and strontium cation to the sum of iron cation and manganese cation of 0.6-2, and the content of strontium cation and manganese cation can be adjusted, namely the value of x is within the range of 0-0.1, and the value of y is within the range of 0-0.3. However, the preparation method of the catalyst is complex, and the requirements on required raw materials and reaction conditions are high, so that the catalyst is not beneficial to large-scale popularization.
Citation 2 discloses a mesoporous La0.8Sr0.2CoO3Loaded with nano CeO2Catalyst, preparation method and application thereof. Which is prepared from mesoporous perovskite La with high specific surface area0.8Sr0.2CoO3Using cerium nitrate solution as cerium source as carrier, loading CeO by hydrothermal method under alkaline condition2In mesoporous La0.8Sr0.2CoO3The method for preparing the supported catalyst on the surface comprises the following specific steps: 1) la with large specific surface area0.8Sr0.2CoO3Mixing the carrier with a cerous nitrate solution under an alkaline condition for hydrothermal loading for a period of time, 2) washing, filtering, drying and roasting the mixture to obtain a supported perovskite catalyst; in which La of large specific surface area0.8Sr0.2CoO3Can be mesoporous SiO2The composite is a hard template. However, since CeO2And Sr, which are enriched on the surface of the catalyst, block the B site element with catalytic activity, and CeO2The activity is weaker than that of the perovskite catalyst, and further improvement of the perovskite activity is limited.
Cited documents:
cited document 1: CN103861610A
Cited document 2: CN106166491A
Disclosure of Invention
Problems to be solved by the invention
In view of the technical problems in the prior art, for example: the preparation method is complex, the requirements on required raw materials and reaction conditions are high, and the large-scale popularization is not facilitated; the invention provides a perovskite catalyst, which overcomes the adverse effect of the surface-enriched strontium element on the activity of the catalyst compared with the common doped perovskite catalyst, and the perovskite catalyst also has high stability, and is an environment-friendly catalyst for efficiently catalyzing and oxidizing Volatile Organic Compounds (VOCs).
Furthermore, the invention also provides a preparation method of the perovskite catalyst, the preparation method is simple and easy to implement and easy for mass production, and the prepared perovskite catalyst has high catalytic activity.
Further, the perovskite catalyst of the invention can be applied to purifying volatile organic exhaust gas, such as toluene catalytic oxidation, and the performance of toluene catalytic oxidation is improved.
Means for solving the problems
[1] A process for preparing a perovskite catalyst, comprising the steps of:
adsorbing the raw material solution by using a template agent to obtain a catalyst precursor;
carrying out heat treatment on the catalyst precursor to obtain a doped perovskite type compound;
at least partially dissolving the composite by which to at least partially remove the B element from the surface of the composite; wherein the content of the first and second substances,
the doped perovskite-type composite has the following composition of formula (I)
A1-xBxCO3(I)
B represents doping in ACO3Metal element in perovskite structure, A element is selected from rare earth metal, B element is selected from alkaline earth metal, C is selected from transition metal, 0<x<1。
[2] The perovskite catalyst preparation method according to [1], wherein the template comprises monodisperse microspheres, preferably, the template comprises one or a combination of more than two of polymethyl methacrylate microspheres, silica microspheres, polystyrene microspheres, amino silica microspheres and carboxyl silica microspheres.
[3] The perovskite catalyst production method according to [1] or [2], wherein the amount of the template is 0.5 to 5% by mass based on the total mass of the raw material; and/or the adsorption time is 5-20 hours.
[4] The process for producing a perovskite catalyst according to any one of [1] to [3], wherein the heat treatment comprises drying and calcination.
[5] The process for producing a perovskite catalyst according to [4], wherein the drying temperature is 15 to 30 ℃; and/or the drying time is 12-36 h.
[6] The process for producing a perovskite catalyst according to [4] or [5], wherein the calcination comprises calcination in an inert atmosphere and/or an air atmosphere; preferably, the heating rate in the roasting process is 0.5-5 ℃/min.
[7] The process for producing a perovskite catalyst according to any one of [1] to [6], wherein the dissolution is carried out in the presence of an acidic solution; preferably, the concentration of the acid solution is 0.1-0.5 mol/L; the dissolution time is 2-4 days.
[8] A perovskite catalyst prepared by the production method as described in any one of [1] to [7 ].
[9]According to [8]]The perovskite catalyst has a three-dimensional macroporous structure, preferably, the average pore diameter of the macroporous structure of the perovskite catalyst is 100-120nm, and the specific surface area is 15-25m2/g。
[10] Use of the perovskite catalyst according to [8] or [9] for purifying a volatile organic exhaust gas.
ADVANTAGEOUS EFFECTS OF INVENTION
Compared with the common doped perovskite catalyst, the perovskite catalyst of the invention overcomes the adverse effect of the surface enriched strontium element on the catalyst activity, has high catalytic activity, has high stability, and is an environment-friendly catalyst for efficiently catalyzing and oxidizing Volatile Organic Compounds (VOCs).
Furthermore, the preparation method of the perovskite catalyst is simple and feasible, and is easy for mass production.
Further, the perovskite catalyst of the present invention may be applied to purify volatile organic exhaust gases, such as: the toluene is catalytically oxidized, and the performance of the catalytic oxidation of the toluene is effectively improved.
Drawings
FIG. 1 shows LaCoO in comparative example 1 and examples 1 to 3 of the present invention3And (3) a performance test chart of the sample for catalyzing and oxidizing the toluene.
FIG. 2 shows the results of example 1 of the present inventionLa0.8Sr0.2CoO3A sample catalytic stability test graph.
FIG. 3 shows La in example 1 of the present invention0.8Sr0.2CoO3A electron micrograph of the sample.
Detailed Description
The present invention will be described in detail below. The technical features described below are explained based on typical embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples. It should be noted that:
in the present specification, the numerical range represented by "numerical value a to numerical value B" means a range including the end point numerical value A, B.
In the present specification, "plural" in "plural", and the like means a numerical value of 2 or more unless otherwise specified.
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 this specification, "optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
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.
The temperature referred to herein as "room temperature" is generally between "15-30 ℃.
First aspect
A first aspect of the invention provides a process for the preparation of a perovskite catalyst comprising the steps of:
adsorbing the raw material solution by using a template agent to obtain a catalyst precursor;
carrying out heat treatment on the catalyst precursor to obtain a doped perovskite type compound;
at least partially dissolving the composite by which to at least partially remove the B element from the surface of the composite; wherein the content of the first and second substances,
the doped perovskite-type composite has the following composition of formula (I)
A1-xBxCO3(I)
B represents doping in ACO3Metal element in perovskite structure, A element is selected from rare earth metal, B element is selected from alkaline earth metal, C is selected from transition metal, 0<x<1。
Compared with the common doped perovskite catalyst, the perovskite catalyst of the invention overcomes the adverse effect of the surface enriched strontium element on the catalyst activity, has high catalytic activity, has high stability, and is an environment-friendly catalyst for efficiently catalyzing and oxidizing Volatile Organic Compounds (VOCs).
< adsorption >
The present invention uses a template to adsorb a raw material solution, thereby obtaining a catalyst precursor. As the raw material solution, A, B, C and salts (including hydrates of salts thereof) of the O element and the like can be used first to form a mixed solution in an aqueous medium.
For the species of element a, in some particular embodiments of the invention, it may be selected from rare earth metals. Further, there may be mentioned, for example, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium and the like.
As to the type of B element, in some particular embodiments of the invention, it may be chosen from alkaline earth metals, which may be enumerated by the metals beryllium, magnesium, calcium, strontium, barium, radium.
The kind of the C element may be selected from various transition metal elements. Noble metals such as palladium, platinum, gold, silver, rhodium, ruthenium, iridium, etc., or non-noble metals such as iron, cobalt, nickel, copper, zinc, titanium, zirconium, vanadium, niobium, cadmium, tungsten, etc.
The soluble salt containing A, B, C and O element may be one or more of inorganic acid salts such as nitrate, sulfate and hydrochloride or their hydrates, or one or more of organic acid salts such as acetate and oxalate or their hydrates.
In addition, as for the aqueous solvent suitable for forming the above-mentioned mixed solution, water or alcohol or a mixture thereof may be used in some specific embodiments of the present invention, and preferably, deionized water or distilled water may be used.
For the template, the purpose is to adsorb effective components in the raw material solution to obtain a catalyst precursor. Specifically, the template agent is immersed in the raw material solution so as to adsorb the active ingredients in the raw material solution, and the substances containing A, B, C and O are recombined at the molecular level through continuous adsorption to obtain a solid precipitate. The time for adsorption is not particularly limited, and the solid precipitate can be sufficiently obtained. Generally, the adsorption time is from 5 to 20 hours, for example: 7 hours, 9 hours, 11 hours, 13 hours, 15 hours, 18 hours, etc. Further, the solid precipitate is separated by means such as filtration, followed by heat treatment.
Further, in the present invention, the amount of the template used and the selection of the template are not particularly limited, and the solid precipitate can be sufficiently obtained. Specifically, the template may be used in an amount of 0.5 to 5% based on the total mass of the raw materials, for example, the template may be used in an amount of 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, or the like.
Further, in the present invention, the template includes monodisperse microspheres, and generally, the diameter error of each sphere of the monodisperse microspheres is 5% or less, and generally, the diameter error refers to microspheres having a particle diameter of 50 μm or less. For example, the monodisperse microspheres may be monodisperse polymer microspheres, such as polymethyl methacrylate (PMMA) microspheres, Polystyrene (PS) microspheres, and the like. The monodisperse microspheres may also be silica microspheres or functionalized silica microspheres, such as amino silica microspheres, carboxy silica microspheres, and the like.
In the invention, the template agent comprises one or the combination of more than two of polymethyl methacrylate microspheres, silicon dioxide microspheres, polystyrene microspheres, amino silicon dioxide microspheres and carboxyl silicon dioxide microspheres.
< Heat treatment >
The method utilizes a template agent to adsorb a raw material solution to obtain a catalyst precursor, namely a solid precipitate; and then heat-treating the solid precipitate obtained above to remove the template agent to obtain the doped perovskite-type composite. The heat treatment may typically include drying and firing.
The drying temperature may be 15 ℃ or higher and 30 ℃ or lower, and for example, drying may be performed at normal temperature. The drying time is not particularly limited, and may be usually 12 to 36 hours, preferably 16 to 32 hours, for example: 18 hours, 20 hours, 24 hours, 28 hours, etc.
For firing, the firing includes firing under an inert atmosphere and/or an air atmosphere. In order to sufficiently obtain a doped perovskite-type composite, the present invention may perform the firing in stages. Specifically, the temperature can be raised from room temperature to 200-400 ℃ under the inert atmosphere for 2-4 h; then cooling to room temperature, switching to air atmosphere, heating to 200-400 ℃, and preserving heat for 0.5-2h at the temperature; then continuously raising the temperature to 800-1000 ℃ in the air atmosphere and preserving the temperature for 3-5 h.
The heating method for the calcination of the present invention is not particularly limited, and may be adjusted depending on the specific apparatus or equipment. In some embodiments, a temperature increase rate of 0.5 to 5 ℃/min, preferably 0.8 to 4 ℃/min, may be used, for example: 1 deg.C/min, 1.5 deg.C/min, 2 deg.C/min, 2.5 deg.C/min, 3 deg.C/min, 3.5 deg.C/min, etc.
Drying and baking as described above to obtain the doped perovskite-type composite of the present invention, which has the following composition of formula (I):
A1-xBxCO3(I)
b represents doping in ACO3Metal element in perovskite structure, A element is selected from rare earth metal, B element is selected from alkaline earth metal, C is selected from transition metal, 0<x<1。
In general, for the above structure, for ACO3When doping perovskite with structure, the ion radius size and ACO of doped element3When the ionic radii of the a element in the perovskite are close, the doped element will form a-site doping. Therefore, the structure represented by the above formula (I) can be regarded as the B element pair having ACO3A-site of the perovskite-type substance having a type structure is doped. While the complex of formula (I) above doped with element (C) still maintains the perovskite structure.
In the present invention, the adsorption and heat treatment are carried out to obtain a substance having the above-described structure, and the molar ratio of the substance containing A, B, C, O as a raw material is such that the formula (I) can be finally obtained.
In addition, for the above x, 0< x <1 may be possible. In some preferred embodiments of the invention, 0< x <0.5, more preferably 0.1< x <0.3 from an operational standpoint. For example, the mixture formed in the first step may be prepared by using the following components in the following molar ratio: rare earth metal salt: alkaline earth metal salt: transition metal salt (0.7-0.9): 0.3-0.1): 1.
< dissolution >
In the present invention, the B element on the surface of the doped perovskite-type composite is at least partially dissolved and removed by the dissolution step, thereby obtaining a solid substance.
For such dissolution, in some particular embodiments of the invention, the above-described complex may be subjected to a soaking treatment using an acidic solution. As for the kind of the acidic solution that can be used, a solution formed with one or more of an inorganic acid or an organic acid may be selected. More specifically, these acidic solutions may be selected from aqueous solutions formed from one or more of nitric acid, sulfuric acid, hydrochloric acid, chloric acid, glacial acetic acid, oxalic acid, formic acid, acetic acid, lactic acid, propionic acid, acrylic acid, and the like.
The surface B element is at least partially dissolved in the dissolving step to be removed, which means that in the present invention, the solubility of the B element is higher than that of the a element and the C element with respect to the acidic solution used. In a further embodiment, when the above-described substance having the structure of formula (I) is soaked with an acidic solution, the oxide of element B has a greater solubility in the acidic solution than the oxides of elements a and C. In addition, in some specific embodiments of the present invention, the element a and the element C do not dissolve in the acidic solution during the above-described dissolution treatment.
The concentration of the acidic solution or the basic solution used in the dissolving step is not particularly limited, and may be 0.1 to 0.5mol/L, preferably 0.2 to 0.4mol/L, for example, 0.3 mol/L. The soaking time is also not particularly limited, and may be 2 to 4 days, preferably 2.5 to 3.5 days, for example: and 3 days. The concentration and the soaking time are mainly controlled and determined according to the required removal amount of the B element. Therefore, the amount of the element B dissolved can be adjusted by the concentration of the acidic solution and the time of soaking.
In some embodiments of the present invention, a suspension containing solids is obtained by the above dissolution treatment, and the solids can be recovered by solid-liquid separation. The specific solid-liquid separation means is not particularly limited, and typically, means such as filtration or suction filtration can be used. After recovering the solid, optionally, washing with water (deionized or distilled) may be carried out to make the solid pH neutral.
Thereafter, in the present invention, the solid obtained in the dissolving step is further dried to obtain the perovskite catalyst. Generally, the temperature of the drying is 50-70 ℃, for example: 55 ℃, 60 ℃, 65 ℃ and the like; the drying time is 10-15h, for example, overnight drying can be carried out, and the specific drying time can be 11h, 12h, 13h, 14h and the like.
Compared with the common doped perovskite catalyst, the doped perovskite catalyst obtained by acid treatment overcomes the adverse effect of the surface-enriched strontium element on the activity of the catalyst, improves the performance of catalyzing and oxidizing toluene, and has higher stability. In addition, the catalyst has the advantages of low price, simple process and the like, and is an environment-friendly catalyst for efficiently catalyzing and oxidizing VOCs.
Second aspect of the invention
A second aspect of the invention provides a perovskite catalyst prepared by the preparation method of the first aspect of the invention.
FIG. 3 is an electron micrograph of example 1 of the present invention, and it can be seen from FIG. 3 that the perovskite catalyst has a three-dimensional macroporous structure. Preferably, the perovskite catalyst has a macroporous structure with an average pore diameter of 100-120nm, for example: 105nm, 110nm, 115nm, etc.; the specific surface area is 15-25m2G, e.g. 16m2/g、18m2/g、20m2/g、22m2/g、24m2And/g, etc.
In the invention, a physical adsorption instrument is adopted to test the specific surface area of the perovskite sample, and the specific surface area is calculated by a Brunauer-Emmett-Teller (BET) method.
Third aspect of the invention
A third aspect of the invention provides a use of the perovskite catalyst prepared according to the preparation method of the first aspect of the invention or the perovskite catalyst of the second aspect in purifying a volatile organic exhaust gas.
Further, the perovskite catalyst of the invention can selectively catalyze and oxidize toluene in Volatile Organic Compounds (VOCs). The method can be particularly applied to the treatment of industrial waste gas in furniture manufacturing, packaging printing, fine chemical industry, petrochemical industry and the like.
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 not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
The method comprises the following steps: weighing 10.39g of lanthanum nitrate, 1.27g of strontium nitrate and 8.73g of cobalt nitrate in 18mL of deionized water, and stirring for 2h at room temperature;
step two: 2g of template agent polymethyl methacrylate (PMMA) microspheres are added into the solution obtained in the first step to be soaked for 10 hours;
step three: filtering the solution in the second step, and drying the residual solid at room temperature for 24 hours;
step four: and (3) placing the dried powder obtained in the third step into a tubular furnace, raising the temperature from room temperature to 300 ℃ at a speed of 1 ℃/min in a nitrogen atmosphere, preserving the temperature for 3 hours, then lowering the temperature to room temperature, switching to an air atmosphere, raising the temperature to 300 ℃ at a speed of 1 ℃/min, preserving the temperature for 1 hour, finally raising the temperature to 900 ℃ and preserving the temperature for 4 hours. After cooling, the sample was La0.8Sr0.2CoO3。
Step five: the La obtained in the fourth step0.8Sr0.2CoO3The powder is placed in 50mL of 0.2mol/L acetic acid for treatment for 3 d;
step six: filtering the sample in the fifth step to remove acid, and washing with a large amount of deionized water until the pH of the filtrate is neutral and about 7;
step seven: drying the sample obtained in the sixth step in an oven at 60 ℃ overnight (about 10-15h) to obtain the strontium-doped lanthanum perovskite cobaltate catalyst with the surface enriched with strontium elements removed, which is expressed as La0.8Sr0.2CoO3-a。
Example 2
The method comprises the following steps: weighing 11.69g of lanthanum nitrate, 0.64g of strontium nitrate and 8.73g of cobalt nitrate in 18mL of deionized water, and stirring for 2h at room temperature;
step two: 2g of template agent polymethyl methacrylate (PMMA) microspheres are added into the solution obtained in the first step to be soaked for 10 hours;
step three: filtering the solution in the second step, and drying the residual solid at room temperature for 24 hours;
step four: and (3) placing the dried powder obtained in the third step into a tubular furnace, raising the temperature from room temperature to 300 ℃ at a speed of 1 ℃/min in a nitrogen atmosphere, preserving the temperature for 3 hours, then lowering the temperature to room temperature, switching to an air atmosphere, raising the temperature to 300 ℃ at a speed of 1 ℃/min, preserving the temperature for 1 hour, finally raising the temperature to 900 ℃ and preserving the temperature for 4 hours. After cooling, the sample was La0.9Sr0.1CoO3。
Step five: the La obtained in the fourth step0.9Sr0.1CoO3The powder is placed in 50mL of 0.2mol/L acetic acid for treatment for 3 d;
step six: filtering the sample in the fifth step to remove acid, and washing with a large amount of deionized water until the pH of the filtrate is neutral and about 7;
step seven: drying the sample obtained in the sixth step in an oven at 60 ℃ overnight (about 10-15h) to obtain the strontium-doped lanthanum perovskite cobaltate catalyst with the surface enriched with strontium elements removed, which is expressed as La0.9Sr0.1CoO3-a。
Example 3
The method comprises the following steps: weighing 9.09g of lanthanum nitrate, 1.91g of strontium nitrate and 8.73g of cobalt nitrate in 18mL of deionized water, and stirring for 2 hours at room temperature;
step two: 2g of template agent polymethyl methacrylate (PMMA) microspheres are added into the solution obtained in the first step to be soaked for 10 hours;
step three: filtering the solution in the second step, and drying the residual solid at room temperature for 24 hours;
step four: and (3) placing the dried powder obtained in the third step into a tubular furnace, raising the temperature from room temperature to 300 ℃ at a speed of 1 ℃/min in a nitrogen atmosphere, preserving the temperature for 3 hours, then lowering the temperature to room temperature, switching to an air atmosphere, raising the temperature to 300 ℃ at a speed of 1 ℃/min, preserving the temperature for 1 hour, finally raising the temperature to 900 ℃ and preserving the temperature for 4 hours. After cooling, the sample was La0.7Sr0.3CoO3。
Step five: the La obtained in the fourth step0.7Sr0.3CoO3The powder is placed in 50mL of 0.2mol/L acetic acid for treatment for 3 d;
step six: filtering the sample in the fifth step to remove acid, and washing with a large amount of deionized water until the pH of the filtrate is neutral and about 7;
step seven: drying the sample obtained in the sixth step in an oven at 60 ℃ overnight (about 10-15h) to obtain the strontium-doped lanthanum perovskite cobaltate catalyst with the surface enriched with strontium elements removed, which is expressed as La0.7Sr0.3CoO3-a。
Comparative example 1
The method comprises the following steps: weighing 13g of lanthanum nitrate and 8.73g of cobalt nitrate into 18mL of deionized water, and stirring for 2h at room temperature;
step two: 2g of template agent polymethyl methacrylate (PMMA) microspheres are added into the solution obtained in the first step to be soaked for 10 hours;
step three: filtering the solution in the second step, and drying the residual solid at room temperature for 24 hours;
step four: and (3) placing the dried powder obtained in the third step into a tubular furnace, raising the temperature from room temperature to 300 ℃ at a speed of 1 ℃/min in a nitrogen atmosphere, preserving the temperature for 3 hours, then lowering the temperature to room temperature, switching to an air atmosphere, raising the temperature to 300 ℃ at a speed of 1 ℃/min, preserving the temperature for 1 hour, finally raising the temperature to 900 ℃ and preserving the temperature for 4 hours. After cooling, the sample was LaCoO3。
FIG. 1 shows LaCoO in comparative example 1 and examples 1-3 of the present invention3And (3) a performance test chart of the sample for catalyzing and oxidizing the toluene. And (3) testing conditions are as follows: tabletting, crushing and screening the catalyst powder, and selecting the catalyst particles with the average size of 50 meshes for evaluating the catalytic oxidation activity of the toluene, wherein the catalyst particles comprise 0.05g of catalyst, 2000ppm of toluene and O 220% and gas space velocity GHSV 120,000h-1。
As can be seen in FIG. 1, La after A-site doping0.8Sr0.2CoO3Sample, La0.9Sr0.1CoO3Sample and La0.7Sr0.3CoO3The sample has reduced catalytic activity because its active sites are covered by surface-enriched strontium elements. After acid treatment，La0.8Sr0.2CoO3A sample, La0.9Sr0.1CoO3A sample and La0.7Sr0.3CoO3The catalytic activity of the sample-a is obviously improved, and the real activity of the perovskite catalyst after the doping of the alkaline earth element is shown.
FIG. 2 shows La in example 10.8Sr0.2CoO3A sample catalytic stability test graph. And (3) testing conditions are as follows: tabletting, crushing and screening the catalyst powder, and selecting the catalyst particles with the average size of 50 meshes for evaluating the catalytic oxidation activity of the toluene, wherein the catalyst particles comprise 0.05g of catalyst, 2000ppm of toluene and O 220% and gas space velocity GHSV 120,000h-1. The whole testing process comprises three complete activity testing cycles (temperature rise process and temperature reduction process, the testing temperature interval is 210-280 ℃, each 5 ℃ is a testing point, each temperature is maintained for 30min, the temperature rise rate between two temperature points in the temperature rise process is 1 ℃/min, and the temperature reduction rate between two temperature points in the temperature reduction process is 0.5 ℃/min), as can be seen from the figure, in the whole testing process, La0.8Sr0.2CoO3The activity of the sample-a is not reduced basically, and the catalyst has good catalytic stability, thereby providing the possibility for the practical application of toluene removal.
Industrial applicability
The perovskite catalyst provided by the invention can be industrially prepared and can be applied to purification of volatile organic waste gas.
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 method of preparing a perovskite catalyst, comprising the steps of:
adsorbing the raw material solution by using a template agent to obtain a catalyst precursor;
carrying out heat treatment on the catalyst precursor to obtain a doped perovskite type compound;
at least partially dissolving the composite by which to at least partially remove the B element from the surface of the composite; wherein the content of the first and second substances,
the doped perovskite-type composite has the following composition of formula (I)
A1-xBxCO3(I)
B represents doping in ACO3Metal element in perovskite structure, A element is selected from rare earth metal, B element is selected from alkaline earth metal, C is selected from transition metal, 0<x<1。
2. The preparation method of the perovskite catalyst according to claim 1, wherein the template comprises monodisperse microspheres, preferably the template comprises one or a combination of more than two of polymethyl methacrylate microspheres, silica microspheres, polystyrene microspheres, amino silica microspheres and carboxyl silica microspheres.
3. The process for preparing a perovskite catalyst as claimed in claim 1 or 2, wherein the template is used in an amount of 0.5 to 5% by mass based on the total mass of the raw material; and/or the adsorption time is 5-20 hours.
4. A process for the preparation of a perovskite catalyst as claimed in any one of claims 1 to 3, wherein the heat treatment comprises drying and calcination.
5. The process for preparing a perovskite catalyst as claimed in claim 4, wherein the drying temperature is 15 to 30 ℃; and/or the drying time is 12-36 h.
6. The production method of a perovskite catalyst as claimed in claim 4 or 5, characterized in that the calcination comprises calcination under an inert atmosphere and/or an air atmosphere; preferably, the heating rate in the roasting process is 0.5-5 ℃/min.
7. The process for producing a perovskite catalyst as claimed in any one of claims 1 to 6, wherein the dissolution is carried out in the presence of an acidic solution; preferably, the concentration of the acid solution is 0.1-0.5 mol/L; the dissolution time is 2-4 days.
8. A perovskite catalyst prepared by the preparation method as set forth in any one of claims 1 to 7.
9. The perovskite catalyst as claimed in claim 8, wherein the perovskite catalyst has a three-dimensional macroporous structure, preferably wherein the macroporous structure of the perovskite catalyst has an average pore diameter of 100-120nm and a specific surface area of 15-25m2/g。
10. Use of a perovskite catalyst according to claim 8 or 9 for purifying volatile organic exhaust gases.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010149904.6A CN111185182B (en) | 2020-03-06 | 2020-03-06 | Perovskite catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010149904.6A CN111185182B (en) | 2020-03-06 | 2020-03-06 | Perovskite catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111185182A true CN111185182A (en) | 2020-05-22 |
| CN111185182B CN111185182B (en) | 2021-10-19 |
Family
ID=70702710
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010149904.6A Active CN111185182B (en) | 2020-03-06 | 2020-03-06 | Perovskite catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111185182B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111916770A (en) * | 2020-09-02 | 2020-11-10 | 厦门理工学院 | High-performance air electrode catalyst and preparation method thereof |
| CN112337461A (en) * | 2020-10-26 | 2021-02-09 | 苏州大学 | Composite material of strontium-doped ordered mesoporous lanthanum manganate-loaded noble metal palladium, preparation method thereof and application thereof in catalytic oxidation of toluene |
| CN113769740A (en) * | 2021-08-11 | 2021-12-10 | 南昌航空大学 | Method for improving catalytic oxidation performance of silver-doped perovskite metal oxide by etching silver-doped perovskite metal oxide with reductive organic acid solution |
| CN114149835A (en) * | 2021-12-08 | 2022-03-08 | 浙江三龙催化剂有限公司 | Novel deoxidation and desulfurization process and application thereof |
| CN114308031A (en) * | 2021-12-31 | 2022-04-12 | 江苏洋井环保服务有限公司 | Perovskite type oxide material doped with noble metal and preparation method thereof |
| CN115155578A (en) * | 2022-06-22 | 2022-10-11 | 清华大学 | Preparation method of monoatomic catalyst with controllable active component and load |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1947834A (en) * | 2006-11-10 | 2007-04-18 | 北京工业大学 | Process for preparing catalyst contg. La(1-x)SrxMO3 used for removing volatile organic matter |
| CN110026185A (en) * | 2018-11-23 | 2019-07-19 | 江苏中创清源科技有限公司 | A kind of modified perovskite type catalyst and preparation method thereof |
-
2020
- 2020-03-06 CN CN202010149904.6A patent/CN111185182B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1947834A (en) * | 2006-11-10 | 2007-04-18 | 北京工业大学 | Process for preparing catalyst contg. La(1-x)SrxMO3 used for removing volatile organic matter |
| CN110026185A (en) * | 2018-11-23 | 2019-07-19 | 江苏中创清源科技有限公司 | A kind of modified perovskite type catalyst and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| S.ROUSSEAU ET AL.: "La(1-x)SrxCo1-yFeyO3 perovskites prepared by sol–gel method：Characterization and relationships with catalytic properties for total oxidation of toluene", 《APPLIED CATALYSIS B：ENVIRONMENTAL》 * |
| ZHENXUAN ZHAO ET AL.: "Three-dimensionally ordered macroporous La0.6Sr0.4FeO3-δ: High-efficiency catalysts for the oxidative removal of toluene", 《MICROPOROUS AND MESOPOROUS MATERIALS》 * |
| 丁全: "La0.7Sr0.3CoO3稀土钙钛矿催化剂的制备及其NSR性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111916770A (en) * | 2020-09-02 | 2020-11-10 | 厦门理工学院 | High-performance air electrode catalyst and preparation method thereof |
| CN111916770B (en) * | 2020-09-02 | 2021-09-24 | 厦门理工学院 | High-performance air electrode catalyst and preparation method thereof |
| CN112337461A (en) * | 2020-10-26 | 2021-02-09 | 苏州大学 | Composite material of strontium-doped ordered mesoporous lanthanum manganate-loaded noble metal palladium, preparation method thereof and application thereof in catalytic oxidation of toluene |
| CN112337461B (en) * | 2020-10-26 | 2023-11-03 | 苏州大学 | Composite material of strontium doped ordered mesoporous lanthanum manganate loaded with noble metal palladium, preparation method thereof and application thereof in catalytic oxidation of toluene |
| CN113769740A (en) * | 2021-08-11 | 2021-12-10 | 南昌航空大学 | Method for improving catalytic oxidation performance of silver-doped perovskite metal oxide by etching silver-doped perovskite metal oxide with reductive organic acid solution |
| CN114149835A (en) * | 2021-12-08 | 2022-03-08 | 浙江三龙催化剂有限公司 | Novel deoxidation and desulfurization process and application thereof |
| CN114308031A (en) * | 2021-12-31 | 2022-04-12 | 江苏洋井环保服务有限公司 | Perovskite type oxide material doped with noble metal and preparation method thereof |
| CN115155578A (en) * | 2022-06-22 | 2022-10-11 | 清华大学 | Preparation method of monoatomic catalyst with controllable active component and load |
| CN115155578B (en) * | 2022-06-22 | 2023-08-15 | 清华大学 | Preparation method of controllable active component and loading single-atom catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111185182B (en) | 2021-10-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111185182B (en) | Perovskite catalyst and preparation method and application thereof | |
| CN109107567B (en) | M-MnOX-CeO2Catalyst and application thereof | |
| JP6471240B2 (en) | Cerium-zirconium composite oxide, production method thereof and use of catalyst | |
| CN109364915B (en) | Perovskite type composite metal oxide catalyst and preparation method thereof | |
| JP4382482B2 (en) | Ceric oxide, method for producing the same, and catalyst for exhaust gas purification | |
| CN103816918A (en) | Weak-crystallization nanometer manganese oxide base adsorbing/catalyzing agent and preparation method thereof | |
| CN100360224C (en) | Formaldehyde gas oxidation catalyst under room temperature | |
| CN111889101A (en) | Modified composite oxide catalyst for synergistic purification of VOCs and NO and preparation method thereof | |
| CN110605114B (en) | Application of mullite oxide supported catalyst in low-temperature selective catalytic reduction denitration | |
| CN107456964A (en) | For the extra specific surface area perovskite type composite oxide catalyst of hydrocarbon low-temperature oxidation and its preparation | |
| CN104772110A (en) | Visible-light response type air purifier photo-catalyst filter screen and preparation method thereof | |
| CN113786828A (en) | Catalyst for synergistic removal of NOx and CVOCs and preparation method and application thereof | |
| CN104971735B (en) | A kind of efficient diesel car tail gas refining oxidation catalyst and its preparation method and application | |
| CN113262787A (en) | Preparation method of iron-based composite catalyst for catalytic ozonation treatment of coal chemical wastewater | |
| JP4450763B2 (en) | Precious metal-containing composite metal oxide for exhaust gas purification catalyst and method for producing the same | |
| CN117772186A (en) | Cerium-manganese composite catalyst supported ceramic membrane and preparation method and application thereof | |
| CN111569922B (en) | Rare earth doped hydrotalcite-like derivative oxide catalyst for catalytic combustion of VOC waste gas and preparation method thereof | |
| JP2006043683A (en) | Catalyst carrier and its manufacturing method and catalyst for cleaning exhaust gas | |
| CN110013846B (en) | Preparation method and application of aluminum-manganese co-pillared montmorillonite-loaded Ce-Cu or Eu-Ce composite catalyst | |
| CN113083324B (en) | Formaldehyde oxidation catalyst used at room temperature and preparation method thereof | |
| CN114570354B (en) | Perovskite catalyst and preparation method thereof | |
| JP2013203609A (en) | Oxygen storable ceramic material, method for producing the same, and catalyst | |
| CN108993544B (en) | Catalyst for removing NOx and VOCs in low-temperature high-sulfur tail gas and preparation and application thereof | |
| CN113648990A (en) | Preparation method and application of iron pillared montmorillonite-loaded Mn-Ce-Sm composite catalyst | |
| JP2003225568A (en) | Catalyst for purifying volatile organic compound and production method therefor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |