CN107930666B - Nano cerium Mn oxide/absorbent charcoal composite material of Oxidation at room temperature formaldehyde and preparation method thereof - Google Patents
Nano cerium Mn oxide/absorbent charcoal composite material of Oxidation at room temperature formaldehyde and preparation method thereof Download PDFInfo
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- CN107930666B CN107930666B CN201711103494.6A CN201711103494A CN107930666B CN 107930666 B CN107930666 B CN 107930666B CN 201711103494 A CN201711103494 A CN 201711103494A CN 107930666 B CN107930666 B CN 107930666B
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- activated carbon
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- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 54
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 230000003647 oxidation Effects 0.000 title claims abstract description 30
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 30
- 239000003610 charcoal Substances 0.000 title claims abstract description 27
- 239000002250 absorbent Substances 0.000 title claims abstract description 25
- 230000002745 absorbent Effects 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title abstract description 117
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 164
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- -1 nitrogenous compound Chemical class 0.000 claims abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000975 co-precipitation Methods 0.000 claims abstract description 7
- 238000012545 processing Methods 0.000 claims abstract description 7
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 239000011572 manganese Substances 0.000 claims description 55
- 238000001914 filtration Methods 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- 229920002873 Polyethylenimine Polymers 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- LQWKWJWJCDXKLK-UHFFFAOYSA-N cerium(3+) manganese(2+) oxygen(2-) Chemical compound [O--].[Mn++].[Ce+3] LQWKWJWJCDXKLK-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- 210000002421 cell wall Anatomy 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- 230000033116 oxidation-reduction process Effects 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 230000002209 hydrophobic effect Effects 0.000 abstract description 4
- 238000004887 air purification Methods 0.000 abstract description 3
- 230000010718 Oxidation Activity Effects 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 229910016978 MnOx Inorganic materials 0.000 description 19
- 239000008367 deionised water Substances 0.000 description 19
- 229910021641 deionized water Inorganic materials 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 17
- 230000000694 effects Effects 0.000 description 17
- 238000003756 stirring Methods 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 14
- 238000006555 catalytic reaction Methods 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 229930040373 Paraformaldehyde Natural products 0.000 description 8
- 229920002866 paraformaldehyde Polymers 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 229910052748 manganese Inorganic materials 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 230000000802 nitrating effect Effects 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- 239000000052 vinegar Substances 0.000 description 7
- 235000021419 vinegar Nutrition 0.000 description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 229910052740 iodine Inorganic materials 0.000 description 6
- 239000011630 iodine Substances 0.000 description 6
- 239000012286 potassium permanganate Substances 0.000 description 6
- 238000012216 screening Methods 0.000 description 6
- 239000012265 solid product Substances 0.000 description 6
- 235000013162 Cocos nucifera Nutrition 0.000 description 5
- 244000060011 Cocos nucifera Species 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- IDIFPUPZOAXKOV-UHFFFAOYSA-N azane ruthenium Chemical compound N.[Ru] IDIFPUPZOAXKOV-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000010903 husk Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 235000013339 cereals Nutrition 0.000 description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 229910052738 indium Inorganic materials 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000004375 physisorption Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000006479 redox reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000002525 ultrasonication Methods 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 150000004675 formic acid derivatives Chemical class 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 229910000667 (NH4)2Ce(NO3)6 Inorganic materials 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910002451 CoOx Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- BLFRRKIOEASQKD-UHFFFAOYSA-N [O].O=C Chemical compound [O].O=C BLFRRKIOEASQKD-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 208000030961 allergic reaction Diseases 0.000 description 1
- FZIZEIAMIREUTN-UHFFFAOYSA-N azane;cerium(3+) Chemical compound N.[Ce+3] FZIZEIAMIREUTN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- YOSLGHBNHHKHST-UHFFFAOYSA-N cerium manganese Chemical compound [Mn].[Mn].[Mn].[Mn].[Mn].[Ce] YOSLGHBNHHKHST-UHFFFAOYSA-N 0.000 description 1
- BYCKXMUEODWQNZ-UHFFFAOYSA-H cerium(3+);oxalate;decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Ce+3].[Ce+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O BYCKXMUEODWQNZ-UHFFFAOYSA-H 0.000 description 1
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical group [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 1
- 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 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning 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
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 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
- 239000008187 granular material Substances 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical group [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
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- INARWLVFBQDLIN-UHFFFAOYSA-L manganese(2+);oxalate;hydrate Chemical compound O.[Mn+2].[O-]C(=O)C([O-])=O INARWLVFBQDLIN-UHFFFAOYSA-L 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Dispersion Chemistry (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 present invention provides nano cerium Mn oxide/absorbent charcoal composite material and preparation method thereof of Oxidation at room temperature formaldehyde.Activated carbon is subjected to sour processing first, then N doping processing is carried out to it using nitrogenous compound, after collosol and gel is heat-treated nitrogen is introduced in activated carbon surface, while obtaining mesoporous activated carbon, the surface polarity of activated carbon is substantially increased, nano cerium Mn oxide is uniformly firmly then loaded in activated carbon surface using coprecipitation in situ.Compared with existing catalyst, nano cerium Mn oxide/the absorbent charcoal composite material can expose more active sites, and have good hydrophobic performance, improve formaldehyde through catalytic oxidation activity, it can be used directly or used after being simply molded, be used for air purification field.Step is simple and convenient to operate, is highly practical.
Description
Technical field
The invention belongs to the air purification fields of formaldehyde through catalytic oxidation, and in particular to it is a kind of can Oxidation at room temperature formaldehyde nanometer
Cerium Mn oxide/absorbent charcoal composite material and preparation method thereof.
Background technology
In recent years, air pollution has become society and faces and becomes the threat mankind with significant problem urgently to be resolved hurrily, PM2.5 and be good for
One of most important outdoor factor of health, and formaldehyde then becomes indoor most important air pollutants.Formaldehyde toxicity is high, works as accumulation
When to a certain concentration, it can cause respiratory system and nervous system allergic reaction, the formaldehyde of Long Term Contact low concentration that can greatly increase
Carcinogenic probability.Formaldehyde is ubiquitous in life, and finishing material and building decoration object are the main sources of indoor formaldehyde, directly
People's health is threatened, therefore effectively the pollution of control formaldehyde in indoor air causes the great attention of people.
Currently, indoor formaldehyde is mainly carried out using the physisorption of commercially available air purifier or absorbent charcoal material
It eliminates.This kind of product is at low cost, preparation method is simple, but easily reaches adsorption saturation, is inhaled if close to adsorption saturation
Attached efficiency substantially reduces, and harmful micro-molecular gas is easy to overflow and causes secondary pollution, needs to replace in time, both time-consuming in this way
Arduously, and cost is increased.Therefore, it carries out catalysis oxidation to generate nontoxic carbon dioxide and water being mesh using catalyst PARA FORMALDEHYDE PRILLS(91,95)
The hot spot of preceding research.
The study found that the noble metals such as platinum (Pt), palladium (Pd), golden (Au) have splendid effect for the catalysis oxidation of formaldehyde
Fruit, but such catalyst is expensive, preparation process is complicated, service life is short.Then people turn to research emphasis by transition
Catalyst prepared by metal oxide, with MnOx、CoOx、CeO2, CuO etc. be the manganese of representative, cobalt, cerium, the oxidation of copper mixed valence
Object achieves good effect.Such catalyst is mainly the following form at present：①MnOx；②X-MnOx(your gold X includes
Category, transition metal oxide, major element and rare earth element)；3. activated carbon, carbon nanotube, aluminium oxide ceramics etc. load MnOx。
Pure MnOxThere is good catalysis oxidation formaldehyde ability at high temperature, but it is active poor at room temperature；Noble metal-MnOxAnd mistake
Cross metal oxide-MnOxWith best low-temperature oxidation formaldehyde ability, but noble metal is expensive；Activated carbon, carbon nanotube,
Aluminium oxide ceramics etc. loads MnOxIt can make MnO by specially treatedxIt is dispersed on carrier, catalyst particle is avoided to reunite,
So that catalyst surface is exposed more active sites, there is good application prospect.
Activated carbon PARA FORMALDEHYDE PRILLS(91,95) has physisorption, MnOxCatalysed oxidn, while activity can be carried out with PARA FORMALDEHYDE PRILLS(91,95)
Charcoal is cheap, wide in variety, therefore activated carbon supported MnOxIt can be used for the catalysis oxidation of formaldehyde, but it is often in higher temperature
It could effectively PARA FORMALDEHYDE PRILLS(91,95) be aoxidized under (200 DEG C of ＞), in the very poor (first at room temperature of the catalytic activity of low temperature especially at room temperature
Aldehyde conversion ratio ＜ 10%).Therefore, noble metal-MnOxWith transition metal oxide-MnOxThe synergistic effect of equal composite catalysts makes
Obtaining PARA FORMALDEHYDE PRILLS(91,95) at low temperature has good catalysis oxidation ability.As CN103071489A discloses a kind of bearing for eliminating formaldehyde at room temperature
Then load type activated carbon catalysis material and preparation method are soaked successively after being pre-processed to activated carbon using nitric acid and hydrogen peroxide
Stain metal nitrate and precious metal chloride obtain carried noble metal by redox reaction and the compound of metal oxide are urged
Agent.It is added to noble metal in the catalyst, cost is made to increase, and noble metal and metal oxide are difficult in activated carbon surface
It is evenly dispersed, thus load capacity it is low, in conjunction with force difference, the inactivation easy to fall off during Reusability, and this be also at present such urge
The common defect of agent.Therefore, it can be that such catalyst need to improve the chemical bonding between composite catalyst and activated carbon surface
The key technical problem to be solved.
Invention content
The present invention is intended to provide a kind of preparation method is simple, load capacity is high, Load Balanced is firm, can Oxidation at room temperature formaldehyde
Nano cerium Mn oxide/absorbent charcoal composite material, to solve problems of the prior art.Activated carbon is carried out at acid first
Reason, then carries out N doping processing using nitrogenous compound to it, and nitrogen is introduced in activated carbon surface after collosol and gel is heat-treated
Element substantially increases the surface polarity of activated carbon while obtaining mesoporous activated carbon, then uses coprecipitation in situ
Nano cerium Mn oxide is uniformly firmly loaded in activated carbon surface.Compared with existing catalyst, the nano cerium Mn oxide/
Absorbent charcoal composite material can expose more active sites, and have good hydrophobic performance, improve formaldehyde catalysis oxygen
Change activity, can be used directly or used after being simply molded, is used for air purification field.
To achieve the goals above, the present invention adopts the following technical scheme that：
A kind of nano cerium Mn oxide/absorbent charcoal composite material of Oxidation at room temperature formaldehyde, including：
The mesoporous activated carbon of nitrating；
The nano cerium Mn oxide being carried on the mesoporous activated carbon of the nitrating.
Preferably, the load capacity of mesoporous activated carbon of the nano cerium Mn oxide in nitrating is 5~15wt%.
Preferably, the cerium Mn oxide is with CeO2-MnOxThe form of (x=1.6~2) exists.
Preferably, in the mesoporous activated carbon of the nitrating, mesoporous proportion is 50% or more.
The present invention also provides a kind of preparation sides of nano cerium Mn oxide/absorbent charcoal composite material of Oxidation at room temperature formaldehyde
Method, including：
Nitrating is carried out to acid treated activated carbon using sol-gal process, obtains xerogel；
High-temperature heat treatment is carried out to above-mentioned xerogel, obtains the mesoporous activated carbon of nitrating；
Using coprecipitation in situ above-mentioned nitrating mesoporous activated carbon area load nano cerium Mn oxide to get nanometer
Cerium Mn oxide/absorbent charcoal composite material.
Preferably, the sol-gal process the specific steps are：Activated carbon and nitrogenous compound is set to live in macromolecule surface
Property agent existence condition under form gel, washing, filtering, dry xerogel.
Preferably, the nitrogenous compound is at least one of melamine, urea, biuret, thiocarbamide.
Preferably, the high molecular surfactant be polyvinylpyrrolidone, polyethyleneimine, poly maleimide and
One kind in its derivative, acrylic acid copolymer-maleic anhydride, acrylate copolymer.
Preferably, the nitrogenous compound and pretreated quality of activated carbon ratio are 1:5~10.
The present invention also provides sol-gal processes to improve activated carbon surface nano cerium Mn oxide load capacity and uniformity
In application.
Beneficial effects of the present invention
(1) preparation method of nano cerium Mn oxide/absorbent charcoal composite material provided by the invention, cerium manganese oxidation obtained
Composition granule grain size is between 5~20nm, and nano-scale particle is one during activated carbon surface carries out in-situ oxidation reduction reaction
Partial particulate enters in the mesoporous duct with macropore of activated carbon, is supported on the inner wall in activated carbon duct through co-precipitation, other
Particle loading is in activated carbon surface.Activated carbon is surface-treated through strong acid and nitrogenous compound, introduces the stronger oxygen-containing function of polarity
Group and nitrogen-containing functional group, substantially increase the load capacity of nano cerium Mn oxide, are gone back through co-precipitation oxidation in activated carbon surface
Original reaction forms the uniform load of nano particle, increases effective ratio area, and keeps nano grain surface exposure more
Active site, while the hydrophobic performance of composite material is improved, be conducive to the catalysis oxidation of formaldehyde.
(2) nano cerium Mn oxide/absorbent charcoal composite material provided by the invention, with the activated carbon phase without N doping
Than the activated carbon specific surface area (N obtained through N doping2Adsorption isothermal curve BET method measures) it significantly increases and (can increase
100%), and mesopore volume and average pore size are also improved, and wherein average pore size is can be controlled between 30~50nm, this is follow-up
The load of nano cerium Mn oxide provide good condition (nano cerium Mn oxide size tunable system is between 5~20nm),
The reunion of particle and the blocking to activated carbon hole can be prevented to the full extent, improve the specific surface area of catalyst, realization is received
Rice cerium Mn oxide is in the evenly dispersed of activated carbon surface.Therefore, more work can be exposed in PARA FORMALDEHYDE PRILLS(91,95) catalytic oxidation process
Property site, this plays facilitation for the follow-up formaldehyde oxidation rate that improves.
(3) nano cerium Mn oxide/absorbent charcoal composite material provided by the invention, cerium Mn oxide is with CeO2-MnOx(x=
1.6~2) form exists, MnOxIn Mn with Mn4+And Mn3+Mixing valent state form exist, MnOxThe work of surface exposure
Property site be oxidation of formaldehyde main place, lattice surface oxygen has very strong activity, during the reaction first by formaldehyde point
Solution is formates, and then formates is converted into CO and is adsorbed on MnOxSurface, then the CO of activity oxygen element and adsorption is anti-
Final CO should be generated2And H2O, and easily oxygen is regenerated Lattice Oxygen through the air, Mn4+And Mn3+Reversible transition be
Catalysis reaction provides endlessly power.Wherein CeO2The reaction of catalysis oxidation formaldehyde is not participated in directly, but it has
Very strong oxygen storage capacity, the active oxygen element needed in reaction is preferentially by CeO2Surface generates, thus takes part in MnOxMiddle Lattice Oxygen
Circular response, improve MnOxThe rate of catalysis oxidation formaldehyde reaction.The physisorption of activated carbon PARA FORMALDEHYDE PRILLS(91,95) simultaneously,
The enough reaction time is provided for whole process.
(4) nano cerium Mn oxide/absorbent charcoal composite material provided by the invention, CeO2Addition be conducive to MnOxSurface
The activation of upper Lattice Oxygen, and catalyst can be made to expose more active sites after N doping is handled, greatly improve formaldehyde oxygen
Change rate, shows as H2Low temperature is shifted at temperature programmed reduction peak, to improve the catalysis oxidation formaldehyde of low temperature catalyst
Energy.
(5) nano cerium Mn oxide/absorbent charcoal composite material prepared by the present invention reacts it in continuous flow fixed bed
Formaldehyde through catalytic oxidation activity rating is carried out in device.Formaldehyde gas uses gaseous mixture (N in 0 DEG C of low temperature thermostat bath2/O2=79%/
21%) it is bubbled and enters reactor, it is reachable to measure formaldehyde conversion at room temperature by concentration of formaldehyde 100ppm, GHSV=60L/ (gh)
50% or so.
(6) preparation method of the present invention is simple, PARA FORMALDEHYDE PRILLS(91,95) high conversion efficiency, highly practical, easy to spread.
Specific implementation mode
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
A kind of nano cerium Mn oxide/absorbent charcoal composite material of Oxidation at room temperature formaldehyde
(1) Activated Carbon Pretreatment
The activated carbon for screening mesh number 80-150, is immersed in the mixed solution of 65~70wt% nitric acid and 98wt% sulfuric acid
In, 4~5h is pre-processed at 80 DEG C.After filtering using deionized water cleaning for several times to pH be 6~7 between, in 120 DEG C of baking ovens do
Dry 8h.
(2) ruthenium ammonia synthesis catalyst
By above-mentioned pretreated activated carbon and high molecular surfactant according to mass ratio 3~6:1 ratio is stirring
(1000r/min) is add to deionized water under effect.Then nitrogenous compound is added, stirs 1h at room temperature, then at 60 DEG C
Lower ultrasonication 3h obtains brown gel, and supernatant liquor is filtered off after standing 1h, 3~5 times wash with distilled water, turns after filtering
It moves on to 1h in 100 DEG C of baking ovens and obtains xerogel.Then 2~3h is calcined in 500~700 DEG C of Muffle furnace, after being cooled to room temperature
Obtain modified activated carbon particle.
(3) preparation of nano cerium Mn oxide/absorbent charcoal composite material
By KMnO4With cerous salt according to molar ratio 2:1 ratio is add to deionized water under stirring to be made
Then solution is added spirit of vinegar and adjusts pH between 4~5.Then the above-mentioned active carbon particle being modified is added, is acutely stirring
It mixes under effect, the manganous salt aqueous solution prepared in advance is added, is reacted for 24 hours at 80 DEG C.The total moles ratio of metal Mn and Ce be 2~
6:1.After reaction, solid product is obtained by filtration, is cleaned 4~5 times using ethyl alcohol and deionized water, then at 300~700 DEG C
Muffle furnace in calcining 4~10h obtain nano cerium Mn oxide/absorbent charcoal composite material.
The activated carbon be coconut husk, coal quality or wood substance grain shaped activated carbon one kind, iodine number >=900mg/g, ash content≤
15%.
In the ruthenium ammonia synthesis catalyst, high molecular surfactant is polyvinylpyrrolidone, polyethyleneimine, poly- horse
Carry out one kind in acid imide and its derivative, acrylic acid copolymer-maleic anhydride, acrylate copolymer.
In the ruthenium ammonia synthesis catalyst, nitrogenous compound is 1 with pretreated quality of activated carbon ratio:5~10.
In the ruthenium ammonia synthesis catalyst, nitrogenous compound is at least one of melamine, urea, biuret, thiocarbamide.
In the ruthenium ammonia synthesis catalyst, supersonic oscillations frequency is 20kHz.
In the preparation of the nano cerium Mn oxide/absorbent charcoal composite material, cerous salt is cerous acetate, cerous nitrate, sulphur
One kind in sour cerium ammonium, cerium oxalate hydrate.
In the preparation of the nano cerium Mn oxide/absorbent charcoal composite material, spirit of vinegar is to be diluted through deionized water
Acetum of the concentration in 40~60wt%.
In the preparation of the nano cerium Mn oxide/absorbent charcoal composite material, mixing speed when being vigorously stirred is 3000
~5000r/min.
In the preparation of the nano cerium Mn oxide/absorbent charcoal composite material, manganous salt is manganese acetate, manganese nitrate, chlorine
One kind in change manganese, manganese phosphate, manganese oxalate hydrate, the solution that the manganous salt aqueous solution diluted for deionized water, two
Valence manganese salt mass fraction is 20~40wt%.
In the preparation of the nano cerium Mn oxide/absorbent charcoal composite material, the load of cerium Mn oxide on the activated carbon
Amount is 5~15wt%.
The advantage of the invention is that：1. being pre-processed to activated carbon using nitric acid and the concentrated sulfuric acid, activity is substantially increased
Charcoal mesoporous (2~50nm of aperture) and macropore (aperture ＞ 50nm) ratio, intermediary hole proportion is 50% or more, while in work
Property the upper polarity oxygen-containing functional group of carbon surface grafting；2. then after nitrogenous compound colloidal sol, gel and heat treatment, in activated carbon
Surface introduces polarity nitrogen-atoms, further improves the chemical bond between cerium manganese oxide nano-particles and activated carbon surface
Can, and the hydrophobic performance of composite material is improved, this has good facilitation for room temperature catalytic oxidation formaldehyde；3. passing through
Surface acid is modified and nitrogen is modified, can realize that cerium manganese oxide nano-particles exist by the redox reaction in situ that is co-precipitated
Activated carbon surface is uniformly distributed, and keeps load more firm, while improving the catalytic oxidation performance of formaldehyde under low temperature.
Embodiment 1
The present embodiment preparation method is as follows：
The coconut husk granular active carbon (iodine number 1000mg/g) for screening mesh number 80~150, is immersed in 65~70wt%
In the mixed solution of nitric acid and 98wt% sulfuric acid, 4h is pre-processed at 80 DEG C.It is 6 to pH to be cleaned for several times using deionized water after filtering
Between~7, the dry 8h in 120 DEG C of baking ovens.
Take above-mentioned pretreated activated carbon 100g and polyvinylpyrrolidone 25g under stirring (1000r/min)
It is add to deionized water.Then 16g melamines are added, stir 1h at room temperature, then the ultrasonication 3h at 60 DEG C, obtains
To brown gel, supernatant liquor is filtered off after standing 1h, 3~5 times wash with distilled water, 1h in 100 DEG C of baking ovens is transferred to after filtering
Obtain xerogel.Then 3h is calcined in 500 DEG C of Muffle furnace, modified activated carbon particle is obtained after being cooled to room temperature.
By 1.58g KMnO4(0.01mol) and 2.17g Ce (NO3)3·6H2O (0.005mol) is added under stirring
To solution is made in 100mL deionized waters, the spirit of vinegar of 50wt% is then added dropwise and adjusts pH between 4~5.Then it is added
(the NO of Mn containing 0.005mol prepared in advance are added under the effect that is vigorously stirred in the above-mentioned active carbon particles being modified of 10g3)2's
Aqueous solution reacts for 24 hours at 80 DEG C.The total moles ratio of metal Mn and Ce are 3:1.After reaction, solid product is obtained by filtration, makes
It is cleaned 4~5 times with ethyl alcohol and deionized water, then calcines 6h in 500 DEG C of Muffle furnace and obtain nano cerium Mn oxide/activity
Carbon composite.
Embodiment 2
The present embodiment preparation method is as follows：
The coal quality granular active carbon (iodine number 1200mg/g) for screening mesh number 80~150, is immersed in 65~70wt%
In the mixed solution of nitric acid and 98wt% sulfuric acid, 4h is pre-processed at 80 DEG C.It is 6 to pH to be cleaned for several times using deionized water after filtering
Between~7, the dry 8h in 120 DEG C of baking ovens.
Taking above-mentioned pretreated activated carbon 100g and polyethyleneimine 20g, (1000r/min) is added under stirring
Into deionized water.Then 16g urea is added, stirs 1h at room temperature, then the ultrasonication 3h at 60 DEG C, it is solidifying to obtain brown
Glue filters off supernatant liquor after standing 1h, 3~5 times wash with distilled water, and 1h in 100 DEG C of baking ovens is transferred to after filtering and obtains dry coagulate
Glue.Then 3h is calcined in 500 DEG C of Muffle furnace, modified activated carbon particle is obtained after being cooled to room temperature.
By 1.58g KMnO4(0.01mol) and 1.945g CeAc3·4H2O (0.005mol) is added under stirring
Solution is made in 100mL deionized waters, the spirit of vinegar of 50wt% is then added dropwise and adjusts pH between 4~5.Then 15g is added
The MnAc containing 0.015mol prepared in advance is added under the effect that is vigorously stirred in the above-mentioned active carbon particle being modified2It is water-soluble
Liquid reacts for 24 hours at 80 DEG C.The total moles ratio of metal Mn and Ce are 5:1.After reaction, solid product is obtained by filtration, uses second
Alcohol and deionized water are cleaned 4~5 times, and 4h is then calcined in 600 DEG C of Muffle furnace, and to obtain nano cerium Mn oxide/activated carbon multiple
Condensation material.
Embodiment 3
The coconut husk granular active carbon (iodine number 1000mg/g) for screening mesh number 80~150, is immersed in 65~70wt%
In the mixed solution of nitric acid and 98wt% sulfuric acid, 4h is pre-processed at 80 DEG C.It is 6 to pH to be cleaned for several times using deionized water after filtering
Between~7, the dry 8h in 120 DEG C of baking ovens.
Take above-mentioned pretreated activated carbon 100g and acrylic acid copolymer-maleic anhydride 25g under stirring
(1000r/min) is add to deionized water.Then 20g biurets are added, stir 1h at room temperature, then the ultrasonic wave at 60 DEG C
3h is handled, brown gel is obtained, supernatant liquor is filtered off after standing 1h, 3~5 times wash with distilled water, 100 DEG C is transferred to after filtering
1h obtains xerogel in baking oven.Then 2h is calcined in 500 DEG C of Muffle furnace, modified activated carbon is obtained after being cooled to room temperature
Grain.
By 1.58g KMnO4(0.01mol) and 2.74g (NH4)2Ce(NO3)6(0.005mol) is added under stirring
Solution is made in 100mL deionized waters, the spirit of vinegar of 50wt% is then added dropwise and adjusts pH between 4~5.Then 20g is added
(the NO of Mn containing 0.005mol prepared in advance are added under the effect that is vigorously stirred in the above-mentioned active carbon particle being modified3)2Water
Solution reacts for 24 hours at 80 DEG C.The total moles ratio of metal Mn and Ce are 6:1.After reaction, solid product is obtained by filtration, uses
Ethyl alcohol and deionized water are cleaned 4~5 times, are then calcined 6h in 500 DEG C of Muffle furnace and are obtained nano cerium Mn oxide/activated carbon
Composite material.
Comparative example 1
This comparative example does not carry out sour processing to activated carbon and surface is modified, and preparation method is as follows：
The coconut husk granular active carbon (iodine number 1000mg/g) for screening mesh number 80~150, the dry 8h in 120 DEG C of baking ovens.
By 1.58g KMnO4(0.01mol) and 2.17g Ce (NO3)3·6H2O (0.005mol) is added to 100mL under stirring
Solution is made in deionized water, the spirit of vinegar of 50wt% is then added dropwise and adjusts pH between 4~5.Then it is added at 10g dryings
(the NO of Mn containing 0.005mol prepared in advance are added under the effect that is vigorously stirred in active carbon particle after reason3)2Aqueous solution, 80
It is reacted for 24 hours at DEG C.The total moles ratio of metal Mn and Ce are 3:1.After reaction, solid product is obtained by filtration, using ethyl alcohol and
Deionized water is cleaned 4~5 times, is then calcined 6h in 500 DEG C of Muffle furnace and is obtained nano cerium Mn oxide/activated carbon composite wood
Material.
Comparative example 2
This comparative example has carried out sour processing to activated carbon, does not carry out surface modification, and preparation method is as follows：
The coconut husk granular active carbon (iodine number 1000mg/g) for screening mesh number 80~150, is immersed in 65~70wt%
In the mixed solution of nitric acid and 98wt% sulfuric acid, 4h is pre-processed at 80 DEG C.It is 6 to pH to be cleaned for several times using deionized water after filtering
Between~7, the dry 8h in 120 DEG C of baking ovens.
By 1.58g KMnO4(0.01mol) and 2.17g Ce (NO3)3·6H2O (0.005mol) is added under stirring
To solution is made in 100mL deionized waters, the spirit of vinegar of 50wt% is then added dropwise and adjusts pH between 4~5.Then it is added
(the NO of Mn containing 0.005mol prepared in advance are added under the effect that is vigorously stirred in the above-mentioned processed active carbon particles of acid of 10g3)2
Aqueous solution reacts for 24 hours at 80 DEG C.The total moles ratio of metal Mn and Ce are 3:1.After reaction, solid product is obtained by filtration, makes
It is cleaned 4~5 times with ethyl alcohol and deionized water, then calcines 6h in 500 DEG C of Muffle furnace and obtain nano cerium Mn oxide/activity
Carbon composite.
Composite material made from Examples 1 to 3 and comparative example 1,2 is placed in continuous fixed bed reactor and carries out first
The activity rating of aldehyde catalysis oxidation.Formaldehyde gas uses gaseous mixture (N in 0 DEG C of low temperature thermostat bath2/O2=79%/21%) be bubbled into
Enter reactor, concentration of formaldehyde 100ppm, GHSV=60L/ (gh) test the conversion ratio of (23 DEG C) formaldehyde (HCHO) at room temperature
And temperature when reaching 90% conversion ratio, the results are shown in table below：
Finally it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not limited to this hair
It is bright, although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still
It can modify to the technical solution recorded in previous embodiment, or equivalent replacement is carried out to which part.It is all in this hair
Within bright spirit and principle, any modification, equivalent replacement, improvement and so on should be included in protection scope of the present invention
Within.Although the above-mentioned specific implementation mode to the present invention is described, it is not intended to limit the protection scope of the present invention, institute
Belong to field technology personnel and should be understood that based on the technical solutions of the present invention those skilled in the art need not pay wound
The various modifications or changes that the property made labour can be made are still within protection scope of the present invention.
Claims (4)
1. a kind of nano cerium Mn oxide/nitrogen-dopped activated carbon composite material of Oxidation at room temperature formaldehyde, which is characterized in that pass through first
Sour processing and N doping obtain mesoporous activated carbon, then handle Jie with N doping in the acid by redox coprecipitation
Nano cerium manganese oxide catalyst is equably loaded in the cell walls of mesoporous activated carbon, is mixed to obtain nano cerium Mn oxide/nitrogen
Miscellaneous absorbent charcoal composite material；
The N doping uses sol-gal process；
The sol-gal process the specific steps are：Make acid treated activated carbon and nitrogenous compound in high-molecular surface active
Gel, washing, filtering, dry xerogel are formed under agent existence condition；
High-temperature heat treatment is carried out to above-mentioned xerogel, obtains the mesoporous activated carbon of N doping.
2. composite material as described in claim 1, which is characterized in that
The mesoporous activated carbon further includes part macropore, intermediary hole institute mainly based on mesoporous after acid processing and N doping
Accounting example 50% or more, average pore size between 30~50nm,
The cerium manganese oxide catalyst is nano particle, particle diameter distribution in 5~20nm,
Cerium Mn oxide load capacity in activated carbon is 5~15wt%.
3. a kind of preparation method of nano cerium Mn oxide/nitrogen-dopped activated carbon composite material of Oxidation at room temperature formaldehyde, feature
It is, including：
N doping is carried out to acid treated activated carbon using sol-gal process, obtains xerogel；
High-temperature heat treatment is carried out to above-mentioned xerogel, obtains the mesoporous activated carbon of N doping；
It is urged in the mesoporous activated carbon internal load nano cerium Mn oxide of above-mentioned N doping using in-situ oxidation reduction coprecipitation
Agent is to get nano cerium Mn oxide/nitrogen-dopped activated carbon composite material；
The sol-gal process the specific steps are：Make acid treated activated carbon and nitrogenous compound in high-molecular surface active
Gel, washing, filtering, dry xerogel are formed under agent existence condition.
4. method as claimed in claim 3, which is characterized in that the nitrogenous compound be melamine, urea, biuret,
At least one of thiocarbamide,
The high molecular surfactant is polyvinylpyrrolidone, polyethyleneimine, poly maleimide and its derivative, third
One kind in olefin(e) acid copolymer-maleic anhydride, acrylate copolymer,
The nitrogenous compound is 1 with acid treated quality of activated carbon ratio:5~10.
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| CN104741130A (en) * | 2013-12-27 | 2015-07-01 | 江苏瑞丰科技实业有限公司 | Normal temperature formaldehyde removal catalysis material |
| CN105457643B (en) * | 2015-12-25 | 2017-12-05 | 湖北大学 | A kind of preparation method of activated carbon supported type catalyst for Electrocatalysis Degradation organic wastewater |
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