CN116637628B - Air purifying agent, preparation method and application thereof - Google Patents
Air purifying agent, preparation method and application thereof Download PDFInfo
- Publication number
- CN116637628B CN116637628B CN202310425357.3A CN202310425357A CN116637628B CN 116637628 B CN116637628 B CN 116637628B CN 202310425357 A CN202310425357 A CN 202310425357A CN 116637628 B CN116637628 B CN 116637628B
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- Prior art keywords
- powder
- cobalt
- solution
- manganese oxide
- silver
- Prior art date
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- 239000012629 purifying agent Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 103
- 229910052613 tourmaline Inorganic materials 0.000 claims abstract description 42
- 229940070527 tourmaline Drugs 0.000 claims abstract description 42
- 239000011032 tourmaline Substances 0.000 claims abstract description 42
- 239000004332 silver Substances 0.000 claims abstract description 37
- 229910052709 silver Inorganic materials 0.000 claims abstract description 32
- XEUFSQHGFWJHAP-UHFFFAOYSA-N cobalt(2+) manganese(2+) oxygen(2-) Chemical compound [O--].[O--].[Mn++].[Co++] XEUFSQHGFWJHAP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000007864 aqueous solution Substances 0.000 claims description 26
- 239000002131 composite material Substances 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 22
- 238000001914 filtration Methods 0.000 claims description 20
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 20
- 239000000725 suspension Substances 0.000 claims description 20
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 claims description 19
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 18
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 16
- 238000007873 sieving Methods 0.000 claims description 15
- 238000000498 ball milling Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 150000001868 cobalt Chemical class 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 11
- 239000003638 chemical reducing agent Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 235000010323 ascorbic acid Nutrition 0.000 claims description 8
- 229960005070 ascorbic acid Drugs 0.000 claims description 8
- 239000011668 ascorbic acid Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 claims description 7
- 238000007908 dry granulation Methods 0.000 claims description 7
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 claims description 7
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 claims description 7
- 150000002696 manganese Chemical class 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 2
- ALIMWUQMDCBYFM-UHFFFAOYSA-N manganese(2+);dinitrate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ALIMWUQMDCBYFM-UHFFFAOYSA-N 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 156
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 8
- 239000001569 carbon dioxide Substances 0.000 abstract description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 28
- 239000007787 solid Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 18
- 229910044991 metal oxide Inorganic materials 0.000 description 15
- 150000004706 metal oxides Chemical class 0.000 description 13
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 12
- -1 rectorite Substances 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000009210 therapy by ultrasound Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 241000282414 Homo sapiens Species 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 230000036541 health Effects 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 229910001923 silver oxide Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000000809 air pollutant Substances 0.000 description 4
- 231100001243 air pollutant Toxicity 0.000 description 4
- 238000004887 air purification Methods 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- 229910052901 montmorillonite Inorganic materials 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004113 Sepiolite Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000012792 core layer Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 229910052624 sepiolite Inorganic materials 0.000 description 2
- 235000019355 sepiolite Nutrition 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- OTLLEIBWKHEHGU-UHFFFAOYSA-N 2-[5-[[5-(6-aminopurin-9-yl)-3,4-dihydroxyoxolan-2-yl]methoxy]-3,4-dihydroxy-6-(hydroxymethyl)oxan-2-yl]oxy-3,5-dihydroxy-4-phosphonooxyhexanedioic acid Chemical compound C1=NC=2C(N)=NC=NC=2N1C(C(C1O)O)OC1COC1C(CO)OC(OC(C(O)C(OP(O)(O)=O)C(O)C(O)=O)C(O)=O)C(O)C1O OTLLEIBWKHEHGU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241000192125 Firmicutes Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ARIWANIATODDMH-UHFFFAOYSA-N Lauric acid monoglyceride Natural products CCCCCCCCCCCC(=O)OCC(O)CO ARIWANIATODDMH-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002354 daily effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 239000002095 exotoxin Substances 0.000 description 1
- 231100000776 exotoxin Toxicity 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000003905 indoor air pollution Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Classifications
-
- 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
- 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
- B01D53/46—Removing components of defined structure
- B01D53/72—Organic compounds not provided for in groups B01D53/48 - B01D53/70, e.g. hydrocarbons
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8986—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or rhenium
-
- 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
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
-
- 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
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/16—Reducing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Analytical Chemistry (AREA)
- Biomedical Technology (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses an air purifying agent, a preparation method and application thereof. The cobalt-manganese oxide is prepared through hydrothermal method, silver is introduced on the cobalt-manganese oxide to improve the catalytic performance of the cobalt-manganese oxide, and the cobalt-manganese oxide is further ball-milled and granulated with modified tourmaline powder to obtain the air purifying agent. The air purifying agent disclosed by the invention is convenient to use, has the capability of thoroughly purifying free formaldehyde in air, is long in action time, has a higher effect in an environment with higher relative humidity, can oxidize the free formaldehyde into carbon dioxide, and can be widely applied to removal of the free formaldehyde in indoor environments.
Description
Technical Field
The invention belongs to the technical field of air purification, and particularly relates to an air purifying agent, a preparation method and application thereof.
Background
Common air pollutants include inhalable particles, formaldehyde, total volatile organic compounds, carbon monoxide, benzene, nitrogen oxides, ammonia and the like, and toxic and harmful substances are extremely harmful to human health. With the rapid growth of cities, air pollution has become an important issue in many developing countries. In recent years, the real estate industry in China develops rapidly, and the market is driven to increase in demand for decorative materials. On one hand, the development speed is too high, and on the other hand, the quality of the decoration materials is different, so that the content of organic volatile organic compounds, formaldehyde and benzene in the material is too high; on the other hand, due to the development of energy-saving building technology, the tightness of modern buildings is greatly enhanced, resulting in an increase in the concentration of indoor pollutants. According to investigation and statistics, 80% of indoor environment, the content of environmental pollutants in the air exceeds the national standard requirement, the physical health of people is seriously affected, and the life safety of human beings is threatened.
The life of a person spends about 70% of the time indoors, and the person absorbs 12 cubic meters of air every day, so that the importance of air quality to the health of the human body is self-evident. Among the ten factors promulgated by the world health organization that threaten human health, indoor air pollution is in the list of hertz and has become a healthy "stealth killer". Among many air pollutants, formaldehyde may be continuously harmful to the human body because it is released from furniture for a long period of time. Therefore, it is particularly important for removing formaldehyde from indoor air.
In order to create a clean and environment-friendly living, working and living environment, air purification technology has received a great deal of attention. In recent years, some natural mineral materials such as zeolite, diatomite, montmorillonite, rectorite, sepiolite, tourmaline and the like have the characteristics of abundant resources, low price, strong adsorptivity, environment friendliness and the like, and are widely paid attention as novel adsorption/degradation materials.
CN 108855121A discloses an air purifying agent made from potassium permanganate, manganese acetate, n-butyl titanate, montmorillonite powder, rice husk, sodium metaaluminate, nickel nitrate, etc.; the invention has excellent nickel-based catalytic performance and high adsorption of montmorillonite, and achieves the aim of removing various pollutants such as organic matters, suspended particles, bacteria and the like in the air.
CN 103861421A discloses an air purifying agent, which is prepared by mixing diatomite powder, zeolite powder, medical stone powder, tourmaline powder, activated carbon powder, sepiolite powder and titanium dioxide powder, granulating and drying; the air purifying agent has large and uniform specific surface area and good adsorption and decomposition effects on harmful substances in the air, and is an ideal material for environmental purification of indoor, in-car and other closed spaces and various air purifiers.
CN 108246046A discloses an antibacterial air purifying agent, its preparation method and application. The sterilizing air purifying agent comprises a surface layer and a core layer, wherein the surface layer is a bacteriostatic and bactericidal film containing lauric acid monoglyceride, and the core layer is a mixture composed of tourmaline powder and medical stone particles loaded with nano zinc oxide. The purifying agent is safe and nontoxic, and can be used for spaces such as household refrigerators and the like needing sterilization and air purification; can effectively inhibit bacteria from producing exotoxin; killing gram positive bacteria, gram negative bacteria and the like, and the sterilization rate can reach 99 percent; can generate negative ions and has the function of air purification.
Although the natural minerals used in the methods have wide sources, simple preparation procedures and good removal effect on air pollutants, the natural mineral carriers have large specific surface area, a large amount of silicon hydroxyl groups exist on the surfaces, and water is easy to be adsorbed in the environment with high relative humidity, so that the adsorption/degradation capability of the whole purifying agent is reduced; in an environment with high relative humidity, the active ingredients of the air purifying agent are easy to deactivate, so that the removal efficiency is obviously reduced. In addition, many prior art technologies incorporate photocatalysts such as titanium dioxide, zinc oxide, zirconium dioxide, etc., but these materials have limited photocatalytic capabilities in indoor environments lacking ultraviolet light irradiation.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention is to provide an air purifier capable of effectively removing formaldehyde from air in a daily indoor environment and maintaining high removal efficiency in an environment with high relative humidity.
In order to achieve the above object, the present invention provides a method for preparing an air purifying agent, comprising the steps of:
(1) Dissolving soluble cobalt salt and soluble manganese salt in water under stirring to form a uniform solution I; adding sodium hydroxide aqueous solution into the continuously stirred solution I to adjust the pH value of the solution I, and continuously stirring the solution I to form solution II; carrying out hydrothermal reaction on the solution II, naturally cooling to room temperature, filtering, washing and drying to obtain insoluble matters; calcining the insoluble matter to obtain cobalt manganese oxide powder;
(2) Dispersing the cobalt manganese oxide powder prepared in the step (1) in water under ultrasonic to obtain uniform suspension a; adding silver nitrate into the suspension a which is continuously stirred, adding a reducing agent solution, and stirring for reaction; filtering, washing, drying, crushing and sieving to obtain silver/cobalt manganese oxide composite powder;
(3) Ball-milling and mixing the silver/cobalt manganese oxide composite powder obtained in the step (2) with tourmaline powder to obtain a silver/cobalt manganese oxide/tourmaline mixture, and performing dry granulation and molding to obtain the air purifying agent.
Preferably, in the step (1), the mass ratio of the soluble cobalt salt to the soluble manganese salt is 1: (2-3); the volume ratio of the mass of the soluble cobalt salt to the water is 1: (20-30) g/mL; the stirring speed is 300-500 r/min; the concentration of the sodium hydroxide aqueous solution is 0.6-2 mol/L, and the pH value is adjusted to 9.0-11.0; continuously stirring for 0.5-2 h at the stirring rate of 300-500 r/min; the temperature of the hydrothermal reaction is 160-180 ℃, and the hydrothermal reaction time is 4-8 hours; the washing is to wash with water and ethanol for three times respectively, and the drying is to dry in a constant temperature oven at 80-100 ℃ for 4-6 h; the calcination is carried out for 2-4 hours from the temperature of room temperature of 25 ℃ to 400-600 ℃ at the temperature rising rate of 3-5 ℃/min.
Further preferably, the soluble cobalt salt in the step (1) is one of cobalt acetate tetrahydrate and cobalt nitrate hexahydrate; the soluble manganese salt is one of manganese acetate tetrahydrate and manganese nitrate tetrahydrate; in the step (1), after the pH is regulated, the mass ratio of the cobalt salt to the soluble cobalt salt is (1-2): 1.
Preferably, the ultrasonic power in the step (2) is 50-200W, the frequency is 20-130 KHz, the temperature is 20-40 ℃ and the time is 20-60 min; the mass to water volume ratio of the cobalt manganese oxide powder is (10-50): 1g/L; stirring continuously at a stirring rate of 300-500 r/min after the suspension is subjected to ultrasonic treatment, wherein the mass ratio of the added silver nitrate to the cobalt manganese oxide powder is 1: (10-20); the volume ratio of the reducing agent solution to the suspension a is (0.1-0.5): 1, adding a reducing agent solution into a continuously stirred suspension a, wherein the reducing agent solution is one of a sodium borohydride aqueous solution, an ascorbic acid aqueous solution and a sodium bisulphite aqueous solution with the concentration of 0.1-0.2 mol/L; after adding the reducer solution, continuing to react for 1-3 h at the stirring rate of 300-500 r/min; the washing is to wash with water and ethanol for three times respectively, and the drying is to dry in a constant temperature oven at 80-100 ℃ for 4-6 h; the crushing and sieving are carried out by sieving with 300-500 meshes of sieve after crushing, and collecting powder under the sieve.
Preferably, in the step (3), the weight ratio of the silver/cobalt manganese oxide composite powder to tourmaline powder is 1: (5-10); the ball milling speed is 200-300 r/min.
Further preferably, the tourmaline powder in the step (3) is modified by a modification method comprising: placing tourmaline powder with 300-500 meshes into hydrochloric acid or nitric acid aqueous solution with 1-3 mol/L, soaking for 2-4 h, filtering, washing pH to 6.0-7.5 with water, placing insoluble substances into a constant temperature oven, drying for 4-6h at 80-100 ℃, then sieving with 300-500 meshes of sieve, and collecting powder under the sieve to obtain the modified tourmaline powder.
According to another aspect of the present invention, there is provided the use of the above air cleaner for cleaning indoor air: and uniformly placing the air purifying agent into a closed newly decorated house.
The invention has the beneficial effects that:
(1) According to the invention, the cobalt manganese oxide is prepared by a hydrothermal method, silver is reduced on the surface of the cobalt manganese oxide and ball-milled and granulated with modified tourmaline, and the composite metal oxide/natural mineral type air purifying agent is prepared, and the raw material source is wide, the raw material is nontoxic or low in toxicity, the preparation method is simple, and the composite metal oxide/natural mineral type air purifying agent is suitable for household use and industrial production.
(2) The air purifying agent has the capability of thoroughly purifying formaldehyde which is free in the air, does not need external conditions such as illumination and the like, can still keep relatively high removal activity in an environment with high relative humidity, and can be widely applied to the removal of air pollutants in indoor environments.
(3) The air purifying agent has long action duration, can still maintain the removal capability after 180 days of use, can be processed into different shapes according to the needs, and is very convenient to use.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
Example 1 preparation of an air cleaner
(1) Dissolving 5g of cobalt acetate tetrahydrate and 12g of manganese acetate tetrahydrate in 150mL of water at a stirring rate of 500r/min to form a uniform solution I; adding 1mol/L sodium hydroxide aqueous solution into the solution I which is continuously stirred at 500r/min, adjusting the pH value to 9.5, and continuously stirring for 1h to form solution II; transferring the solution II to a 200mL polytetrafluoroethylene reaction kettle, transferring to a 180 ℃ oven for hydrothermal reaction for 6 hours, naturally cooling to room temperature, filtering, washing with water and ethanol three times to obtain insoluble substances, and placing in a constant temperature oven for drying at 100 ℃ for 5 hours to obtain solid powder; placing the solid powder in a muffle furnace, and calcining for 2 hours at a heating rate of 3 ℃/min from room temperature of 25 ℃ to 450 ℃ to obtain cobalt manganese oxide powder;
(2) Dispersing 50g of the cobalt manganese oxide powder prepared in the step (1) in 1L of water, and carrying out ultrasonic treatment for 30min at the ultrasonic power of 100W, the frequency of 50KHz and the temperature of 25 ℃ to obtain a uniform suspension a; adding 5g of silver nitrate into a suspension a which is continuously stirred at a stirring rate of 500r/min, adding 100mL of an ascorbic acid aqueous solution with a concentration of 0.1mol/L, and reacting for 1h at a stirring rate of 500 r/min; filtering, washing with water and ethanol for three times to obtain insoluble substances, and drying in a constant temperature oven at 100deg.C for 5 hr to obtain solid powder; crushing the solid powder, sieving with a 300-mesh sieve, and collecting powder under the sieve to obtain silver/cobalt manganese oxide composite powder;
(3) Ball-milling and mixing 30g of the silver/cobalt manganese oxide composite powder prepared in the step (2) with 200g of tourmaline powder, ball-milling for 2 hours at 300r/min to obtain a silver/cobalt manganese oxide/tourmaline mixture, and performing dry granulation and molding to prepare a spherical shape with the diameter of 8mm, namely the air purifying agent prepared in the embodiment.
Comparative example 1 preparation of an air purifying agent
(1) 17G of cobalt acetate tetrahydrate is dissolved in 150mL of water under the stirring speed of 500r/min to form a uniform solution I; adding 1mol/L sodium hydroxide aqueous solution into the solution I which is continuously stirred at 500r/min, adjusting the pH value to 9.5, and continuously stirring for 1h to form solution II; transferring the solution II to a 200mL polytetrafluoroethylene reaction kettle, transferring to a 180 ℃ oven for hydrothermal reaction for 6 hours, naturally cooling to room temperature, filtering, washing with water and ethanol three times to obtain insoluble substances, and placing in a constant temperature oven for drying at 100 ℃ for 5 hours to obtain solid powder; placing the solid powder in a muffle furnace, and calcining for 2 hours at a heating rate of 3 ℃/min from room temperature of 25 ℃ to 450 ℃ to obtain cobaltosic oxide powder;
(2) Dispersing 50g of the cobaltosic oxide powder prepared in the step (1) in 1L of water, and carrying out ultrasonic treatment for 30min at the ultrasonic power of 100W, the frequency of 50KHz and the temperature of 25 ℃ to obtain a uniform suspension a; adding 5g of silver nitrate into a suspension a which is continuously stirred at a stirring rate of 500r/min, adding 100mL of an ascorbic acid aqueous solution with a concentration of 0.1mol/L, and reacting for 1h at a stirring rate of 500 r/min; filtering, washing with water and ethanol for three times to obtain insoluble substances, and drying in a constant temperature oven at 100deg.C for 5 hr to obtain solid powder; crushing the solid powder, sieving with a 300-mesh sieve, and collecting powder under the sieve to obtain silver/cobaltosic oxide composite powder;
(3) Putting 30g of the silver/cobaltosic oxide composite powder prepared in the step (2) and 200g of tourmaline powder into a ball mill, ball-milling for 2 hours at 300r/min to obtain a silver/cobaltosic oxide/tourmaline mixture, and performing dry granulation and molding to prepare a spherical shape with the diameter of 8mm, namely the air purifying agent prepared in the comparative example;
Comparative example 2 preparation of an air purifying agent
(1) 17G of manganese acetate tetrahydrate is dissolved in 150mL of water under the stirring speed of 500r/min to form a uniform solution I; adding 1mol/L sodium hydroxide aqueous solution into the solution I which is continuously stirred at 500r/min, adjusting the pH value to 9.5, and continuously stirring for 1h to form solution II; transferring the solution II to a 200mL polytetrafluoroethylene reaction kettle, transferring to a 180 ℃ oven for hydrothermal reaction for 6 hours, naturally cooling to room temperature, filtering, washing with water and ethanol three times to obtain insoluble substances, and placing in a constant temperature oven for drying at 100 ℃ for 5 hours to obtain solid powder; placing the solid powder in a muffle furnace, and calcining for 2 hours at a heating rate of 3 ℃/min from room temperature of 25 ℃ to 450 ℃ to obtain manganese sesquioxide powder;
(2) Dispersing 50g of the manganese sesquioxide powder prepared in the step (1) in 1L of water, and carrying out ultrasonic treatment for 30min at the ultrasonic power of 100W, the frequency of 50KHz and the temperature of 25 ℃ to obtain a uniform suspension a; adding 5g of silver nitrate into a suspension a which is continuously stirred at a stirring rate of 500r/min, adding 100mL of an ascorbic acid aqueous solution with a concentration of 0.1mol/L, and reacting for 1h at a stirring rate of 500 r/min; filtering, washing with water and ethanol for three times to obtain insoluble substances, and drying in a constant temperature oven at 100deg.C for 5 hr to obtain solid powder; crushing the solid powder, sieving with a 300-mesh sieve, and collecting powder under the sieve to obtain silver/manganese trioxide composite powder;
(3) Putting 30g of the silver/manganese sesquioxide compound powder prepared in the step (2) and 200g of tourmaline powder into a ball mill, ball-milling for 2 hours at 300r/min to obtain a silver/manganese sesquioxide/modified tourmaline mixture, and performing dry granulation and molding to prepare a spherical shape with the diameter of 8mm, namely the air purifying agent prepared in the comparative example.
Example 2 preparation of an air cleaner
(1) Dissolving 5g of cobalt acetate tetrahydrate and 12g of manganese acetate tetrahydrate in 150mL of water at a stirring rate of 500r/min to form a uniform solution I; adding 1mol/L sodium hydroxide aqueous solution into solution I which is continuously stirred at 500r/min, adjusting the pH to 9.5, adding 6g urea, and continuously stirring for 1h to form solution II; transferring the solution II to a 200mL polytetrafluoroethylene reaction kettle, transferring to a 180 ℃ oven for hydrothermal reaction for 6 hours, naturally cooling to room temperature, filtering, washing with water and ethanol three times to obtain insoluble substances, and placing in a constant temperature oven for drying at 100 ℃ for 5 hours to obtain solid powder; placing the solid powder in a muffle furnace, and calcining for 2 hours at a heating rate of 3 ℃/min from room temperature of 25 ℃ to 450 ℃ to obtain cobalt manganese oxide powder;
(2) Dispersing 50g of the cobalt manganese oxide powder prepared in the step (1) in 1L of water, and carrying out ultrasonic treatment for 30min at the ultrasonic power of 100W, the frequency of 50KHz and the temperature of 25 ℃ to obtain a uniform suspension a; adding 5g of silver nitrate into a suspension a which is continuously stirred at a stirring rate of 500r/min, adding 100mL of an ascorbic acid aqueous solution with a concentration of 0.1mol/L, and reacting for 1h at a stirring rate of 500 r/min; filtering, washing with water and ethanol for three times to obtain insoluble substances, and drying in a constant temperature oven at 100deg.C for 5 hr to obtain solid powder; crushing the solid powder, sieving with a 300-mesh sieve, and collecting powder under the sieve to obtain silver/cobalt manganese oxide composite powder;
(3) Ball-milling and mixing 30g of the silver/cobalt manganese oxide composite powder prepared in the step (2) with 200g of tourmaline powder, ball-milling for 2 hours at 300r/min to obtain a silver/cobalt manganese oxide/tourmaline mixture, and performing dry granulation and molding to prepare a spherical shape with the diameter of 8mm, namely the air purifying agent prepared in the embodiment.
Example 3 preparation of an air cleaner
(1) Dissolving 5g of cobalt acetate tetrahydrate and 12g of manganese acetate tetrahydrate in 150mL of water at a stirring rate of 500r/min to form a uniform solution I; adding 1mol/L sodium hydroxide aqueous solution into solution I which is continuously stirred at 500r/min, adjusting the pH to 9.5, adding 6g urea, and continuously stirring for 1h to form solution II; transferring the solution II to a 200mL polytetrafluoroethylene reaction kettle, transferring to a 180 ℃ oven for hydrothermal reaction for 6 hours, naturally cooling to room temperature, filtering, washing with water and ethanol three times to obtain insoluble substances, and placing in a constant temperature oven for drying at 100 ℃ for 5 hours to obtain solid powder; placing the solid powder in a muffle furnace, and calcining for 2 hours at a heating rate of 3 ℃/min from room temperature of 25 ℃ to 450 ℃ to obtain cobalt manganese oxide powder;
(2) Dispersing 50g of the cobalt manganese oxide powder prepared in the step (1) in 1L of water, and carrying out ultrasonic treatment for 30min at the ultrasonic power of 100W, the frequency of 50KHz and the temperature of 25 ℃ to obtain a uniform suspension a; adding 5g of silver nitrate into a suspension a which is continuously stirred at a stirring rate of 500r/min, adding 100mL of an ascorbic acid aqueous solution with a concentration of 0.1mol/L, and reacting for 1h at a stirring rate of 500 r/min; filtering, washing with water and ethanol for three times to obtain insoluble substances, and drying in a constant temperature oven at 100deg.C for 5 hr to obtain solid powder; crushing the solid powder, sieving with a 300-mesh sieve, and collecting powder under the sieve to obtain silver/cobalt manganese oxide composite powder;
(3) Putting 30g of the silver/cobalt manganese oxide composite powder prepared in the step (2) and 200g of modified tourmaline powder into a ball mill, ball-milling for 2 hours at 300r/min to obtain a silver/cobalt manganese oxide/modified tourmaline mixture, and performing dry granulation and molding to prepare a sphere with the diameter of 8mm, namely the air purifying agent prepared in the embodiment;
The preparation method of the modified tourmaline powder comprises the following steps: placing tourmaline powder with 300 meshes in 2mol/L nitric acid aqueous solution, soaking for 2 hours, filtering, washing the pH to 7.0 with water, placing insoluble substances in a constant temperature oven, drying at 100 ℃ for 4 hours, then sieving with a 300-mesh sieve, and collecting powder under the sieve to obtain the modified tourmaline powder.
Comparative example 3 preparation of an air purifying agent
(1) Dissolving 5g of cobalt acetate tetrahydrate and 12g of manganese acetate tetrahydrate in 150mL of water at a stirring rate of 500r/min to form a uniform solution I; adding 1mol/L sodium hydroxide aqueous solution into solution I which is continuously stirred at 500r/min, adjusting the pH to 9.5, adding 6g urea, and continuously stirring for 1h to form solution II; transferring the solution II to a 200mL polytetrafluoroethylene reaction kettle, transferring to a 180 ℃ oven for hydrothermal reaction for 6 hours, naturally cooling to room temperature, filtering, washing with water and ethanol three times to obtain insoluble substances, and placing in a constant temperature oven for drying at 100 ℃ for 5 hours to obtain solid powder; placing the solid powder in a muffle furnace, and calcining for 2 hours at a heating rate of 3 ℃/min from room temperature of 25 ℃ to 450 ℃ to obtain cobalt manganese oxide powder;
(2) Dispersing 50g of the cobalt manganese oxide powder prepared in the step (1) in 1L of water, and carrying out ultrasonic treatment for 30min at the ultrasonic power of 100W, the frequency of 50KHz and the temperature of 25 ℃ to obtain a uniform suspension a; adding 5g of silver nitrate into a suspension a which is continuously stirred at a stirring rate of 500r/min, adding 100mL of an ascorbic acid aqueous solution with a concentration of 0.1mol/L, and reacting for 1h at a stirring rate of 500 r/min; filtering, washing with water and ethanol for three times to obtain insoluble substances, and drying in a constant temperature oven at 100deg.C for 5 hr to obtain solid powder; crushing the solid powder, sieving with a 300-mesh sieve, and collecting powder under the sieve to obtain silver/cobalt manganese oxide composite powder; and (3) granulating and forming by a dry method to prepare a spherical shape with the diameter of 8mm, namely the air purifying agent prepared in the comparative example.
Comparative example 4 preparation of an air purifying agent
Placing tourmaline powder with 300 meshes in 2mol/L nitric acid aqueous solution, soaking for 2 hours, filtering, washing the pH to 7.0 with water, placing insoluble substances in a constant temperature oven, drying at 100 ℃ for 4 hours, then sieving with a 300-mesh sieve, and collecting powder under the sieve to obtain modified tourmaline powder; ball milling 230g modified tourmaline powder at 300r/min for 2h, dry granulating and molding to obtain spherical shape with diameter of 8mm, which is the air purifying agent prepared in this comparative example.
Test example 1 effect of air cleaner on removal of Formaldehyde
Introducing formaldehyde gas into a test cabin with the length, width and height of 1m to ensure that the initial formaldehyde concentration in the cabin is 1.5mg/m 3; 20g of the air cleaners prepared in examples 1 to 3 and comparative examples 1 to 4 of the present invention were placed, respectively, and the removal test of formaldehyde was completed within 1 hour while keeping the temperature in the cabin at room temperature of 25℃and the relative humidity in the cabin at 50%, and the results are shown in Table 1.
TABLE 1 removal rate of formaldehyde for 1h by air cleaners prepared in examples 1 to 3 and comparative examples 1 to 4 of the present invention
| Formaldehyde removal after 1h (%) | |
| Example 1 | 68.1 |
| Comparative example 1 | 42.1 |
| Comparative example 2 | 46.3 |
| Example 2 | 83.1 |
| Example 3 | 98.4 |
| Comparative example 3 | 32.6 |
| Comparative example 4 | 11.3 |
It can be seen that the formaldehyde removal rate of comparative example 4 was only 11.3%, which indicates that formaldehyde was only adsorbed on the surface of the remover and no further oxidation reaction occurred; the existence of silver plays a vital role in oxidative degradation of formaldehyde at room temperature of 25 ℃ in the air remover prepared by the invention. The removal rate of formaldehyde in comparative example 1 and comparative example 2 prepared from one-component metal oxide is not more than 50%, which indicates that silver-containing cobaltosic oxide composite tourmaline and silver-containing manganese sesquioxide composite tourmaline are difficult to remove free formaldehyde molecules. The removal rate of the silver-containing cobalt-manganese metal oxide composite tourmaline prepared in the embodiment 1 to formaldehyde is 68.1%, which is probably that the composite metal oxide has higher electron transfer rate, a large amount of oxygen vacancies exist in the composite metal oxide, silver can effectively adsorb active oxygen species, and the tourmaline has a large amount of hydroxyl groups and negative oxygen ions, so that good synergistic effect is generated, and the removal rate of the silver-containing cobalt-manganese metal oxide composite tourmaline to formaldehyde is obviously improved. The example 2 in which urea is added during the preparation of metal oxide has a significant increase in formaldehyde removal rate compared to the example 1 in which urea is not added, probably because of the swelling effect on the metal oxide, which increases the specific surface area, and the incorporation of some nitrogen into the crystal lattice of the metal oxide, which greatly enhances the dispersion of silver on the surface of the metal oxide, increases the reactive sites, and promotes the formaldehyde reaction on the surface of the scavenger. Comparative example 3, which was prepared without adding tourmaline, had a formaldehyde removal rate of 32.6%, while example 3, which was prepared by ball milling with silver and modified tourmaline, exhibited the highest formaldehyde removal rate of 98.4% by adding urea during the preparation of metal oxide, probably because the acid treatment activation energy increased the tourmaline surface area and the number of surface hydroxyl groups; the introduction of nitrogen increases the specific surface area of the metal oxide and the dispersibility of silver species, and improves the reactive sites; the composite metal oxide has stronger electron transfer rate, more oxygen vacancies exist in the composite metal oxide, a good synergistic effect is generated, the adsorption of formaldehyde on the surface of the purifying agent is enhanced, the catalytic degradation is further promoted, and the formaldehyde removal rate is greatly improved.
Test example 2 influence of relative humidity on degradation of formaldehyde by air cleaners
Introducing formaldehyde gas into a test cabin with the length, width and height of 1m to ensure that the initial formaldehyde concentration in the cabin is 1.5mg/m 3, and placing 20g of the air purifying agent prepared in the embodiment 3 of the invention; the temperature in the cabin was kept at room temperature of 25 ℃, and when the relative humidity in the cabin was 5%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 85%, the formaldehyde removal test was completed within 1 hour, and the gas composition in the cabin was monitored. The change in the concentration of the gas in the cabin during the test was monitored, and the concentration of formaldehyde was decreased and the concentration of carbon dioxide was significantly increased at different relative humidities, indicating that formaldehyde was converted to carbon dioxide. The conversion rate of the air purifying agent to formaldehyde is lower than 65% when the relative humidity is 5% and 85%, while the conversion rate of the air purifying agent prepared by the invention to formaldehyde is more than 90% when the relative humidity is 20% -80%, and the result shows that the air purifying agent prepared by the invention has better tolerance to indoor environment and can effectively convert formaldehyde into carbon dioxide. However, the influence of the relative humidity on the air purifying agent may be because, at a lower relative humidity, water vapor is difficult to form hydroxyl groups on the surface of the air purifying agent, and formaldehyde molecules are difficult to adsorb on the surface of the air purifying agent; in addition, the air cleaner prepared by the invention has no simple adsorption effect on formaldehyde, and a large amount of hydroxyl groups are consumed on the surface of the air cleaner by formaldehyde with low relative humidity, so that the silver/cobalt manganese oxide compound as an active ingredient is difficult to generate hydroxyl free radicals, and the conversion rate of formaldehyde is low. In the environment with higher relative humidity, the air purifying agent has higher removal effect, probably because more water vapor exists, hydroxyl groups are easy to form on the surface of the removing agent to enhance the adsorption effect on formaldehyde molecules, the hydroxyl loss in the process of catalyzing and oxidizing formaldehyde is improved, and hydroxyl free radicals are also easier to form. At this time, active oxygen species adsorbed on the silver surface, oxygen holes existing in cobalt manganese oxide are easier, negative oxygen ions of tourmaline are easier to act with adsorbed formaldehyde, and good synergistic effect is generated between the active oxygen species and the cobalt manganese oxide, so that the active oxygen species and the cobalt manganese oxide can be in a larger relative humidity range. When the relative humidity in the environment is more than 80%, water molecules can be in competitive adsorption with formaldehyde molecules and occupy active sites on the surface of the remover, so that the removal rate of formaldehyde gas is greatly reduced.
Application example of air purifying agent for removing formaldehyde in enclosed room
50G of the air purifying agent prepared in example 3 of the present invention was equally divided into 5 parts and placed in 5 air-permeable nonwoven bags, and the air-permeable nonwoven bags containing the air purifying agent were evenly placed in a newly decorated house having an area of 25m 2 and an initial formaldehyde concentration of 0.82mg/m 3. The formaldehyde concentration in the house is monitored, and the result shows that the formaldehyde concentration in the house is reduced to 0.03mg/m 3 after three days; the formaldehyde in the house was continuously monitored over 180 days, and the result showed that the formaldehyde concentration in the house was 0.05mg/m 3 after 180 days. The removers after 180 days of leaving were taken out, and the same removal test as in test example 1 was completed again, whereby the removal rate of formaldehyde was 95.1%. These results show that the air purifying agent prepared by the invention can quickly reduce the formaldehyde concentration in the enclosed environment to within 0.1mg/m 3 of the national standard, and still maintain high formaldehyde removal rate after long-term use.
The foregoing describes in detail preferred embodiments of the present invention. It should be understood that numerous modifications and variations can be made in accordance with the concepts of the invention by one of ordinary skill in the art without undue burden. Therefore, all technical solutions which can be obtained by logic analysis, reasoning or limited experiments based on the prior art by the person skilled in the art according to the inventive concept shall be within the scope of protection defined by the claims.
Claims (8)
1. The preparation method of the air purifying agent is characterized by comprising the following steps of:
(1) Dissolving soluble cobalt salt and soluble manganese salt in water under stirring to form a uniform solution I; adding sodium hydroxide aqueous solution into the continuously stirred solution I to adjust the pH value of the solution I, and continuously stirring the solution I to form solution II; carrying out hydrothermal reaction on the solution II, naturally cooling to room temperature, filtering, washing and drying to obtain insoluble matters; calcining the insoluble matter to obtain cobalt manganese oxide powder;
(2) Dispersing the cobalt manganese oxide powder prepared in the step (1) in water under ultrasonic to obtain uniform suspension a; adding silver nitrate into the suspension a which is continuously stirred, adding a reducing agent solution, and stirring for reaction; filtering, washing, drying, crushing and sieving to obtain silver/cobalt manganese oxide composite powder;
(3) Ball-milling and mixing the silver/cobalt manganese oxide composite powder obtained in the step (2) with tourmaline powder to obtain a silver/cobalt manganese oxide/tourmaline mixture, and performing dry granulation and molding to obtain the air purifying agent;
in the step (1), the mass ratio of the soluble cobalt salt to the soluble manganese salt is 1: (2-3); the volume ratio of the mass of the soluble cobalt salt to the water is 1: (20-30) g/mL;
the stirring rates in the step (1) and the step (2) are respectively 300-500 r/min independently; the drying is carried out in a constant temperature oven at 80-100 ℃ for 4-6 h independently;
In the step (1), after the pH is regulated, the mass ratio of the cobalt salt to the soluble cobalt salt is (1-2): 1 urea;
The temperature rising rate of the calcination in the step (1) is 3-5 ℃/min, and the calcination is carried out for 2-4 hours from the temperature of 25 ℃ to 400-600 ℃;
The ultrasonic power in the step (2) is 50-200W, the frequency is 20-130 KHz, the temperature is 20-40 ℃, and the time is 20-60 min; the mass ratio of the cobalt manganese oxide powder to the water is (10-50): 1 g/L; the mass ratio of the added silver nitrate to the cobalt manganese oxide powder is 1: (10-20); the volume ratio of the reducing agent solution to the suspension a is (0.1-0.5): 1, a step of; the sieving is carried out by sieving with a 300-500 mesh screen, and powder under the screen is collected;
The mass ratio of the silver/cobalt manganese oxide composite powder to tourmaline powder in the step (3) is 1: (5-10); ball milling speed is 200-300 r/min; the tourmaline powder is modified, and the modification treatment steps are as follows: placing tourmaline powder with 300-500 meshes in 1-3 mol/L hydrochloric acid or nitric acid aqueous solution, soaking for 2-4 hours, filtering, washing with water until the pH value is 6.0-7.5, placing insoluble substances in a constant temperature oven, drying for 4-6 hours at 80-100 ℃, then screening with a 300-500 mesh screen, and collecting powder under the screen to obtain the modified tourmaline powder.
2. The method of claim 1, wherein the soluble cobalt salt in step (1) is one of cobalt acetate tetrahydrate and cobalt nitrate hexahydrate; the soluble manganese salt is one of manganese acetate tetrahydrate and manganese nitrate tetrahydrate.
3. The method for preparing an air cleaner according to claim 1, wherein the aqueous solution of sodium hydroxide is added to the solution i which is continuously stirred in the step (1) to adjust the pH thereof to 9.0 to 11.0.
4. The method for preparing an air purifying agent according to claim 1, wherein the hydrothermal reaction temperature in the step (1) is 160-180 ℃ and the hydrothermal reaction time is 4-8 hours.
5. The method of claim 1, wherein the reducing agent solution in the step (2) is one of a sodium borohydride aqueous solution, an ascorbic acid aqueous solution, and a sodium bisulphite aqueous solution of 0.1-0.2 mol/L.
6. The method for preparing an air cleaner according to claim 1, wherein the step (2) of adding the reducing agent solution is performed by stirring the reducing agent solution, and then the reaction is continued for 1-3 hours at a stirring rate of 300-500 r/min.
7. An air purifying agent which is characterized by being prepared by the preparation method according to any one of claims 1 to 6.
8. Use of the air cleaner according to claim 7 for cleaning indoor air.
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