CN114749151B - Formaldehyde adsorbent for air purification and preparation method and application thereof - Google Patents
Formaldehyde adsorbent for air purification and preparation method and application thereof Download PDFInfo
- Publication number
- CN114749151B CN114749151B CN202210484206.0A CN202210484206A CN114749151B CN 114749151 B CN114749151 B CN 114749151B CN 202210484206 A CN202210484206 A CN 202210484206A CN 114749151 B CN114749151 B CN 114749151B
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- formaldehyde
- air purification
- mesoporous carbon
- solution
- temperature
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 279
- 239000003463 adsorbent Substances 0.000 title claims abstract description 55
- 238000004887 air purification Methods 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 69
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000003756 stirring Methods 0.000 claims abstract description 43
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000005011 phenolic resin Substances 0.000 claims abstract description 37
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000001914 filtration Methods 0.000 claims abstract description 25
- 238000005406 washing Methods 0.000 claims abstract description 23
- 230000003647 oxidation Effects 0.000 claims abstract description 21
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000012719 thermal polymerization Methods 0.000 claims abstract description 17
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 14
- 239000010941 cobalt Substances 0.000 claims abstract description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 150000003751 zinc Chemical class 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 238000010000 carbonizing Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 70
- 238000000034 method Methods 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 22
- 239000003575 carbonaceous material Substances 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 16
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 16
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000001307 helium Substances 0.000 claims description 13
- 229910052734 helium Inorganic materials 0.000 claims description 13
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- 230000007935 neutral effect Effects 0.000 claims description 11
- 239000012286 potassium permanganate Substances 0.000 claims description 11
- 230000001105 regulatory effect Effects 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 238000003763 carbonization Methods 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 9
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 9
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 8
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007800 oxidant agent Substances 0.000 claims description 7
- 150000001879 copper Chemical class 0.000 claims description 6
- 150000002696 manganese Chemical class 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- 229920000428 triblock copolymer Polymers 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 36
- 238000001179 sorption measurement Methods 0.000 abstract description 30
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052802 copper Inorganic materials 0.000 abstract description 5
- 239000010949 copper Substances 0.000 abstract description 5
- 229910052748 manganese Inorganic materials 0.000 abstract description 5
- 239000011572 manganese Substances 0.000 abstract description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005286 illumination Methods 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 31
- 239000007789 gas Substances 0.000 description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 239000012855 volatile organic compound Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
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- 238000010146 3D printing Methods 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 239000004964 aerogel Substances 0.000 description 4
- 239000002775 capsule Substances 0.000 description 4
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- 239000011248 coating agent Substances 0.000 description 4
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- 239000003344 environmental pollutant Substances 0.000 description 4
- -1 formaldehyde, benzene series Chemical class 0.000 description 4
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- 231100000719 pollutant Toxicity 0.000 description 4
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
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- 239000002156 adsorbate Substances 0.000 description 2
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
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- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
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Classifications
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01D53/02—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 by adsorption, e.g. preparative gas chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- 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
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The invention belongs to the technical field of air purification, and particularly relates to a formaldehyde adsorbent for air purification and a preparation method and application thereof. The preparation method comprises the following steps: preparing phenolic resin ethanol solution, performing thermal polymerization, carbonizing to obtain mesoporous carbon containing manganese and copper, and performing oxidation treatment to obtain oxidized mesoporous carbon; and dissolving a cobalt source in deionized water, adding mesoporous carbon subjected to oxidation treatment, stirring uniformly to obtain a mixture solution, adding 2-methylimidazole, ferric salt and zinc salt into the mixture solution, stirring, filtering, washing, drying, and roasting under an inert atmosphere to obtain the methanol adsorbent. The formaldehyde adsorbent prepared by the invention has excellent adsorption and removal capacity on formaldehyde, can oxidize formaldehyde under illumination conditions, and effectively removes formaldehyde in air.
Description
Technical Field
The invention belongs to the technical field of air purification. More particularly, to a formaldehyde adsorbent for air purification, a preparation method and application thereof.
Background
Air pollution, particularly indoor air pollution, poses serious hazards to the human body, and 60% of human diseases have been reported to be from air pollution. Interior decoration, use of household chemicals, and human activity produce a large amount of pollutants such as formaldehyde, benzene series, ammonia, and the like. Formaldehyde is one of volatile organic compounds, and has strong irritation to ocular mucosa, nose and upper respiratory tract, and can cause allergic asthma and bronchitis, and formaldehyde has toxicity to nervous system, liver, kidney and digestive system of human body. Eliminating formaldehyde pollution, purifying indoor air and being very important to human health.
The current indoor air purification mainly adopts filtration and adsorption. Filtration mainly removes suspended substances in the air, such as dust, smoke, etc. Volatile Organic Compounds (VOCs) in the air must be removed by adsorption, but adsorption only transfers the organic compounds in the air to the adsorbent, but the organic compounds are not eliminated, and as the adsorption amount increases, the adsorption performance decreases, and finally the adsorption tends to be saturated and the air purifying capacity is lost. The photocatalysis can eliminate pollutants in the air, particularly can effectively degrade volatile organic compounds in the air, is a new air purification method developed in recent years, and can degrade organic compounds into water and carbon dioxide at normal temperature and normal pressure without secondary pollution.
The activated carbon has the characteristics of large specific surface area, high adsorption rate, moderate pore size distribution and the like, and has remarkable advantages in the aspect of adsorbing and separating formaldehyde pollutants. According to the adsorption mode, activated carbon adsorption is classified into physical adsorption and chemical adsorption. In the physical adsorption process, the pore size gradient distribution determines the adsorption capacity and rate, macropores and mesopores play a role in transporting formaldehyde molecules, micropores have huge specific surface area, can provide enough stay sites for pollutants, and the surface of the activated carbon adsorbs the formaldehyde molecules by utilizing Van der Waals force generated under the action of asymmetric dipole moment. The chemical adsorption is that the functional groups such as carboxyl, phenolic hydroxyl and the like of the activated carbon react with formaldehyde adsorbate molecules, so that the adsorption is stable and irreversible. From the physical adsorption and chemical adsorption processes of activated carbon, the pore size distribution and surface functional groups of activated carbon are extremely important for the adsorption process of adsorbates.
CN114315236a discloses a method for preparing porous block aerogel for adsorbing and degrading VOCs gas by 3D printing technology. Uniformly mixing isopropanol, polydimethylsiloxane and hydroxypropyl methylcellulose, adding silicon dioxide aerogel powder and titanium dioxide photocatalytic powder, and preparing 3D printing slurry by ball milling and mixing; then preparing the sample into a 3D printing aerogel sample with a macroscopic porous specific structure by a direct-writing type 3D printer; aging at normal temperature, drying at proper temperature to remove organic solvent and further crosslinking and solidifying the binder to provide a certain mechanical strength; and finally, carrying out heat treatment on the silicon dioxide aerogel in an electric furnace to obtain the 3D printing silica aerogel for adsorbing and degrading VOCs. The adsorption performance of the 3D printing silica aerogel on VOCs represented by formaldehyde and toluene is higher than that of the commercial activated carbon by more than 20%, the absorptivity can reach 100%, and the degradation rate can reach more than 25%.
CN113181767a discloses a capsule type slow release formaldehyde scavenger and a preparation process thereof, which belongs to the technical field of formaldehyde scavenging, and comprises a slow release carrier pellet core and a coating capsule, wherein the slow release carrier pellet core comprises the following raw materials in parts by weight: 40-70 parts of activated carbon substrate, 30-60 parts of titanium dioxide substrate, 5-10 parts of molding material, 2-20 parts of slow-release material, 1-5 parts of plasticizer and 0.5-1.5 parts of anti-adhesion agent, wherein the coated capsule is a polytetrafluoroethylene breathable waterproof coating, and the preparation process comprises matrix preparation, mixing, granulating, slow-release liquid preparation and coating. By mixing the titanium dioxide oxide in the activated carbon matrix, after the activated carbon is fused with the molding material and the slow-release material, the slow-release capsule can continuously adsorb and purify formaldehyde under photocatalysis, and the surface film can isolate external water vapor from wetting, so that the slow-release efficiency is improved, the coating placement time is obviously prolonged, and the continuous purification capability of formaldehyde is met.
CN113101961A discloses a load Ag/C 3 N 4 Active carbon composite material of nano particles, melamine and silver nitrate are mixed and pyrolyzed to prepare Ag/g-C 3 N 4 Nanometer particles, and then are compounded with porous active carbon material to prepare the loaded Ag/C 3 N 4 Active carbon composite material of nano particles, porous active carbon as carrier, and Ag/g-C uniformly loaded 3 N 4 Nanoparticles, ag/g-C 3 N 4 The nanoparticle has excellent photochemical activity, can generate more photogenerated carriers under the irradiation of light, and g-C 3 N 4 The Ag doped with the matrix has excellent conductivity and can promote photogenerationElectron transfer to promote separation of photo-generated electrons and holes, and make Ag/g-C 3 N 4 The nano particles show better photocatalytic activity, and are combined with porous activated carbon, so that the nano particles have good formaldehyde adsorption and photodegradation effects, and have excellent photocatalytic antibacterial activity on bacteria such as escherichia coli and microorganisms.
CN111514883a discloses a carbon-based catalyst for decomposing formaldehyde at room temperature and a preparation method thereof, wherein molded activated carbon is used as a carrier, an isovolumetric impregnation is used for loading a catalytic component, and a formaldehyde elimination catalyst is obtained after high-temperature calcination. The carbon-based catalyst can purify formaldehyde at room temperature, and the prepared titanium dioxide-containing catalyst has the performance of eliminating formaldehyde by photocatalysis and catalytic oxidation, combines the adsorption effect of active carbon, the oxidation effect of manganese oxide and the photocatalysis effect of titanium dioxide, and improves the purification efficiency of formaldehyde. The preparation process does not use noble metal, has the characteristics of high efficiency and environmental protection, and simultaneously uses the formed active carbon to purify formaldehyde, is convenient for recycling and has no secondary pollution.
In summary, although the prior art has an effect of removing formaldehyde by combining an oxidizing agent or a photocatalyst with an adsorbent, the treating ability of the adsorbent is still not strong enough and the period of removing formaldehyde at a low concentration is long, so that it is highly demanded to develop a new formaldehyde adsorbent having an excellent removing ability for formaldehyde.
Disclosure of Invention
The invention aims to overcome the defects and the shortcomings in the prior art and provide a formaldehyde adsorbent for air purification and a preparation method and application thereof. The preparation method comprises the following steps: preparing phenolic resin ethanol solution, performing thermal polymerization, carbonizing to obtain mesoporous carbon containing manganese and copper, and performing oxidation treatment to obtain oxidized mesoporous carbon; and dissolving a cobalt source in deionized water, adding mesoporous carbon subjected to oxidation treatment, stirring uniformly to obtain a mixture solution, adding 2-methylimidazole, ferric salt and zinc salt into the mixture solution, stirring, filtering, washing, drying, and roasting under an inert atmosphere to obtain the methanol adsorbent. The formaldehyde adsorbent prepared by the invention has excellent adsorption and removal capacity on formaldehyde, can oxidize formaldehyde under illumination conditions, and effectively removes formaldehyde in air.
The invention aims to provide a preparation method of a formaldehyde adsorbent for air purification.
Another object of the present invention is to provide a formaldehyde adsorbent for air purification and its use.
The above object of the present invention is achieved by the following technical scheme:
a method for preparing a formaldehyde adsorbent for air purification, the method comprising the steps of:
(1) Preparation of mesoporous carbon
Dissolving phenol and formaldehyde in an alkaline solution, uniformly stirring at a certain temperature, cooling to room temperature, regulating the solution to be neutral through hydrochloric acid, removing water at a certain temperature under a vacuum condition, and dissolving the obtained phenolic resin in ethanol to prepare phenolic resin ethanol solution; dissolving triblock copolymer, manganese salt and copper salt in phenolic resin mixed solution, evaporating at room temperature, and performing thermal polymerization to obtain a precursor; roasting and carbonizing the precursor to obtain a mesoporous carbon material;
(2) Adding the mesoporous carbon obtained in the step (1) into an oxidant solution for oxidation treatment, and then filtering and washing to obtain oxidized mesoporous carbon;
(3) Dissolving a cobalt source in deionized water, adding mesoporous carbon obtained in the step (2), stirring uniformly to obtain a mixture solution, adding 2-methylimidazole, ferric salt and zinc salt into the mixture solution, stirring, filtering, washing, drying, and roasting under an inert atmosphere to obtain the methanol adsorbent.
Preferably, in the step (1), the stirring temperature is 50-70 ℃; the vacuum temperature is 80-100 ℃, and the concentration of the phenolic resin ethanol solution is 20-30 wt%.
Preferably, in the step (1), the temperature of the thermal polymerization is 70-90 ℃, and the time of the thermal polymerization is 16-24 hours; the roasting condition is that the temperature is raised to 750-850 ℃ at the heating rate of 4-8 ℃/min under inert gas for roasting and carbonization, and the temperature is kept for 2-5 h.
Preferably, in step (1), the triblock copolymer is at least one of P123, F127; the alkaline solution is at least one of sodium hydroxide solution and potassium hydroxide solution; the inert gas is one of helium and argon; the manganese salt is at least one of manganese nitrate, manganese acetate and manganese chloride, and the copper salt is at least one of copper nitrate, copper acetate and copper chloride.
Preferably, in step (1), the molar ratio of phenol to formaldehyde is 1:2 to 4; the ratio of the phenol to the triblock copolymer to the manganese salt to the copper salt is 10-14 mmol:1g:0.2 to 0.4mmol:0.2 to 0.4mmol.
Preferably, in the step (2), the oxidant is potassium permanganate or hydrogen peroxide, and the oxidation treatment condition is that the oxidant is treated in 2mol/L potassium permanganate or hydrogen peroxide for 0.5-1.5 h.
Preferably, in the step (3), the stirring condition is that stirring is carried out for 16-22 hours at 20-30 ℃; the drying is that the drying treatment is carried out for 10 to 14 hours at the temperature of 80 to 120 ℃; the calcination temperature is 450-550 ℃ and the treatment is carried out for 2-4 hours; the ratio of mesoporous carbon to cobalt source is 1g:0.01 to 0.03mol, wherein the mole ratio of the cobalt source to the 2-methylimidazole is 1:4 to 8; the molar ratio of the cobalt source to the ferric salt to the zinc salt is 1:0.02-0.06:0.02-0.06.
Preferably, in the step (3), the inert atmosphere is one of nitrogen, argon and helium; the cobalt salt is at least one of cobalt nitrate, cobalt acetate and cobalt chloride, the ferric salt is at least one of ferric nitrate, ferric acetate and ferric chloride, and the zinc salt is at least one of zinc acetate, zinc chloride and zinc nitrate.
A formaldehyde adsorbent for air purification prepared based on the above-described method for preparing a formaldehyde adsorbent for air purification.
The application of the formaldehyde adsorbent for air purification is characterized in that the formaldehyde adsorbent is used for purifying formaldehyde in air.
The invention has the following beneficial effects:
(1) According to the invention, manganese and copper modified mesoporous carbon is prepared, then oxidized mesoporous carbon is obtained through oxidation treatment, then the oxidized mesoporous carbon is put into a source solution, 2-methylimidazole, ferric salt and zinc salt are added into the mixture solution after cobalt is adsorbed, and the prepared iron and zinc modified metal organic framework is carbonized to obtain a modified mesoporous carbon material which has excellent adsorption capacity to formaldehyde, and due to the existence of metal, the adsorbed formaldehyde can be effectively removed, so that the modified mesoporous carbon material has excellent purification capacity to formaldehyde.
(2) The mesoporous carbon modified by manganese and copper can obviously modify the adsorption capacity of the mesoporous carbon, and has excellent catalytic oxidation capacity on formaldehyde due to the existence of manganese and copper.
(3) Through oxidation treatment of mesoporous carbon, oxygen-containing groups on the surface of the mesoporous carbon can be increased, so that the adsorption of cobalt is facilitated, and further, the dispersibility of cobalt and the purification capability of formaldehyde are improved.
(4) Iron and zinc are added into the prepared metal framework, and after the modification of the iron and the zinc and carbonization, the generated metal oxide formaldehyde has excellent photocatalytic degradation capability, so that the purification capability of formaldehyde is further improved.
Detailed Description
The present invention is further illustrated below with reference to specific examples, which are not intended to limit the invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Reagents and materials used in the following examples are commercially available unless otherwise specified.
Example 1
A method for preparing a formaldehyde adsorbent for air purification, the method comprising the steps of:
(1) Preparation of mesoporous carbon
Dissolving 12mmol of phenol and 36mmol of formaldehyde in 10ml of 0.6mol/L sodium hydroxide solution, uniformly stirring at 60 ℃, cooling to room temperature, regulating the solution to be neutral through hydrochloric acid, removing water under the vacuum condition of 90 ℃, and dissolving the obtained phenolic resin in ethanol to prepare a 35wt% phenolic resin ethanol solution; 1g of P123, 0.3mmol of manganese nitrate and 0.3mmol of copper nitrate are dissolved in a phenolic resin mixed solution, then evaporated at room temperature, and subjected to thermal polymerization at 80 ℃, and then heat-treated at the temperature for 20 hours to obtain a precursor; heating the precursor to 800 ℃ at a heating rate of 6 ℃/min under helium gas to perform roasting carbonization, and preserving heat for 4 hours to obtain a mesoporous carbon material;
(2) Adding the mesoporous carbon material obtained in the step (1) into 50mL of 2mol/L potassium permanganate solution, and treating for 1h; then filtering and washing to obtain mesoporous carbon subjected to oxidation treatment;
(3) Dissolving 0.02mol of cobalt nitrate in 10mL of deionized water, adding 1g of mesoporous carbon obtained in the step (2), stirring uniformly to obtain a mixture solution, adding 0.12mol of 2-methylimidazole, 0.6mmol of ferric nitrate and 0.6mmol of zinc nitrate into the mixture solution, stirring at 25 ℃ for 20h, filtering, washing, drying at 100 ℃ for 12h, and roasting at 500 ℃ for 3h under nitrogen to obtain the methanol adsorbent.
Example 2
A method for preparing a formaldehyde adsorbent for air purification, the method comprising the steps of:
(1) Preparation of mesoporous carbon
Dissolving 14mmol of phenol and 56mmol of formaldehyde in 10ml of 0.7mol/L potassium hydroxide solution, uniformly stirring at 70 ℃, cooling to room temperature, regulating the solution to be neutral through hydrochloric acid, removing water under the vacuum condition of 100 ℃, and dissolving the obtained phenolic resin in ethanol to prepare a 30wt% phenolic resin ethanol solution; 1g of F127, 0.4mmol of manganese chloride and 0.2mmol of copper acetate are dissolved in a phenolic resin mixed solution, then evaporated at room temperature, and subjected to thermal polymerization at 90 ℃, and then heat-treated at the temperature for 16 hours to obtain a precursor; and heating the precursor to 850 ℃ at a heating rate of 8 ℃/min under inert gas, roasting and carbonizing, and preserving heat for 2 hours to obtain the mesoporous carbon material.
(2) Adding the mesoporous carbon obtained in the step (1) into 50mL of 2mol/L hydrogen peroxide solution, and treating for 1.5h; then filtering and washing to obtain mesoporous carbon subjected to oxidation treatment;
(3) Dissolving 0.03mol of cobalt chloride in 10mL of deionized water, adding 1g of mesoporous carbon obtained in the step (2), stirring uniformly to obtain a mixture solution, adding 0.24mol of 2-methylimidazole, 1.8mmol of ferric chloride and 0.6mmol of zinc acetate into the mixture solution, stirring at 30 ℃ for 16h, filtering, washing, drying at 120 ℃ for 10h, and roasting at 550 ℃ for 2h under argon to obtain the methanol adsorbent.
Example 3
A method for preparing a formaldehyde adsorbent for air purification, the method comprising the steps of:
(1) Preparation of mesoporous carbon
Dissolving 10mmol of phenol and 20mmol of formaldehyde in 10ml of 0.5mol/L sodium hydroxide solution, uniformly stirring at 50 ℃, cooling to room temperature, regulating the solution to be neutral through hydrochloric acid, removing water under the vacuum condition of 80 ℃, and dissolving the obtained phenolic resin in ethanol to prepare a 20wt% phenolic resin ethanol solution; 1g of P123, 0.2mmol of manganese acetate and 0.4mmol of copper chloride are dissolved in a phenolic resin mixed solution, then evaporated at room temperature, and subjected to thermal polymerization at 70 ℃, and then subjected to thermal treatment at the temperature for 24 hours to obtain a precursor; and heating the precursor to 750 ℃ at a heating rate of 4 ℃/min under helium gas, roasting and carbonizing, and preserving heat for 5 hours to obtain the mesoporous carbon material.
(2) Adding the mesoporous carbon obtained in the step (1) into 50mL of 2mol/L potassium permanganate solution, and treating for 0.5-1.5 h; then filtering and washing to obtain mesoporous carbon subjected to oxidation treatment;
(3) Dissolving 0.01mol of cobalt acetate in 10mL of deionized water, adding 1g of mesoporous carbon obtained in the step (2), stirring uniformly to obtain a mixture solution, adding 0.04mol of 2-methylimidazole, 0.2mmol of ferric acetate and 0.6mmol of zinc chloride into the mixture solution, stirring at 20 ℃ for 22h, filtering, washing, drying at 80 ℃ for 14h, and roasting at 450 ℃ for 4h in helium atmosphere to obtain the methanol adsorbent.
Comparative example 1
A method for preparing a formaldehyde adsorbent for air purification, the method comprising the steps of:
(1) Preparation of mesoporous carbon
Dissolving 12mmol of phenol and 36mmol of formaldehyde in 10ml of 0.6mol/L sodium hydroxide solution, uniformly stirring at 60 ℃, cooling to room temperature, regulating the solution to be neutral through hydrochloric acid, removing water under the vacuum condition of 90 ℃, and dissolving the obtained phenolic resin in ethanol to prepare a 35wt% phenolic resin ethanol solution; 1g of P123 and 0.6mmol of manganese nitrate are dissolved in a phenolic resin mixed solution, then evaporated at room temperature, and subjected to thermal polymerization at 80 ℃, and then heat-treated at the temperature for 20 hours to obtain a precursor; heating the precursor to 800 ℃ at a heating rate of 6 ℃/min under helium gas to perform roasting carbonization, and preserving heat for 4 hours to obtain a mesoporous carbon material;
(2) Adding the mesoporous carbon material obtained in the step (1) into 50mL of 2mol/L potassium permanganate solution, and treating for 1h; then filtering and washing to obtain mesoporous carbon subjected to oxidation treatment;
(3) Dissolving 0.02mol of cobalt nitrate in 10mL of deionized water, adding 1g of mesoporous carbon obtained in the step (2), stirring uniformly to obtain a mixture solution, adding 0.12mol of 2-methylimidazole, 0.6mmol of ferric nitrate and 0.6mmol of zinc nitrate into the mixture solution, stirring at 25 ℃ for 20h, filtering, washing, drying at 100 ℃ for 12h, and roasting at 500 ℃ for 3h under nitrogen to obtain the methanol adsorbent.
Comparative example 2
A method for preparing a formaldehyde adsorbent for air purification, the method comprising the steps of:
(1) Preparation of mesoporous carbon
Dissolving 12mmol of phenol and 36mmol of formaldehyde in 10ml of 0.6mol/L sodium hydroxide solution, uniformly stirring at 60 ℃, cooling to room temperature, regulating the solution to be neutral through hydrochloric acid, removing water under the vacuum condition of 90 ℃, and dissolving the obtained phenolic resin in ethanol to prepare a 35wt% phenolic resin ethanol solution; 1g of P123 and 0.6mmol of copper nitrate are dissolved in a phenolic resin mixed solution, then evaporated at room temperature, and subjected to thermal polymerization at 80 ℃, and then heat-treated at the temperature for 20 hours to obtain a precursor; heating the precursor to 800 ℃ at a heating rate of 6 ℃/min under helium gas to perform roasting carbonization, and preserving heat for 4 hours to obtain a mesoporous carbon material;
(2) Adding the mesoporous carbon material obtained in the step (1) into 50mL of 2mol/L potassium permanganate solution, and treating for 1h; then filtering and washing to obtain mesoporous carbon subjected to oxidation treatment;
(3) Dissolving 0.02mol of cobalt nitrate in 10mL of deionized water, adding 1g of mesoporous carbon obtained in the step (2), stirring uniformly to obtain a mixture solution, adding 0.12mol of 2-methylimidazole, 0.6mmol of ferric nitrate and 0.6mmol of zinc nitrate into the mixture solution, stirring at 25 ℃ for 20h, filtering, washing, drying at 100 ℃ for 12h, and roasting at 500 ℃ for 3h under nitrogen to obtain the methanol adsorbent.
Comparative example 3
A method for preparing a formaldehyde adsorbent for air purification, the method comprising the steps of:
(1) Preparation of mesoporous carbon
Dissolving 12mmol of phenol and 36mmol of formaldehyde in 10ml of 0.6mol/L sodium hydroxide solution, uniformly stirring at 60 ℃, cooling to room temperature, regulating the solution to be neutral through hydrochloric acid, removing water under the vacuum condition of 90 ℃, and dissolving the obtained phenolic resin in ethanol to prepare a 35wt% phenolic resin ethanol solution; 1g of P123, 0.3mmol of manganese nitrate and 0.3mmol of copper nitrate are dissolved in a phenolic resin mixed solution, then evaporated at room temperature, and subjected to thermal polymerization at 80 ℃, and then heat-treated at the temperature for 20 hours to obtain a precursor; heating the precursor to 800 ℃ at a heating rate of 6 ℃/min under helium gas to perform roasting carbonization, and preserving heat for 4 hours to obtain a mesoporous carbon material;
(2) Adding the mesoporous carbon material obtained in the step (1) into 50mL of 2mol/L potassium permanganate solution, and treating for 1h; then filtering and washing to obtain mesoporous carbon subjected to oxidation treatment;
(3) Dissolving 0.02mol of cobalt nitrate in 10mL of deionized water, adding 1g of mesoporous carbon obtained in the step (2), stirring uniformly to obtain a mixture solution, adding 0.12mol of 2-methylimidazole and 1.2mmol of ferric nitrate into the mixture solution, stirring at 25 ℃ for 20h, filtering, washing, drying at 100 ℃ for 12h, and roasting at 500 ℃ for 3h under nitrogen to obtain the methanol adsorbent.
Comparative example 4
A method for preparing a formaldehyde adsorbent for air purification, the method comprising the steps of:
(1) Preparation of mesoporous carbon
Dissolving 12mmol of phenol and 36mmol of formaldehyde in 10ml of 0.6mol/L sodium hydroxide solution, uniformly stirring at 60 ℃, cooling to room temperature, regulating the solution to be neutral through hydrochloric acid, removing water under the vacuum condition of 90 ℃, and dissolving the obtained phenolic resin in ethanol to prepare a 35wt% phenolic resin ethanol solution; 1g of P123, 0.3mmol of manganese nitrate and 0.3mmol of copper nitrate are dissolved in a phenolic resin mixed solution, then evaporated at room temperature, and subjected to thermal polymerization at 80 ℃, and then heat-treated at the temperature for 20 hours to obtain a precursor; and heating the precursor to 800 ℃ at a heating rate of 6 ℃/min under helium gas to perform roasting carbonization, and preserving heat for 4 hours to obtain the mesoporous carbon material.
(2) Adding the mesoporous carbon material obtained in the step (1) into 50mL of 2mol/L potassium permanganate solution, and treating for 1h; then filtering and washing to obtain mesoporous carbon subjected to oxidation treatment;
(3) Dissolving 0.02mol of cobalt nitrate in 10mL of deionized water, adding 1g of mesoporous carbon obtained in the step (2), stirring uniformly to obtain a mixture solution, adding 0.12mol of 2-methylimidazole and 1.2mmol of zinc nitrate into the mixture solution, stirring at 25 ℃ for 20h, filtering, washing, drying at 100 ℃ for 12h, and roasting at 500 ℃ for 3h under nitrogen to obtain the methanol adsorbent.
Comparative example 5
A method for preparing a formaldehyde adsorbent for air purification, the method comprising the steps of:
(1) Preparation of mesoporous carbon
Dissolving 12mmol of phenol and 36mmol of formaldehyde in 10mL of 0.6mol/L sodium hydroxide solution, uniformly stirring at 60 ℃, cooling to room temperature, regulating the solution to be neutral through hydrochloric acid, removing water under the vacuum condition at 90 ℃, and dissolving the obtained phenolic resin in ethanol to prepare a 35wt% phenolic resin ethanol solution; 1g of P123, 0.3mmol of manganese nitrate and 0.3mmol of copper nitrate are dissolved in a phenolic resin mixed solution, then evaporated at room temperature, and subjected to thermal polymerization at 80 ℃, and then heat-treated at the temperature for 20 hours to obtain a precursor; heating the precursor to 800 ℃ at a heating rate of 6 ℃/min under helium gas to perform roasting carbonization, and preserving heat for 4 hours to obtain a mesoporous carbon material;
(2) Dissolving 0.02mol of cobalt nitrate in 10mL of deionized water, adding 1g of mesoporous carbon obtained in the step (1), stirring uniformly to obtain a mixture solution, adding 0.12mol of 2-methylimidazole, 0.6mmol of ferric nitrate and 0.6mmol of zinc nitrate into the mixture solution, stirring at 25 ℃ for 20h, filtering, washing, drying at 100 ℃ for 12h, and roasting at 500 ℃ for 3h under nitrogen to obtain the methanol adsorbent.
Comparative example 6
A method for preparing a formaldehyde adsorbent for air purification, the method comprising the steps of:
(1) Preparation of mesoporous carbon
Dissolving 12mmol of phenol and 36mmol of formaldehyde in 10ml of 0.6mol/L sodium hydroxide solution, uniformly stirring at 60 ℃, cooling to room temperature, regulating the solution to be neutral through hydrochloric acid, removing water under the vacuum condition of 90 ℃, and dissolving the obtained phenolic resin in ethanol to prepare a 35wt% phenolic resin ethanol solution; 1g of P123, 0.3mmol of manganese nitrate and 0.3mmol of copper nitrate are dissolved in a phenolic resin mixed solution, then evaporated at room temperature, and subjected to thermal polymerization at 80 ℃, and then heat-treated at the temperature for 20 hours to obtain a precursor; heating the precursor to 800 ℃ at a heating rate of 6 ℃/min under helium gas to perform roasting carbonization, and preserving heat for 4 hours to obtain a mesoporous carbon material;
(2) Adding the mesoporous carbon material obtained in the step (1) into 50mL of 2mol/L potassium permanganate solution, and treating for 1h; then filtering and washing to obtain mesoporous carbon subjected to oxidation treatment;
(3) Dissolving 0.02mol of cobalt nitrate in 10mL of deionized water, stirring uniformly to obtain a mixture solution, adding 0.12mol of 2-methylimidazole, 0.6mmol of ferric nitrate and 0.6mmol of zinc nitrate into the mixture solution, stirring at 25 ℃ for 20h, adding 1g of mesoporous carbon obtained in the step (2), stirring for 0.5min, filtering, washing, drying at 100 ℃ for 12h, and roasting at 500 ℃ for 3h under nitrogen to obtain the methanol adsorbent.
Experiments on adsorption and degradation of formaldehyde were performed on the air-purified formaldehyde adsorbents of examples 1 to 3 and comparative examples 1 to 6, and specific test results are shown in table 1.
Adsorption test of formaldehyde: and placing 20g of sample into a closed container, wherein the volume of the container is 1000L, introducing 100ppm of formaldehyde as VOCs to be detected, extracting gas in the closed environment through a sampling needle, detecting the initial concentration of toluene in the container by using an acetylacetone method, and checking the removal rate at 60 minutes.
Degradation test of formaldehyde: putting 20g of sample into a closed container, wherein the volume of the sample is 1000L, introducing 100ppm of formaldehyde to serve as VOCs to be detected, extracting gas in the closed environment through a sampling needle, detecting the initial concentration of toluene in the container by using an acetylacetone method, then filling 100ppm of formaldehyde gas into the closed environment for many times until the concentration of the VOCs in the closed environment is equal to the initial concentration measured and remains unchanged after 60min, and opening 300W xenon lamp light to perform degradation performance test to measure the formaldehyde degradation rate at 30 min.
TABLE 1
As can be seen from Table 1, the air-purified formaldehyde adsorbent prepared in the present application has advantageous adsorption and removal capabilities for formaldehyde, and it is demonstrated by comparison of examples 1-3 with comparative examples 1-6 that the components of the present invention have a coordinated interaction with each other, and it is the coordinated interaction between the components that promotes an increase in adsorption and degradation capabilities of the formaldehyde adsorbent.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a formaldehyde adsorbent for air purification is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) Preparation of mesoporous carbon
Dissolving phenol and formaldehyde in an alkaline solution, uniformly stirring at a certain temperature, cooling to room temperature, regulating the solution to be neutral through hydrochloric acid, removing water at a certain temperature under a vacuum condition, and dissolving the obtained phenolic resin in ethanol to prepare phenolic resin ethanol solution; dissolving triblock copolymer, manganese salt and copper salt in phenolic resin mixed solution, evaporating at room temperature, and performing thermal polymerization to obtain a precursor; roasting and carbonizing the precursor to obtain a mesoporous carbon material;
(2) Adding the mesoporous carbon material obtained in the step (1) into an oxidant solution for oxidation treatment, and then filtering and washing to obtain oxidized mesoporous carbon;
(3) Dissolving a cobalt source in deionized water, adding mesoporous carbon obtained in the step (2), stirring uniformly to obtain a mixture solution, adding 2-methylimidazole, ferric salt and zinc salt into the mixture solution, stirring, filtering, washing, drying, and roasting under an inert atmosphere to obtain the formaldehyde adsorbent.
2. The method for preparing a formaldehyde adsorbent for air purification according to claim 1, wherein: in the step (1), the stirring temperature is 50-70 ℃; the vacuum temperature is 80-100 ℃, and the concentration of the phenolic resin ethanol solution is 20-30wt%.
3. The method for preparing a formaldehyde adsorbent for air purification according to claim 1, wherein: in the step (1), the temperature of the thermal polymerization is 70-90 ℃, and the time of the thermal polymerization is 16-24 hours; the roasting condition is that the temperature is raised to 750-850 ℃ at the heating rate of 4-8 ℃/min under inert gas for roasting and carbonization, and the temperature is kept for 2-5 h.
4. A method for preparing a formaldehyde adsorbent for air purification according to claim 3, characterized in that: in step (1), the triblock copolymer is at least one of P123, F127; the alkaline solution is at least one of sodium hydroxide solution and potassium hydroxide solution; the inert gas is one of helium and argon; the manganese salt is at least one of manganese nitrate, manganese acetate and manganese chloride, and the copper salt is at least one of copper nitrate, copper acetate and copper chloride.
5. A method for producing a formaldehyde adsorbent for air purification according to any one of claims 1 to 4, characterized in that: in step (1), the molar ratio of phenol to formaldehyde is 1: 2-4; the ratio of the phenol to the triblock copolymer to the manganese salt to the copper salt is 10-14 mmol:1g: 0.2-0.4 mmol:0.2 to 0.4mmol.
6. The method for preparing a formaldehyde adsorbent for air purification according to claim 1, wherein: in the step (2), the oxidant is potassium permanganate or hydrogen peroxide, and the oxidation treatment condition is that the oxidant is treated in 2mol/L potassium permanganate or hydrogen peroxide for 0.5-1.5 h.
7. The method for preparing a formaldehyde adsorbent for air purification according to claim 1, wherein: in the step (3), stirring for 16-22 hours at the temperature of 20-30 ℃; the drying is carried out for 10-14 hours at the temperature of 80-120 ℃; the roasting temperature is 450-550 ℃ and the treatment is carried out for 2-4 hours; the ratio of mesoporous carbon to cobalt source is 1g: 0.01-0.03 mol, wherein the molar ratio of the cobalt source to the 2-methylimidazole is 1: 4-8; the molar ratio of the cobalt source to the ferric salt to the zinc salt is 1:0.02-0.06:0.02-0.06.
8. The method for preparing a formaldehyde adsorbent for air purification according to claim 1, wherein: in the step (3), the inert atmosphere is one of nitrogen, argon and helium; the cobalt source is at least one of cobalt nitrate, cobalt acetate and cobalt chloride, the ferric salt is at least one of ferric nitrate, ferric acetate and ferric chloride, and the zinc salt is at least one of zinc acetate, zinc chloride and zinc nitrate.
9. A formaldehyde adsorbent for air purification prepared by the method for preparing a formaldehyde adsorbent for air purification according to any one of claims 1 to 8.
10. Use of a formaldehyde adsorbent for air purification according to claim 9, characterized in that the formaldehyde adsorbent is used for formaldehyde purification in air.
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