CN112536044A - Method for treating air pollution by using composite catalyst - Google Patents
Method for treating air pollution by using composite catalyst Download PDFInfo
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- CN112536044A CN112536044A CN202011605903.4A CN202011605903A CN112536044A CN 112536044 A CN112536044 A CN 112536044A CN 202011605903 A CN202011605903 A CN 202011605903A CN 112536044 A CN112536044 A CN 112536044A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000003915 air pollution Methods 0.000 title claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 67
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 239000000126 substance Substances 0.000 claims abstract description 35
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000010992 reflux Methods 0.000 claims abstract description 26
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- VXWSFRMTBJZULV-UHFFFAOYSA-H iron(3+) sulfate hydrate Chemical compound O.[Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VXWSFRMTBJZULV-UHFFFAOYSA-H 0.000 claims abstract description 16
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000032683 aging Effects 0.000 claims abstract description 13
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 238000002791 soaking Methods 0.000 claims abstract description 6
- 239000012065 filter cake Substances 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 17
- 238000009210 therapy by ultrasound Methods 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 9
- 239000012295 chemical reaction liquid Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 6
- 238000001704 evaporation Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 22
- 238000010438 heat treatment Methods 0.000 description 21
- 239000011259 mixed solution Substances 0.000 description 16
- 230000008030 elimination Effects 0.000 description 14
- 238000003379 elimination reaction Methods 0.000 description 14
- 239000011787 zinc oxide Substances 0.000 description 11
- 238000005406 washing Methods 0.000 description 10
- 238000011068 loading method Methods 0.000 description 9
- 239000012855 volatile organic compound Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910016978 MnOx Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000004887 air purification Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- BSIUFWMDOOFBSP-UHFFFAOYSA-N 2-azanylethanol Chemical compound NCCO.NCCO BSIUFWMDOOFBSP-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- -1 amine salt Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000009982 effect on human Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002061 nanopillar Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- B01J23/89—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
- B01J23/892—Nickel and noble metals
-
- 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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
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- 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
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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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/06—Polluted air
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- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
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- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Biomedical Technology (AREA)
- Thermal Sciences (AREA)
- Optics & Photonics (AREA)
- Plasma & Fusion (AREA)
- Toxicology (AREA)
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Abstract
The invention belongs to the environmental pollution treatment technology, and discloses a method for treating air pollution by using a composite catalyst, which comprises the steps of enabling polluted air to flow through the composite catalyst to finish the treatment of air pollution; the preparation method of the composite catalyst comprises the steps of dispersing ferric sulfate hydrate in ethanol, reacting in a high-pressure reaction kettle after reflux stirring, calcining in a muffle furnace by air, and naturally cooling to room temperature to obtain a calcined substance; the calcined product, nickel nitrate hexahydrate (Ni (NO)3)3·6H2O), ethanolamine and ethanol are mixed, and dried after reflux reaction to obtain a dried substance; soaking the dried matter in water solution containing chloroplatinic acid at room temperature, ultrasonic treating, ageing for 15 hr, evaporating water from the mixed liquid, transferring to muffle furnace in air condition, and roasting at 500 deg.c for 2 hr to obtain catalyst with platinum as active component for purifying formaldehyde and high eliminating rate.
Description
Technical Field
The invention relates to the technical field of environmental treatment, relates to an air purification material technology, and particularly relates to a method for treating air pollution by using a composite catalyst.
Background
Currently applied indoorsThe air purification technology mainly comprises the following steps: adsorption, photocatalytic degradation, plasma degradation, catalytic combustion, and the like. The adsorption method is to adsorb the VOCs in a room by using adsorbents such as activated carbon and molecular sieves so as to purify the gas, but the adsorption material has limited adsorption capacity and needs to be regenerated or replaced periodically, and the adsorption material is easy to desorb at high temperature so as to cause secondary pollution. The photocatalytic degradation method is to utilize nano TiO2VOCs are adsorbed and decomposed as a photocatalyst, but this method has disadvantages such as easy deactivation of the catalyst, low efficiency, and long time consumption. The plasma degradation method is to generate a large amount of active species such as high-energy electrons through discharge in modes such as dielectric barrier and the like, and the active species react with the indoor VOCs to further achieve the purpose of eliminating the VOCs.
The prior art relates to a method for preparing an ultrasonic auxiliary aqueous solution of a highly oriented zinc oxide nano-pillar array, which comprises the following specific steps: firstly, preparing a stable ZnO sol precursor by using zinc salt as a raw material, ethylene glycol monomethyl ether as a solvent and organic amine salt as a chelating agent; uniformly depositing the ZnO sol precursor on a glass substrate by adopting a dip-coating method or a spin coating method, forming a transparent ZnO seed crystal layer after heat treatment, and inducing the growth of a subsequent ZnO nano-column array; preparing ZnO nano-column growth solution by using zinc salt, water and hexamethylenetetramine according to a ratio; and fourthly, the substrate covered with the ZnO seed crystal layer is put into ZnO nano-column growth liquid, ultrasonic pretreatment is carried out at room temperature, and then the temperature is raised to 95 ℃ and kept for 6 hours. And after the reaction is finished, washing the substrate by deionized water, and naturally drying to obtain the one-dimensional ZnO nano-column array which is orderly arranged. The diameter of the prepared ZnO nano-column array is reduced to be less than 100nm, and the growing verticality of the ZnO nano-column array is ensured. In addition, the catalyst takes an adsorbing material as a carrier, and TiO is loaded on the carrier2，MnOxAnd a reduced noble metal, wherein TiO2The loading amount of the adsorbent is 0-60% of the mass of the adsorbent; MnOxThe loading amount of the catalyst is 0.1-10% of the mass of the adsorbing material, the loading amount of the reduced noble metal is 0.01-1% of the mass of the adsorbing material, and the reduced noble metal is selected from platinum, palladium, gold and silverOne or two or more than two of the titanium dioxide are modified by adopting an ion doping modification mode, and the titanium dioxide can be used for purifying VOCs (volatile organic compounds) such as formaldehyde, benzene, toluene and the like in indoor air and utilizing and eliminating O3Gaseous pollutants. Although most of the purification materials prepared by the prior art can adsorb and degrade part of indoor pollution gas, the preparation method needs to be simplified, and the removal effect needs to be improved. Therefore, it is very important to develop a purification material that can purify VOCs in a high humidity environment.
Disclosure of Invention
The invention aims to solve the technical problem of developing a novel catalyst for removing toluene, and has the technical effects of low temperature and high efficiency. The catalyst prepared by the invention has good low-temperature activity and removal efficiency at room temperature and ambient humidity, and can completely convert formaldehyde into carbon dioxide and water. The invention has simple preparation process, easy operation and low content of noble metal, does not need additional energy devices such as additional wind, light, heat, electricity and the like, and is suitable for purifying the formaldehyde harmful gas in the indoor air.
In order to solve the technical problem, the solution of the invention is as follows:
the method for treating air pollution by using the composite catalyst is characterized in that polluted air flows through the composite catalyst to finish the treatment of air pollution; dispersing ferric sulfate hydrate in ethanol, refluxing and stirring, then reacting for 18 hours at 140 ℃ in a high-pressure reaction kettle, filtering reaction liquid, drying a filter cake, and calcining to obtain a calcined substance; mixing the calcined substance, nickel nitrate hexahydrate, ethanolamine, ethanol and water, carrying out reflux reaction, then filtering reaction liquid, drying a filter cake to obtain a dried substance, soaking the dried substance in an aqueous solution containing chloroplatinic acid, carrying out ultrasonic treatment, then aging, and then roasting to obtain the composite catalyst.
The invention takes ferric sulfate hydrate and nickel nitrate hexahydrate as metal sources to prepare the bimetallic carrier, and then loads active component platinum to obtain the composite catalyst, other metals or precious metal raw materials are not needed, the preparation method is simple, the weight percentage of platinum in the composite catalyst is 0.1-1%, and the composite catalyst is applied to air pollution treatment, especially formaldehyde pollution treatment, and has the technical effects of low temperature and high efficiency.
In the invention, the time of reflux stirring is 100-150 minutes; drying at 60-70 ℃ for 1-3 h, calcining at 700-750 ℃, 20-30 min, and heating at 10 ℃/min for 7-9 h; the ultrasonic treatment time is 80-100 minutes; the aging time is 10-20 hours; roasting at 450-550 ℃ for 100-130 minutes; the weight ratio of the calcined substance to the nickel nitrate hexahydrate to the ethanolamine is 1: 1.8-2.5: 0.5.
According to actual needs, the prepared composite catalyst powder is loaded on the wall surface of a honeycomb ceramic body or a screen structure or an open-cell foam body made of metal, or the composite catalyst is made into a spherical shape or a plate shape; then the catalyst can play a role in purification at low temperature after being placed in a polluted gas atmosphere.
The preparation method of the composite catalyst provided by the invention comprises the following steps:
dispersing ferric sulfate hydrate in ethanol, refluxing and stirring for 2h, then reacting for 18h at 140 ℃ in a high-pressure reaction kettle, naturally cooling to room temperature, filtering reaction liquid, washing a filter cake twice by using ethanol, drying for 2h at 70 ℃, then heating to 750 ℃ from room temperature at a heating rate of 10 ℃/min in a muffle furnace in air, keeping for 20min, and naturally cooling to room temperature to obtain a calcined substance; mixing the calcined substance, nickel nitrate hexahydrate and ethanolamine with ethanol and water, carrying out reflux reaction for 8 hours, naturally cooling to room temperature, filtering reaction liquid, washing a filter cake twice with ethanol, and drying at 70 ℃ for 2 hours to obtain a dried substance; and (3) soaking the dried substance in an aqueous solution containing chloroplatinic acid at room temperature, carrying out ultrasonic treatment for 90 minutes, aging for 15 hours, evaporating the water in the mixed solution, transferring the mixed solution into a muffle furnace under an air condition, and roasting for 2 hours at 500 ℃ to obtain the composite catalyst.
Compared with the prior art, the invention has the following beneficial effects:
the preparation process of the catalyst is simple, the operation is convenient, the preparation process is safe and controllable, and no pollutant is generated; the catalyst has small dosage, is suitable for purifying and eliminating indoor formaldehyde with different types and different concentrations, does not need a specific light source or a specific device, can work at a lower temperature, and saves energy; in the catalyst, active platinum is uniformly loaded on the iron-nickel composite material. Therefore, the catalyst has excellent stability and purification performance.
Detailed Description
The present invention is described in detail below.
Dispersing ferric sulfate hydrate in ethanol, refluxing and stirring for 2h, then reacting for 18h at 140 ℃ in a high-pressure reaction kettle, naturally cooling to room temperature, filtering reaction liquid, washing a filter cake twice by using ethanol, drying for 2h at 70 ℃, then heating to 750 ℃ from room temperature at a heating rate of 10 ℃/min in a muffle furnace in air, keeping for 20min, and naturally cooling to room temperature to obtain a calcined substance; mixing the calcined substance, nickel nitrate hexahydrate and ethanolamine (2-hydroxyethylamine) with ethanol and water, performing reflux reaction for 8 hours, naturally cooling to room temperature, filtering reaction liquid, washing a filter cake twice with ethanol, and drying at 70 ℃ for 2 hours to obtain a dried substance; and (3) soaking the dried substance in an aqueous solution containing chloroplatinic acid at room temperature, carrying out ultrasonic treatment for 90 minutes, aging for 15 hours, evaporating the water in the mixed solution, transferring the mixed solution into a muffle furnace under an air condition, and roasting for 2 hours at 500 ℃ to obtain the composite catalyst. The preparation method of the invention does not need other steps; before the catalyst is used, the open-cell foam body can be used as a structural carrier of the catalyst by being made into various structures according to actual needs, such as being supported on the wall surface of a honeycomb ceramic body or a screen structure made of metal. The catalyst may be used in the form of spheres or plates. After the catalyst is placed in a gas atmosphere containing VOCs, the catalyst is properly heated, the catalyst can react with the VOCs at low temperature to play a role in purification, and the conversion rate can reach 100%.
All the raw materials are commercial products, and the specific preparation operation and the test method are conventional methods in the field; to better illustrate the present invention and facilitate understanding of the technical solution of the present invention, typical single non-limiting examples of the present invention are as follows (consistent with the examples and comparative examples of the invention application filed by the applicant on the same day under the name of the invention air pollution treatment agent and the preparation method and application thereof):
example 1
Dispersing 1g of ferric sulfate hydrate (CAS number: 15244-10-7) in 500mL of ethanol, stirring under reflux for 2h, then reacting in a high-pressure reaction kettle at 140 ℃ for 18h, naturally cooling to room temperature, filtering, washing a filter cake twice with ethanol, drying at 70 ℃ for 2h, then heating from room temperature to 750 ℃ in a muffle furnace in air at a heating rate of 10 ℃/min, keeping for 20min, and naturally cooling to room temperature to obtain a calcined substance; 0.1g of the calcined product, 0.2g of nickel nitrate hexahydrate (Ni (NO)3)3·6H2O), 0.05g ethanolamine, 15mL ethanol and 10mL water are mixed, reflux reaction is carried out for 8 hours, the mixture is naturally cooled to room temperature, filter cake is washed twice by ethanol after filtration, and the filter cake is dried for 2 hours at 70 ℃ to obtain a dried substance; soaking the dried substance in an aqueous solution containing chloroplatinic acid at room temperature, carrying out ultrasonic treatment at 50kHz for 90 minutes, standing and aging for 15 hours, evaporating the water in the mixed solution at 80 ℃, transferring the mixed solution into a muffle furnace under the air condition, roasting at 500 ℃ for 2 hours at the heating rate of 30 ℃/min to obtain the composite catalyst, wherein the loading amount of platinum is 0.5wt%, and the platinum is uniformly loaded on the iron-nickel bimetallic carrier according to a scanning electron microscope and a transmission electron microscope.
Taking 0.1g of the catalyst (grinding the catalyst and then sieving the ground catalyst by a 60-mesh sieve), placing the catalyst in a tubular fixed bed reactor for a conventional experiment without reduction treatment, wherein the experimental conditions are as follows: 21% of oxygen, 79% of nitrogen and 400 ppm of formaldehyde; the relative humidity is 50%, the reaction space velocity (GHSV) is 60000 mL/(gh), the reaction temperature is room temperature, the elimination rate after 2 hours of reaction is 96%, and the elimination rate after 5 hours of reaction is 100%; after seven days of continuous reaction, the elimination rate of formaldehyde is 100%.
The following comparative catalysts were obtained by performing a one-way change on the basis of example 1, and the same formaldehyde elimination experiment was performed.
Comparative example 1
The nickel nitrate hexahydrate is replaced by cobalt sulfate heptahydrate (CAS number 10026-24-1), the rest is unchanged, the composite catalyst is obtained, and the formaldehyde elimination rate after 2 hours of reaction is 78%.
Comparative example 2
Omitting ethanolamine, and keeping the rest unchanged to obtain the composite catalyst, wherein the formaldehyde elimination rate after reacting for 2 hours is 62%.
Comparative example 3
And (3) replacing the reflux reaction for 8 hours with the reflux reaction for 15 hours, and keeping the rest of the reflux reaction unchanged to obtain the composite catalyst, wherein the formaldehyde elimination rate after the reaction for 2 hours is 82%.
Comparative example 4
The calcination at 500 ℃ for 2 hours is replaced by the calcination at 600 ℃ for 2 hours, and the rest is not changed to obtain the composite catalyst, wherein the formaldehyde elimination rate after the reaction for 2 hours is 85 percent.
Comparative example 5
Dipping the calcined substance into an aqueous solution containing chloroplatinic acid, carrying out ultrasonic treatment for 90 minutes at 50kHz, standing and aging for 15 hours, evaporating the water in the mixed solution at 80 ℃, transferring the mixed solution into a muffle furnace under the air condition, roasting for 2 hours at 500 ℃, and raising the temperature at a rate of 30 ℃/min to obtain the composite catalyst, wherein the loading capacity of platinum is 0.5wt%, and the formaldehyde elimination rate after 2 hours of reaction is 31%.
Comparative example 6
And replacing the dried substance with active carbon, and keeping the rest unchanged to obtain the composite catalyst, wherein the formaldehyde elimination rate after 2 hours of reaction is 53%.
Example 2
Dispersing 1g of ferric sulfate hydrate (CAS number: 15244-10-7) in 500mL of ethanol, refluxing and stirring for 2.5h, then reacting for 18h at 140 ℃ in a high-pressure reaction kettle, naturally cooling to room temperature, filtering, washing a filter cake twice with ethanol, drying for 2h at 70 ℃, then heating from room temperature to 750 ℃ in a muffle furnace in air at a heating rate of 10 ℃/min, keeping for 20min, and naturally cooling to room temperature to obtain a calcined substance; 0.1g of the calcined product, 0.2g of nickel nitrate hexahydrate (Ni (NO)3)3·6H2O), 0.05g ethanolamine, 15mL ethanol and 10mL water are mixed, reflux reaction is carried out for 8 hours, the mixture is naturally cooled to room temperature, filter cake is washed twice by ethanol after filtration, and the filter cake is dried for 2 hours at 70 ℃ to obtain a dried substance; immersing the dried product in a solution containing chlorine at room temperatureIn the aqueous solution of platinic acid, 50kHz ultrasonic treatment is carried out for 90 minutes, standing and aging are carried out for 15 hours, then water in the mixed solution is evaporated at the temperature of 80 ℃, the mixed solution is moved to a muffle furnace under the air condition, roasting is carried out for 2 hours at the temperature of 500 ℃, the heating rate is 30 ℃/min, the composite catalyst is obtained, the loading capacity of platinum is 0.5wt%, and the formaldehyde elimination rate after 2 hours of reaction is 93%.
Example 3
Dispersing 1g of ferric sulfate hydrate (CAS number: 15244-10-7) in 500mL of ethanol, refluxing and stirring for 2.5h, then reacting for 18h at 140 ℃ in a high-pressure reaction kettle, naturally cooling to room temperature, filtering, washing a filter cake twice with ethanol, drying for 2h at 70 ℃, then heating to 700 ℃ from room temperature at a heating rate of 10 ℃/min in a muffle furnace in air, keeping for 25min, and naturally cooling to room temperature to obtain a calcined substance; 0.1g of the calcined product, 0.22g of nickel nitrate hexahydrate (Ni (NO)3)3·6H2O), 0.05g ethanolamine, 15mL ethanol and 10mL water are mixed, reflux reaction is carried out for 8 hours, the mixture is naturally cooled to room temperature, filter cake is washed twice by ethanol after filtration, and the filter cake is dried for 2 hours at 70 ℃ to obtain a dried substance; at room temperature, the dried substance is immersed in an aqueous solution containing chloroplatinic acid, ultrasonic treatment is carried out at 50kHz for 90 minutes, standing and aging are carried out for 15 hours, then water in the mixed solution is evaporated at 80 ℃, the mixed solution is moved to a muffle furnace under the air condition, roasting is carried out at 500 ℃ for 2 hours, the heating rate is 30 ℃/min, and the composite catalyst is obtained, wherein the loading capacity of platinum is 0.5wt%, and the formaldehyde elimination rate after 2 hours of reaction is 90%.
Example 4
Dispersing 1g of ferric sulfate hydrate (CAS number: 15244-10-7) in 500mL of ethanol, refluxing and stirring for 2.5h, then reacting for 18h at 140 ℃ in a high-pressure reaction kettle, naturally cooling to room temperature, filtering, washing a filter cake twice with ethanol, drying for 2h at 70 ℃, then heating from room temperature to 750 ℃ in a muffle furnace in air at a heating rate of 10 ℃/min, keeping for 20min, and naturally cooling to room temperature to obtain a calcined substance; 0.1g of the calcined product, 0.2g of nickel nitrate hexahydrate (Ni (NO)3)3·6H2O), 0.05g ethanolamine, 15mL ethanol and 10mL water, reflux reaction for 7 hours, natural cooling to room temperature, filtering, and filtering the filter cakeWashing with alcohol twice, and drying at 70 deg.C for 2 hr to obtain dried substance; at room temperature, the dried substance is immersed in an aqueous solution containing chloroplatinic acid, ultrasonic treatment is carried out at 60kHz for 90 minutes, standing and aging are carried out for 15 hours, then water in the mixed solution is evaporated at 80 ℃, the mixed solution is moved to a muffle furnace under the air condition, roasting is carried out at 500 ℃ for 2 hours, the heating rate is 30 ℃/min, and the composite catalyst is obtained, wherein the loading capacity of platinum is 0.5wt%, and the formaldehyde elimination rate after 2 hours of reaction is 90%.
Example 5
Dispersing 1g of ferric sulfate hydrate (CAS number: 15244-10-7) in 500mL of ethanol, refluxing and stirring for 2.5h, then reacting for 18h at 140 ℃ in a high-pressure reaction kettle, naturally cooling to room temperature, filtering, washing a filter cake twice with ethanol, drying for 2h at 70 ℃, then heating from room temperature to 750 ℃ in a muffle furnace in air at a heating rate of 10 ℃/min, keeping for 20min, and naturally cooling to room temperature to obtain a calcined substance; 0.1g of the calcined product, 0.18g of nickel nitrate hexahydrate (Ni (NO)3)3·6H2O), 0.05g ethanolamine, 15mL ethanol and 10mL water are mixed, reflux reaction is carried out for 8 hours, the mixture is naturally cooled to room temperature, filter cake is washed twice by ethanol after filtration, and the filter cake is dried for 2 hours at 70 ℃ to obtain a dried substance; at room temperature, the dried substance is immersed in an aqueous solution containing chloroplatinic acid, ultrasonic treatment is carried out at 50kHz for 90 minutes, standing and aging are carried out for 15 hours, then water in the mixed solution is evaporated at 80 ℃, the mixed solution is moved to a muffle furnace under the air condition, roasting is carried out at 450 ℃ for 2 hours, the heating rate is 30 ℃/min, and the composite catalyst is obtained, wherein the loading capacity of platinum is 0.5wt%, and the formaldehyde elimination rate after 2 hours of reaction is 86%.
The catalyst can efficiently, stably and thoroughly remove formaldehyde in air in a real environment with room temperature and normal humidity, has no adverse side effect on human bodies, and can be widely applied to preparation of various formaldehyde-removing air purifiers. The applicant states that the present invention is illustrated by the above examples to show the detailed composition of the catalyst, but the present invention is not limited to the above detailed composition, i.e. it is not meant that the present invention must rely on the above detailed composition to be carried out. It should be understood by those skilled in the art that any modification of the present invention, equivalent replacement of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The method for treating air pollution by using the composite catalyst is characterized in that the preparation method of the composite catalyst comprises the following steps of dispersing ferric sulfate hydrate in ethanol, refluxing and stirring, then reacting in a high-pressure reaction kettle at 140 ℃ for 18h, then filtering reaction liquid, drying a filter cake and then calcining to obtain a calcined substance; mixing the calcined substance, nickel nitrate hexahydrate, ethanolamine, ethanol and water, carrying out reflux reaction, then filtering reaction liquid, drying a filter cake to obtain a dried substance, soaking the dried substance in an aqueous solution containing chloroplatinic acid, carrying out ultrasonic treatment, then aging, and then roasting to obtain the composite catalyst.
2. The method for treating air pollution by using the composite catalyst according to claim 1, wherein the time of the reflux stirring is 100 to 150 minutes; the drying is carried out for 1-3 h at the temperature of 60-70 ℃.
3. The method for treating air pollution by using the composite catalyst according to claim 1, wherein the calcination temperature is 700 to 750 ℃, the calcination time is 20 to 30 minutes, and the temperature increase rate is 10 ℃/min.
4. The method for treating air pollution by using the composite catalyst as claimed in claim 1, wherein the time of the reflux reaction is 7 to 9 hours.
5. The method for treating air pollution by using the composite catalyst according to claim 1, wherein the time of the ultrasonic treatment is 80 to 100 minutes; the aging time is 10-20 hours; the roasting temperature is 450-550 ℃, and the roasting time is 100-130 minutes.
6. The method for treating air pollution using the composite catalyst as recited in claim 1, wherein the treatment of air pollution is performed by passing polluted air through the composite catalyst at room temperature.
7. The method for treating air pollution by using the composite catalyst as claimed in claim 1, wherein the weight ratio of the calcined product, the nickel nitrate hexahydrate and the ethanolamine is 1: 1.8-2.5: 0.5.
8. The method for treating air pollution using the composite catalyst according to claim 1, wherein the weight percentage of platinum in the composite catalyst is 0.1 to 1%.
9. The method for treating air pollution using the composite catalyst as claimed in claim 1, wherein the reaction space velocity when the polluted air is passed through the composite catalyst is 60000 mL/(gh).
10. The method for treating air pollution using the composite catalyst according to claim 1, wherein the pollution is formaldehyde pollution.
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| CN113398904A (en) * | 2021-05-06 | 2021-09-17 | 桂林电子科技大学 | Preparation method and application of catalyst for medium-low temperature photo-thermoelectric synergistic catalytic oxidation of VOCs (volatile organic compounds) |
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| CN106492792A (en) * | 2017-01-05 | 2017-03-15 | 吉林化工学院 | A kind of loaded catalyst of eliminating formaldehyde at room temperature and preparation method thereof |
| CN106540741A (en) * | 2016-10-19 | 2017-03-29 | 浙江大学 | It is used at room temperature eliminating catalyst of formaldehyde and preparation method thereof |
| CN110743570A (en) * | 2019-11-19 | 2020-02-04 | 宋学杰 | Preparation method of catalyst containing porous structure base material and method for decomposing formaldehyde by using catalyst |
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| CN106540741A (en) * | 2016-10-19 | 2017-03-29 | 浙江大学 | It is used at room temperature eliminating catalyst of formaldehyde and preparation method thereof |
| CN106492792A (en) * | 2017-01-05 | 2017-03-15 | 吉林化工学院 | A kind of loaded catalyst of eliminating formaldehyde at room temperature and preparation method thereof |
| CN110743570A (en) * | 2019-11-19 | 2020-02-04 | 宋学杰 | Preparation method of catalyst containing porous structure base material and method for decomposing formaldehyde by using catalyst |
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| CN113398904A (en) * | 2021-05-06 | 2021-09-17 | 桂林电子科技大学 | Preparation method and application of catalyst for medium-low temperature photo-thermoelectric synergistic catalytic oxidation of VOCs (volatile organic compounds) |
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