CN110975865B - Preparation method of photocatalytic complexing agent for purifying air with high light conductivity and high adsorption performance - Google Patents
Preparation method of photocatalytic complexing agent for purifying air with high light conductivity and high adsorption performance Download PDFInfo
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 43
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000008139 complexing agent Substances 0.000 title claims abstract description 15
- 239000002131 composite material Substances 0.000 claims abstract description 43
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 6
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 6
- 238000013329 compounding Methods 0.000 claims abstract description 4
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 39
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 33
- 239000000843 powder Substances 0.000 claims description 30
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 29
- 239000003365 glass fiber Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000008262 pumice Substances 0.000 claims description 15
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 12
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 12
- 241001330002 Bambuseae Species 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 12
- 239000011425 bamboo Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 9
- 238000004887 air purification Methods 0.000 claims description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 7
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- 150000003608 titanium Chemical class 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000013067 intermediate product Substances 0.000 claims description 2
- 238000000746 purification Methods 0.000 abstract description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 97
- 239000011941 photocatalyst Substances 0.000 description 17
- 239000004408 titanium dioxide Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 230000008859 change Effects 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000003980 solgel method Methods 0.000 description 4
- 238000000151 deposition Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 238000013032 photocatalytic reaction Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
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- 239000010931 gold Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
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- 238000007254 oxidation reaction Methods 0.000 description 2
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- 239000011148 porous material Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229960004424 carbon dioxide Drugs 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000001089 mineralizing effect Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 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
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000013598 vector Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- 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
- 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
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- B01J35/39—
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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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0063—Granulating
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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
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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
- B01J37/344—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 electromagnetic wave energy
- B01J37/345—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 electromagnetic wave energy of ultraviolet wave energy
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/80—Type of catalytic reaction
- B01D2255/802—Photocatalytic
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention discloses a preparation method of a photocatalytic complexing agent for purifying air, which has high light conductivity and high adsorption performance, and comprises the following steps: 1) synthesizing a composite adsorption carrier; 2) synthesis of Pd/TiO 2 Compounding colloidal solution: wherein Pd/TiO 2 The Pd content in the composite colloidal solution is controlled to be 0.001-0.1 wt%; 3) immersing the composite adsorption carrier prepared in the step 1) into the Pd/TiO prepared in the step 2) 2 The composite colloidal solution is put for 10 to 120min and then taken out and dried at the temperature of between 25 and 100 ℃ to prepare the photocatalytic complexing agent for purifying the air with high light conductivity; the invention has high purification efficiency, good water resistance and high adsorption performance.
Description
Technical Field
The invention relates to the technical field of air purification materials, in particular to a preparation method of a photocatalytic complexing agent for purifying air with high light conductivity and high adsorption performance.
Background
At present, various products for purifying air exist in the market, such as activated carbon, photocatalyst (photocatalysis), aldehyde removing agent and the like, but the number of photocatalytic activated carbon particles or photocatalytic composite porous adsorption products is relatively small, part of photocatalytic composite products are prepared by mainly taking titanium-based liquid or titanium dioxide sol liquid as precursor liquid and carrying out soaking, drying, high-temperature treatment and other processes, the air purifying effect of some photocatalysis is not ideal, and the photocatalysis loading method mainly comprises a powder sintering method, a soaking pulling method, a sol-gel method, a chemical vapor deposition method and the like. Although these methods produce TiO 2 Small particle size but poor stability, easy agglomeration of nano particles, reduced photocatalytic activity, complex preparation process, difficult technical application and popularization, high cost, large energy consumption especially through high-temperature crystallization sintering at the temperature of 500-800 ℃, poor bonding firmness of the titanium dioxide film and a base material and shedding or powder falling easily caused by improper sintering crystallization treatment, the photocatalyst is deposited on the surface of porous adsorption carriers such as active carbon, zeolite, molecular sieve and the like, and the photocatalyst is difficult to deposit in small holes or micro channels in the adsorption carriers, for example, in the preparation of photocatalytic active carbon particles by a sol-gel method, a titanium dioxide film is mainly deposited on mesopores (with the aperture being about 2-50 nm), macropores (with the pore diameter being more than or equal to 50 nm) and the surface of active carbon of an active carbon carrier, and can rarely enter micropores or microchannels of an inner layer of the active carbon adsorption, and the method has great difficulty in popularization and application due to equipment cost and process conditions. And when the activated carbon carrier is used for purifying and treating formaldehyde micromolecules, the formaldehyde molecules stay and are adsorbed in the micro-channels after the formaldehyde molecules are saturated, so that the efficiency of degrading formaldehyde by photocatalysis is influenced, and the formaldehyde molecules can only be transferred to the macropores or the photocatalyst on the outer surface of the carrier in a diffusion mode to be decomposed.
The photocatalyst prepared by mixing titanium dioxide powder and activated carbon powder or the activated carbon particle catalyst can be prepared by fully contacting the titanium dioxide catalyst and the activated carbon adsorbent, but the process has a high-temperature treatment process and high cost. For example, CN108722388A discloses a photocatalyst for air purification. The catalyst is prepared by mixing zinc oxide, activated carbon and titanium dioxide powder and then firing at a high temperature. Meanwhile, the activated carbon particles on the market have the defects of poor water resistance, low mechanical strength, low light utilization rate and the like. When the active carbon particles with poor water resistance are exposed to water or a humid environment for a long time, the surface of the active carbon can crack and pulverize to influence the photocatalytic film on the outer surface layer of the active carbon.
The photocatalytic degradation of organic matters requires oxygen molecules (O) in the air 2 ) Or water molecules (H) 2 O) and generate free radicals with strong oxidizing properties such as oxygen radicals (. O) 2 ) And hydroxyl radicals (. OH). These free radicals can sterilize or inhibit bacteria, decompose organic pollutants, and finally make organicDecomposing and mineralizing the substances into nontoxic water (H) 2 O) and carbon dioxide (CO) 2 ) Therefore, the air purifier has extremely strong functions of sterilization, deodorization, mildew prevention and air purification, and sufficient oxygen molecules or water molecules can greatly improve the efficiency of decomposing organic matters and purifying air. Therefore, the adsorption performance of the activated carbon particles to water molecules influences the efficiency of photocatalytic degradation of organic pollutants.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art: provides a preparation method of a photocatalytic complexing agent for purifying air with high purification efficiency, good water resistance and high light conductivity, which efficiently utilizes a light source and has high adsorption performance.
The photocatalytic purification product prepared by uniformly mixing the adsorbent and the photocatalyst can avoid the defects that the photocatalyst prepared by methods such as a dip-coating method, a sol-gel method, a liquid phase deposition method and the like is mainly deposited on the outer surface of the adsorption particles and a macroporous pore passage, but how to introduce a light source into the adsorption inner layer of the purification product for photocatalytic reaction and improve the photocatalytic efficiency is worthy of research.
The technical solution of the invention is as follows: a preparation method of a photocatalytic complexing agent for purifying air with high light conductivity and high adsorption performance comprises the following steps:
1) synthesizing a composite adsorption carrier: fully mixing and stirring the following components in parts by weight, granulating, molding, and drying at 30-100 ℃: 30-50 parts of bamboo activated carbon powder, 10-30 parts of nano titanium dioxide powder, 5-10 parts of glass fiber, 20-40 parts of pumice powder, 10-20 parts of silica sol with the solid content of 20 percent and 1-10 parts of hydrogen peroxide with the mass fraction of 30 percent;
2) synthesis of Pd/TiO 2 Compounding colloidal solution: firstly, dissolving palladium nitrate in concentrated nitric acid, stirring uniformly, heating to 25-80 ℃, dropwise adding a titanium salt precursor under stirring, continuously stirring for 30-60min, and adding water to control the pH value to be lower than 5; then continuously stirring for 10-24h, continuously stirring for 24-48h under the irradiation of ultraviolet lamp light with the wavelength of 254nm to prepare TiO 2 Pd/TiO with content of 0.2-5.0wt% 2 Composite colloidal solution of Pd/TiO 2 The Pd content in the composite colloidal solution is controlled to be 0.001-0.1 wt%;
3) immersing the composite adsorption carrier prepared in the step 1) into the Pd/TiO prepared in the step 2) 2 And (3) putting the composite colloidal solution in the composite colloidal solution for 10-120min, taking out the composite colloidal solution and drying the composite colloidal solution at the temperature of 25-100 ℃ to obtain the photocatalytic complexing agent for purifying the air with high light guide rate.
The mass percentage of Pd in the palladium nitrate is 39.5%.
The mass fraction of the concentrated nitric acid is 65-68%.
The power of the ultraviolet lamp is 10-50W.
The titanium salt precursor is one or more of ethyl titanate, butyl titanate, titanium isopropoxide and chemical intermediate product titanium oxynitrate.
The granularity range of the bamboo activated carbon powder is 1-150um, and the average grain diameter is 40 um.
The nano titanium dioxide powder is in an anatase crystal form, the particle size is not more than 100nm, and the optimal average particle size range is 5-10 nm.
The size of the glass fiber is 200-400 mu m in length and 20-40 mu m in diameter.
The glass fiber is quartz glass fiber.
The particle size of the pumice powder is 100-200 meshes.
The particle size of the granulation molding is 5-20 mm.
The invention has the beneficial effects that: the preparation method of the photocatalytic complexing agent comprises two steps, namely synthesis of a high-adsorbability photocatalytic composite adsorption carrier and synthesis of palladium-doped titanium dioxide sol.
The first step is to prepare photocatalyst composite adsorption carrier particles at low temperature, and introduce glass fiber and pumice powder, so that the prepared adsorption carrier has the advantages of light weight, good adsorption performance, and good water resistance and strength. The photocatalyst nano titanium dioxide powder, the activated carbon powder and the pumice powder adsorbent are fully mixed, so that the condition that the photocatalyst is mainly deposited on the surfaces of a mesopore, a macropore and a carrier of an adsorption carrier in the conventional photocatalyst deposition preparation process in the market at present is avoided, the nano titanium dioxide powder can enter the interior and the micropores of the adsorption carrier, the light absorption rate is improved through the light refraction and transmission effects of glass fibers, the light is promoted to be reflected for multiple times in the inner space of the carrier, the photocatalytic reaction of the nano titanium dioxide in the carrier is facilitated, and the photocatalytic air purification efficiency is improved.
In the second step, titanium salt is directly hydrolyzed in the preparation of the palladium-doped titanium dioxide sol, the defect that a large amount of organic matters are introduced by the traditional sol-gel method is overcome, and Pd/TiO is prepared by combining the palladium deposition and the titanium dioxide through the process of combining ozone generation by a 254nm ultraviolet lamp and photochemical oxidation 2 The colloid is purified by photochemical oxidation in the preparation process, so that the dialysis method is prevented from using a large amount of water and generating certain waste water, and the equipment cost is high.
By Pd/TiO 2 The colloid solution can be soaked to deposit a certain amount of Pd/TiO on the surface and the macropores of the composite adsorption carrier 2 The film further improves the utilization rate of the composite carrier to ultraviolet-visible light and improves the photocatalytic efficiency. Because the titanium dioxide colloid improves the binding force of the nano palladium and the carrier. If the carrier is directly and simply soaked in the palladium nitrate solution for drying, the combination of the nano palladium-gold and the active carbon or the pumice or the glass fiber in the carrier is not firm, the nano palladium is deposited in the nano titanium dioxide colloid, and then the carrier is soaked, so that the adhesive force of the nano palladium-gold on the carrier is improved. In addition, the palladium-doped titanium dioxide can improve the visible light photocatalytic activity of the titanium dioxide, and promote the functions of organic adsorption, antibiosis, sterilization, photocatalytic decomposition of organic matters and the like. The preparation method disclosed by the invention is simple to operate, the raw materials are easy to obtain, the preparation cost is low, and the preparation method has a wide application prospect in the field of air purification.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
1) Synthesizing a composite adsorption carrier: the following components in parts by weight are mixed and stirred uniformly, granulated, formed and dried at 100 ℃: 50 parts of bamboo activated carbon powder, 20 parts of nano titanium dioxide powder, 10 parts of glass fiber, 30 parts of pumice powder, 15 parts of silica sol with the solid content of 20 percent and 2 parts of hydrogen peroxide with the mass fraction of 30 percent; the particle size range of the bamboo activated carbon powder is 1-150um, and the average particle size is 40 um; the nano titanium dioxide powder is in an anatase crystal form, and the particle size is less than 5 nm; the size of the glass fiber is 200-400 mu m in length and 20-40 mu m in diameter; the glass fiber is quartz glass fiber; the particle size of the pumice powder is 100-200 meshes; the particle size of the granulation molding is 5-20 mm.
2) Synthesis of Pd/TiO 2 Compounding colloidal solution: firstly, dissolving palladium nitrate in concentrated nitric acid, uniformly stirring and heating to 60 ℃, dropwise adding a titanium salt precursor under stirring, continuously stirring for 60min, and adding water to control the pH value to be lower than 5; then continuously stirring for 24h, continuously stirring for 48h under the irradiation of 254nm ultraviolet lamp, and finally controlling the preparation to obtain TiO 2 Pd/TiO in an amount of 3.0wt% 2 Composite colloidal solution of Pd/TiO 2 The Pd content in the composite colloidal solution is controlled to be 0.1 wt%; the mass percentage content of Pd in the palladium nitrate is 39.5%; the mass fraction of the concentrated nitric acid is 65 percent; the power of the ultraviolet lamp is 25W; the titanium salt precursor is ethyl titanate.
3) Immersing the composite adsorption carrier prepared in the step 1) into the Pd/TiO prepared in the step 2) 2 And (3) putting the composite colloidal solution for 120min, taking out the composite colloidal solution and drying the composite colloidal solution at 90 ℃ to prepare the photocatalytic complexing agent for purifying air with high light guiding rate.
Comparative example 1
Preparation of photocatalyst-free adsorption Carrier
The following components in parts by weight are mixed and stirred uniformly, granulated, formed and dried at 100 ℃: 50 parts of bamboo activated carbon powder, 10 parts of glass fiber, 30 parts of pumice powder, 15 parts of silica sol with the solid content of 20 percent and 2 parts of hydrogen peroxide with the mass fraction of 30 percent; the particle size range of the bamboo activated carbon powder is 1-150um, and the average particle size is 40 um; the size of the glass fiber is 200-400um in length and 20-40um in diameter; the glass fiber is quartz glass fiber; the particle size of the pumice powder is 100-200 meshes; the particle size of the granulation molding is 5-20 mm.
Comparative example 2
Preparation of glass fiber-free composite carrier containing photocatalyst
Mixing the following components in parts by weight, stirring uniformly, granulating, forming and drying at 100 ℃: 50 parts of bamboo activated carbon powder, 20 parts of nano titanium dioxide powder, 30 parts of pumice powder, 15 parts of silica sol with the solid content of 20 percent and 2 parts of hydrogen peroxide with the mass fraction of 30 percent; the particle size range of the bamboo activated carbon powder is 1-150um, and the average particle size is 40 um; the nano titanium dioxide powder is in an anatase crystal form, and the particle size is less than 5 nm; the particle size of the pumice powder is 100-200 meshes; the particle size of the granulation molding is 5-20 mm.
Comparative example 3
Preparation of Pd/TiO-free 2 Photocatalyst-containing composite carrier soaked in composite colloidal solution
Mixing the following components in parts by weight, stirring uniformly, granulating, forming and drying at 100 ℃: 50 parts of bamboo activated carbon powder, 20 parts of nano titanium dioxide powder, 10 parts of glass fiber, 30 parts of pumice powder, 15 parts of silica sol with the solid content of 20 percent and 2 parts of hydrogen peroxide with the mass fraction of 30 percent; the particle size range of the bamboo activated carbon powder is 1-150um, and the average particle size is 40 um; the nano titanium dioxide powder is in an anatase crystal form, and the particle size is less than 5 nm; the size of the glass fiber is 200-400um in length and 20-40um in diameter; the glass fiber is quartz glass fiber; the particle size of the pumice powder is 100-200 meshes; the particle size of the granulation molding is 5-20 mm.
Performance testing
200g of the adsorbent carrier prepared in comparative example 1 was weighed, the carrier particles were uniformly spread in a square stainless steel box (box size 20cm long, 20cm wide and 4cm high), and the box containing the adsorbent carrier was placed in a 1m box 3 A sealed evaluation test cabin internally provided with a circulating fan, a strip-shaped fluorescent lamp (2 lamps with the sunlight brand model T5 and the power of 8 w) is uniformly arranged above the middle of the stainless steel box, and the test cabin door is closed for sealing; dripping the formaldehyde solution on an aluminum alloy heating electric plate (the temperature of the heating plate is 60-100 ℃) by a dropper through a test chamber sample inlet, rapidly sealing the sample inlet, and recording the concentration value of the formaldehyde after the rising concentration change on the formaldehyde detector is mild and the concentration change is balanced. Starting circulating fan and fluorescence in test chamberThe lamp accelerates the air flow in the cabin and simultaneously records the change condition of the formaldehyde concentration along with the time;
200g of the photocatalytic composite agent for air purification with high light transmittance, which was prepared in the same manner as in example 1, was weighed and subjected to the same evaluation process as described above in the method for measuring the change of formaldehyde with time using the adsorption carrier in comparative example 1.
In the absence of the adsorption carrier and the photocatalytic complexing agent, a blank test was carried out in the test chamber under the same conditions with formaldehyde.
TABLE 1 comparison of Formaldehyde removal efficiency of two carriers in test chamber
As shown in Table 1, the carrier prepared according to comparative example 1 can remove formaldehyde and has a certain adsorption property to formaldehyde. The example 1 has a photocatalyst compounded on the carrier so that the formaldehyde removal rate is higher than that of the carrier of the comparative example 1. Blank data fluctuations may be due to natural attenuation of formaldehyde or wall adsorption effects.
Comparative evaluation of catalyst Performance
Three carriers of comparative examples 1 to 3 and the photocatalytic complexing agent prepared in example 1 were filled in transparent tubes with an inner diameter of 5cm and a length of 20cm, the transparent tubes were opened at both ends and particles were limited by a screen, the particle size of the carrier particles was 2 to 5mm, formaldehyde gas of a certain concentration was continuously introduced from one end of the transparent tube, the change in the concentration of formaldehyde at the outlet of the other end was measured, and the concentration of formaldehyde at the inlet C was measured in With the outlet formaldehyde concentration C out When the formaldehyde concentration at the outlet tends to be stable, the concentration C of the formaldehyde at the outlet is measured out And calculating the formaldehyde removal rate.
The formula for calculating the formaldehyde removal rate is as follows:
x=（C in -C out ）/C in × 100%
in the formula, x is the removal rate of formaldehyde; c in And C out The formaldehyde concentrations at the inlet and outlet, respectively.
TABLE 2 Formaldehyde removal efficiency of four vectors in a continuous flow device
From table 2 above, it can be seen that: when formaldehyde is adsorbed and saturated, the adsorption carrier without the nano titanium dioxide photocatalyst can not carry out photocatalytic degradation on formaldehyde by turning on the lamp, and the change of the removal rate of the formaldehyde can be ignored. The formaldehyde removal rate can be obviously improved after the glass fiber is introduced into the adsorption carrier particles, and the glass fiber is introduced to enable light to be reflected or refracted for multiple times inside the carrier, so that the light utilization rate is improved, and the photocatalytic reaction is facilitated. EXAMPLE 1 photocatalytic composite Carrier particles were passed over Pd/TiO 2 After the composite colloidal solution is treated, the nano palladium-doped titanium dioxide is deposited on photocatalytic composite carrier particles, so that the surface photocatalytic dosage of mesopores, macropores and the like in the carrier is further enhanced, meanwhile, the nano palladium-doped modified titanium dioxide can improve the photocatalytic activity of the titanium dioxide and promote the improvement of the efficiency of removing formaldehyde by photocatalysis, and the photocatalytic composite agent has a better function of decomposing harmful gases.
The photocatalyst composite prepared in example 1 was coated on a support of 1m 3 The method for testing formaldehyde in the sealed evaluation test cabin is used for testing the effect of removing ammonia gas by the photocatalytic complexing agent after the same evaluation process under the same condition. The test results found 1m 3 The concentration of ammonia gas in the test chamber is 1.50mg/m 3 After 2h, the concentration was reduced to 0.12mg/m 3 And the removal rate is 92%.
The above are merely characteristic embodiments of the present invention, and do not limit the scope of the present invention in any way. All technical solutions formed by equivalent exchanges or equivalent substitutions fall within the protection scope of the present invention.
Claims (5)
1. A preparation method of a photocatalytic complexing agent for air purification with high light guide rate and high adsorption performance is characterized by comprising the following steps:
1) synthesizing a composite adsorption carrier: mixing the following components in parts by weight, stirring uniformly, granulating, forming, and drying at 30-100 ℃: 30-50 parts of bamboo activated carbon powder, 10-30 parts of nano titanium dioxide powder, 5-10 parts of glass fiber, 20-40 parts of pumice powder, 10-20 parts of silica sol with the solid content of 20 percent and 1-10 parts of hydrogen peroxide with the mass fraction of 30 percent;
2) synthesis of Pd/TiO 2 Compounding colloidal solution: firstly, dissolving palladium nitrate in concentrated nitric acid, stirring uniformly, heating to 25-80 ℃, dropwise adding a titanium salt precursor under stirring, continuously stirring for 30-60min, and adding water to control the pH value to be lower than 5; then continuously stirring for 10-24h under the irradiation of ultraviolet lamp with the wavelength of 254nm for 24-48h to prepare TiO 2 Pd/TiO with content of 0.2-5.0wt% 2 Composite colloidal solution of Pd/TiO 2 The Pd content in the composite colloidal solution is controlled to be 0.001-0.1 wt%;
3) immersing the composite adsorption carrier prepared in the step 1) into the Pd/TiO prepared in the step 2) 2 Taking out the composite colloidal solution for 10-120min, and drying at 25-100 ℃ to obtain the photocatalytic complexing agent for purifying air with high light-guiding rate;
the particle size range of the bamboo activated carbon powder is 1-150um, and the average particle size is 40 um;
the nano titanium dioxide powder is in an anatase crystal form, and the particle size is not more than 100 nm;
the size of the glass fiber is 200-400um in length and 20-40um in diameter;
the glass fiber is quartz glass fiber, and the particle size of the pumice powder is 100-200 meshes;
the particle size of the granulation molding is 5-20 mm.
2. The method for preparing the photocatalytic composite agent for purifying air with high light-guiding rate and high adsorption performance as recited in claim 1, wherein the mass percentage of Pd in the palladium nitrate is 39.5%.
3. The method for preparing the photocatalytic composite agent for purifying air with high light conductivity and high adsorption performance as claimed in claim 1, wherein the mass fraction of the concentrated nitric acid is 65-68%.
4. The method for preparing the photocatalytic composite agent for purifying air with high light-guiding rate and high adsorption performance as claimed in claim 1, wherein the power of the ultraviolet lamp is 10-50W.
5. The method for preparing the photocatalytic composite agent for purifying air with high light-guiding rate and high adsorption property as claimed in claim 1, wherein the titanium salt precursor is one or more of ethyl titanate, butyl titanate, titanium isopropoxide and chemical intermediate product titanium oxynitrate.
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