CN114192133A - Titanium dioxide photocatalytic stock solution, digestion membrane and preparation method thereof - Google Patents
Titanium dioxide photocatalytic stock solution, digestion membrane and preparation method thereof Download PDFInfo
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- CN114192133A CN114192133A CN202111612954.4A CN202111612954A CN114192133A CN 114192133 A CN114192133 A CN 114192133A CN 202111612954 A CN202111612954 A CN 202111612954A CN 114192133 A CN114192133 A CN 114192133A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 300
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 132
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 121
- 239000011550 stock solution Substances 0.000 title claims abstract description 66
- 230000029087 digestion Effects 0.000 title claims abstract description 45
- 239000012528 membrane Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 50
- 239000000463 material Substances 0.000 claims abstract description 44
- 230000001070 adhesive effect Effects 0.000 claims abstract description 33
- 238000007146 photocatalysis Methods 0.000 claims abstract description 33
- 239000000853 adhesive Substances 0.000 claims abstract description 32
- 238000001179 sorption measurement Methods 0.000 claims abstract description 29
- 239000002270 dispersing agent Substances 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004115 Sodium Silicate Substances 0.000 claims description 28
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 28
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 17
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000012621 metal-organic framework Substances 0.000 claims description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229920013821 hydroxy alkyl cellulose Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000661 sodium alginate Substances 0.000 claims description 2
- 235000010413 sodium alginate Nutrition 0.000 claims description 2
- 229940005550 sodium alginate Drugs 0.000 claims description 2
- 238000010276 construction Methods 0.000 abstract description 19
- 230000001965 increasing effect Effects 0.000 abstract description 8
- 230000001276 controlling effect Effects 0.000 abstract description 4
- 230000002035 prolonged effect Effects 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 230000003993 interaction Effects 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 description 22
- 231100000719 pollutant Toxicity 0.000 description 22
- 239000002808 molecular sieve Substances 0.000 description 19
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 19
- 239000011230 binding agent Substances 0.000 description 17
- 239000000725 suspension Substances 0.000 description 13
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 4
- 239000004568 cement Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical group [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- -1 and the like Chemical compound 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 239000013310 covalent-organic framework Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000010447 natron Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000009991 scouring Methods 0.000 description 2
- 239000011265 semifinished product Substances 0.000 description 2
- PHIQPXBZDGYJOG-UHFFFAOYSA-N sodium silicate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-][Si]([O-])=O PHIQPXBZDGYJOG-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000013148 Cu-BTC MOF Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229920001875 Ebonite Polymers 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000013291 MIL-100 Substances 0.000 description 1
- 239000013132 MOF-5 Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910020489 SiO3 Inorganic materials 0.000 description 1
- 241000219289 Silene Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 239000010457 zeolite 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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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
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
- B01J35/59—Membranes
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- 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
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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
- B01J37/0215—Coating
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
- C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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Abstract
The invention provides a titanium dioxide photocatalytic stock solution, a digestion membrane and a preparation method thereof, wherein the preparation raw materials of the titanium dioxide photocatalytic stock solution comprise the following components in percentage by mass: 0.1 to 10.0 percent of titanium dioxide powder, 0.1 to 6.0 percent of porous adsorption material, 0.1 to 10.0 percent of dispersant, 1.0 to 20.0 percent of inorganic adhesive and the balance of water. According to the titanium dioxide photocatalysis stock solution, the purpose of increasing the adhesive force of the photocatalysis digestion film on a common surface is achieved by adding the inorganic adhesive, so that the photocatalysis digestion film is not easily subjected to mechanical friction loss, the photocatalysis utility time is prolonged, and the obtained photocatalysis digestion film still has stronger photocatalysis performance by regulating and controlling the interaction of all components in the photocatalysis stock solution, and the functionality of the construction surface is not obviously influenced.
Description
Technical Field
The invention belongs to the technical field of photocatalytic materials, and particularly relates to a titanium dioxide photocatalytic stock solution, a digestion membrane and a preparation method thereof.
Background
In 1972, Japanese scientists Honda and Fujishima discovered that the titanium dioxide nano material supplemented with metal platinum can be used for treating H under the irradiation of ultraviolet light2Complete decomposition of O to H2And O2. This important finding opens up a completely new field of research in photocatalysis. Especially in recent years, a great deal of research proves that the titanium dioxide nano-particles can effectively decompose NO under the irradiation of ultraviolet lightx、SO2VOCs and other gaseous pollutants, and the final product is H2O、CO2And the like. Therefore, titanium dioxide has been widely used as a main photocatalytic component in various products.
The surface construction is carried out by titanium dioxide photocatalysis stock solution, a compact photocatalysis digestion film is formed on various working surfaces, and the method is one of effective methods for purifying gas pollutants by using photocatalysis materials at present. However, the photocatalytic digestion film gradually falls off when subjected to mechanical friction for a long time on the surface of a road or the like, and finally the purification capability of gaseous pollutants is reduced. Generally, after 6 months of construction, the photocatalytic digestion membrane needs to be constructed again to ensure the stability of the purification effect of the gas pollutants. Therefore, it is desirable to provide a photocatalytic digestion film which has strong adhesion to common surfaces and is not easily abraded.
Disclosure of Invention
The invention solves the technical problem of providing a titanium dioxide photocatalytic stock solution, a digestion membrane and a preparation method thereof, which achieve the purpose of increasing the adhesive force of the photocatalytic digestion membrane on the common surface by adding an inorganic adhesive, so that the photocatalytic digestion membrane is not easy to suffer from mechanical friction loss, thereby prolonging the photocatalytic effect time, and the obtained photocatalytic digestion membrane still has stronger photocatalytic performance and has no obvious influence on the functionality of a construction surface by regulating and controlling the interaction of all components in the photocatalytic stock solution.
In order to solve the problems, the invention provides a titanium dioxide photocatalysis stock solution, which comprises the following preparation raw materials in percentage by mass:
0.1 to 10.0 percent of titanium dioxide powder, 0.1 to 6.0 percent of porous adsorption material, 0.1 to 10.0 percent of dispersant, 1.0 to 20.0 percent of inorganic adhesive and the balance of water.
The titanium dioxide photocatalysis stock solution of the invention has the photocatalysis function of titanium dioxide powder, and the photocatalysis principle is as follows: the band gap of the titanium dioxide nano material is 3.2eV, and photons with the wavelength of less than 387.5nm can be absorbed. When the nanomaterial absorbs photons within a suitable wavelength range, valence band electrons transition to the conduction band, forming photo-generated electron-hole pairs. The photo-generated electrons and holes respectively react with O in the environment2Molecule and H2Reaction of O molecules to form O2 ·-Free radical and OH·-A free radical. These radicals have strong oxidizing properties, are effective in reacting with various gaseous pollutants, and ultimately produce harmless products. Furthermore, the porous adsorption material can adsorb gaseous pollutants into the pore channel, and finally, adsorption-desorption dynamic balance is formed on the surface of the porous material, so that gaseous pollutant molecules can be effectively enriched near the photocatalytic digestion membrane, the contact probability of the pollutants and strong oxidizing free radicals is increased, and the photocatalytic performance of the coating is improved. More importantly, because the existing photocatalytic digestion membrane is easy to be worn by mechanical friction, the invention improves the adhesive property of titanium dioxide powder and a porous adsorption material by adding an inorganic adhesive, achieves the purpose of increasing the adhesive force of the photocatalytic digestion membrane on the common surface, and is not easy to be worn by mechanical friction, thereby prolonging the photocatalytic effect time.
Preferably, the preparation raw materials comprise the following components in percentage by mass:
0.5 to 5.0 percent of titanium dioxide powder, 0.5 to 4.0 percent of porous adsorption material, 0.5 to 5.0 percent of dispersant, 2.0 to 10.0 percent of inorganic adhesive and the balance of water.
In the raw materials, if porous adsorption material's content is too much, can cause to clear up the membrane thickly, influence titanium dioxide to the absorption efficiency of ultraviolet band light in the sunshine, gaseous pollutant can't in time obtain purifying after being adsorbed simultaneously, when environmental factor such as temperature changes, adsorbed pollutant is released in the pore, easily causes secondary pollution. Too low a content of the porous adsorption material may reduce the degradation rate of the digestion membrane on the gas pollutants. And when the content of the inorganic binder is higher: 1. the inorganic adhesive can fill the micropore or mesoporous structure of the porous adsorption material to block the adsorption process of gaseous pollutants; 2. after excessive inorganic adhesive is cured, cladding can be formed on the surface of titanium dioxide particles, so that the contact area between the surface of the titanium dioxide and gaseous pollutants is reduced; 3. a thick silicate layer is formed on the construction surface, which affects the functionality. Too little inorganic binder affects the surface adhesion of the digestion film, making it more susceptible to mechanical abrasion and wear. According to the invention, by further regulating and controlling the percentage of each component in the raw materials, the obtained titanium dioxide photocatalysis stock solution has the best photocatalysis performance, the sprayed digestion film has the best wear resistance, and the influence on the functionality of a construction surface is minimum.
Preferably, the titanium dioxide powder is a mixture of rutile titanium dioxide and anatase titanium dioxide. Titanium dioxide exists in nature in three crystal structures: the rutile type, the anatase type and the brookite type are proved by a great deal of experiments of the inventor that the photocatalysis performance can be optimal when the rutile type titanium dioxide and the anatase type titanium dioxide are mixed to form a crystal form.
Preferably, in the titanium dioxide powder, the mass percentage of anatase titanium dioxide is 70% to 90%. Through a large number of experiments of the inventor, the anatase titanium dioxide can be enabled to have the best photocatalytic performance when the mass percent of the anatase titanium dioxide is 70-90%.
Preferably, the particle size of the titanium dioxide powder is 20 to 50 nm.
Preferably, the porous adsorption material is a material with micropores or mesopores, and the material is one or a mixture of more of silicate materials, aluminosilicate materials, porous carbon materials and metal-organic framework materials. Silicate-based materials such as diatomaceous earth, zeolites, molecular sieves, and the like, aluminosilicate-based materials such as kaolin, bentonite, montmorillonite, and the like, metal-organic framework (MOF) or Covalent Organic Framework (COF) materials such as MOF-5, HKUST-1, MIL-100, and the like.
Preferably, the fineness of the porous adsorption material is more than 300 meshes.
Preferably, the dispersing agent is one or a mixture of sodium dodecyl sulfate, hydroxyalkyl cellulose containing alkyl of 1-5 carbon atoms and sodium alginate.
Preferably, the inorganic binder is one or a mixture of two of solid sodium silicate and liquid sodium silicate. After the photocatalytic stock solution is used for surface construction, sodium silicate contained in the photocatalytic stock solution can absorb CO widely existing in the air2、SO2Etc. acid gas or Ca existing in nature2+、Mg2+The plasma is combined and solidified, and finally the porous silicate structure with the bonding effect is formed through dehydration, so that the titanium dioxide nano particles are firmly attached to the construction surface, and the purpose of enhancing the adhesive force of the titanium dioxide nano particles on the surface is achieved. Sodium silicate and sodium silicate are solid or liquid industrial products prepared by firing silicon dioxide and soda ash at high temperature, and are widely applied to multiple industrial fields such as papermaking, building, textile and the like. The chemical composition of natron can be expressed as Na2O·mSiO2·nH2O, where m (modulus) is the difference between natron and the strict chemical sodium silicate (i.e. sodium metasilicate nonahydrate, Na)2SiO3·9H2O, CAS number 13517-24-3). The national standard of the people's republic of China (GB/T4209-. The sodium silicate has faster curing speed and stronger adhesive force compared with the strict chemical sodium silicate. On the other hand, the sodium silicate has good affinity and faster curing speed for most construction surface materials, such as cement roads, walls and the like, compared with other types of inorganic binders, such as calcium hydroxide, and the sodium silicate can be used for quickly and firmly bonding each solid component in the titanium dioxide photocatalysis stock solution to the construction surface by using a smaller amount of sodium silicate. Use of sodium silicate as a binder for increasing digestionThe wear resistance of the film can prolong the service time and can also minimize the functional influence on the construction surface.
In another aspect of the present invention, there is provided a method for preparing the above-mentioned titanium dioxide photocatalytic stock solution, comprising the steps of:
and mixing the preparation raw materials of the titanium dioxide photocatalytic stock solution to obtain the titanium dioxide photocatalytic stock solution.
The invention further provides a titanium dioxide photocatalytic digestion membrane prepared from the titanium dioxide photocatalytic stock solution.
In another aspect, the invention provides a method for preparing the titanium dioxide photocatalytic digestion membrane, which comprises the following steps:
and coating the titanium dioxide photocatalytic stock solution on the surface, and then drying to obtain the titanium dioxide photocatalytic digestion film.
Compared with the prior art, the invention has the following beneficial effects:
1. the titanium dioxide photocatalysis stock solution of the invention has the photocatalysis function of titanium dioxide powder, and the photocatalysis principle is as follows: the band gap of the titanium dioxide nano material is 3.2eV, and the titanium dioxide nano material can absorb photon energy with the wavelength of less than 387.5 nm. When the nanomaterial absorbs photon energy in a proper wavelength range, valence band electrons jump to a conduction band to form photo-generated electron-hole pairs. The photo-generated electrons and holes respectively react with O in the environment2Molecule and H2Reaction of O molecules to form O2 ·-Free radical and OH·-A free radical. These radicals have strong oxidizing properties, are effective in reacting with various gaseous pollutants, and ultimately produce harmless products. Furthermore, the porous adsorption material can adsorb gaseous pollutants into the pore channel, and finally, adsorption-desorption dynamic balance is formed on the surface of the porous material, so that gaseous pollutant molecules can be effectively enriched near the photocatalytic digestion membrane, the contact probability of the pollutants and strong oxidizing free radicals is increased, and the photocatalytic performance of the coating is improved. More importantly, because the existing photocatalytic digestion membrane is easy to be lost due to mechanical friction, the invention adds the inorganic binder to ensure that the dioxygen is easily lostThe bonding performance of the titanium powder and the porous adsorption material is improved, the aim of increasing the adhesive force of the photocatalytic digestion film on the common surface is fulfilled, the photocatalytic digestion film is not easy to suffer from mechanical friction loss, and the photocatalytic effect time is prolonged.
2. In the raw materials, if porous adsorption material content is too much, can cause to clear up the membrane thickly, influence titanium dioxide to the absorption efficiency of ultraviolet wave band light in the sunshine, gaseous pollutant can't in time obtain purifying after being adsorbed simultaneously. When environmental factors such as temperature change, pollutants adsorbed in the pore channels are released, and secondary pollution is easily caused. Too low a content of the porous adsorption material may reduce the degradation rate of the digestion membrane on the gas pollutants. At higher inorganic binder contents: 1. the inorganic adhesive can fill the micropore or mesoporous structure of the porous adsorption material to block the adsorption process of gaseous pollutants; 2. after excessive inorganic adhesive is cured, cladding can be formed on the surface of titanium dioxide particles, so that the contact area between the surface of the titanium dioxide and gaseous pollutants is reduced; 3. a thick silicate layer is formed on the construction surface, which affects the functionality. Too little inorganic binder affects the surface adhesion of the digestion film, making it more susceptible to mechanical abrasion and wear. According to the invention, by further regulating and controlling the percentage of each component in the raw materials, the obtained titanium dioxide photocatalysis stock solution has the best photocatalysis performance, the sprayed digestion film has the best wear resistance, and the influence on the functionality of a construction surface is minimum.
3. The titanium dioxide photocatalysis stock solution uses sodium silicate as an inorganic adhesive, and after the photocatalysis stock solution is used for surface construction, the sodium silicate contained in the titanium dioxide photocatalysis stock solution can absorb CO widely existing in the air2、SO2And various acidic gases or Ca existing in nature2+、Mg2+The plasma is combined and solidified, and finally the porous silicate structure with the bonding effect is formed through dehydration, so that the titanium dioxide nano particles are firmly attached to the construction surface, and the purpose of enhancing the adhesive force of the titanium dioxide nano particles on the surface is achieved. The sodium silicate has good affinity and faster setting for most construction surface materials, such as cement roads, walls, etc., than other types of inorganic binders, such as calcium hydroxideThe conversion speed is high, and the solid components in the titanium dioxide photocatalysis stock solution can be quickly and firmly bonded on the construction surface by using a small amount of sodium silicate. The sodium silicate is used as a binder, so that the wear resistance of the digestion film is increased, the service time is prolonged, and the functional influence on the construction surface is minimized.
4. The titanium dioxide photocatalysis stock solution has the advantages of low cost and simple production process, and the formed nano digestion membrane has strong adhesive force on various surfaces, long catalysis time and wide application prospect.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following examples, the sources of the raw materials are:
p25 titanium dioxide powder was purchased from the Woodson Industries group (Evonik Industries AG) in Germany; rutile titanium dioxide powder was purchased from Longbai group, Inc.; anatase titanium dioxide powder was obtained from Yumen's Silene titanium dioxide manufacturing Co., Ltd;
the solid sodium silicate is purchased from Tianjin neutralization Shengtai chemical Co., Ltd, and the modulus is 2.85;
Example 1
The titanium dioxide photocatalytic stock solution described in this embodiment is prepared from the following raw materials by mass:
2.0 percent of titanium dioxide powder, 13X2.0 percent of porous adsorption material molecular sieve, 2.0 percent of dispersant sodium dodecyl sulfate, 4.0 percent of inorganic adhesive solid sodium silicate and the balance of water.
Wherein the titanium dioxide powder is composed of anatase type titanium dioxide powder and rutile type titanium dioxide powder, and the effective mass content of anatase type is 75%; the primary particle size range is 25-50 nm; the fineness of the molecular sieve 13X is more than 300 meshes.
The preparation method of the titanium dioxide photocatalytic stock solution comprises the following steps:
step one, slowly adding selected titanium dioxide powder and selected molecular sieve 13X powder into pure water for multiple times, and continuously stirring by using a mechanical stirrer to finally obtain a suspension 1;
dissolving the dispersant solid in a small amount of pure water, slowly adding the dispersant solid into the suspension 1 obtained in the step one after the dispersant solid is completely dissolved, and keeping stirring to obtain a suspension 2;
step three, adding the inorganic adhesive into the suspension 2 obtained in the step two, and continuously stirring to obtain a suspension 3;
and step four, homogenizing the suspension 3 in the step three for 20min by using a shear type homogenizer at a rotating speed of 2000r/min to finally obtain white slurry which is a finished product of the titanium dioxide photocatalytic stock solution.
Example 2
The titanium dioxide photocatalytic stock solution described in this embodiment is prepared from the following raw materials by mass:
2.0 percent of titanium dioxide powder, 4.0 percent of porous adsorption material active carbon powder and dispersing agent
4.0 percent of inorganic adhesive liquid sodium silicate and the balance of water.
Wherein the titanium dioxide powder is commercially available P25 titanium dioxide powder, the effective mass content of anatase is 79%, the content of rutile titanium dioxide is 21%, and the particle size is 20-50 nm; the fineness of the activated carbon powder is more than 300 meshes.
The preparation method of the titanium dioxide photocatalytic stock solution comprises the following steps:
step one, slowly adding the selected titanium dioxide powder and the selected activated carbon powder into pure water for multiple times, and continuously and uniformly stirring by using a mechanical stirrer to finally obtain a suspension;
step two, adding the dispersant solid into the suspension liquid obtained in the step one, and keeping stirring until the suspension liquid is uniform;
homogenizing the suspension by a homogenizer to obtain uniform grey white slurry as a semi-finished product;
and step four, adding an inorganic adhesive into the semi-finished product obtained in the step three, and mechanically stirring and uniformly mixing to obtain off-white slurry, namely a finished product of the titanium dioxide photocatalysis stock solution.
Example 3
The titanium dioxide photocatalytic stock solution described in this embodiment is prepared from the following raw materials by mass:
0.5 percent of titanium dioxide powder, 13X1.0 percent of porous adsorption material molecular sieve, 3.0 percent of dispersant sodium dodecyl sulfate, 6.0 percent of inorganic adhesive solid sodium silicate and the balance of water.
Wherein the titanium dioxide powder is composed of anatase type titanium dioxide powder and rutile type titanium dioxide powder, the effective mass content of anatase type is 75%, and the primary particle size range is 25-50 nm; the fineness of the molecular sieve 13X is more than 300 meshes.
The preparation method of the titanium dioxide photocatalytic stock solution of the present example is the same as that of example 1.
Example 4
The titanium dioxide photocatalytic stock solution described in this embodiment is prepared from the following raw materials by mass:
5.0 percent of titanium dioxide powder, 13X0.5 percent of porous adsorption material molecular sieve, 0.5 percent of dispersant sodium dodecyl sulfate, 10.0 percent of inorganic adhesive solid sodium silicate and the balance of water.
Wherein the titanium dioxide powder is commercially available P25 titanium dioxide powder, the effective mass content of anatase is 79%, the content of rutile titanium dioxide is 21%, and the particle size is 20-50 nm; the fineness of the molecular sieve 13X is more than 300 meshes.
The preparation method of the titanium dioxide photocatalytic stock solution of the present example is the same as that of example 1.
Example 5
The titanium dioxide photocatalytic stock solution described in this embodiment is prepared from the following raw materials by mass:
3.0 percent of titanium dioxide powder, 13X1.0 percent of porous adsorption material molecular sieve, 5.0 percent of dispersant sodium dodecyl sulfate, 2.0 percent of inorganic adhesive solid sodium silicate and the balance of water.
Wherein the titanium dioxide powder is commercially available P25 titanium dioxide powder, the effective mass content of anatase is 79%, the content of rutile titanium dioxide is 21%, and the particle size is 20-50 nm; the fineness of the molecular sieve 13X is more than 300 meshes.
The preparation method of the titanium dioxide photocatalytic stock solution of the present example is the same as that of example 1.
Example 6
The titanium dioxide photocatalytic stock solution described in this embodiment is prepared from the following raw materials by mass:
10.0 percent of titanium dioxide powder, 13X3.0 percent of porous adsorption material molecular sieve, 10.0 percent of dispersant sodium dodecyl sulfate, 20.0 percent of inorganic adhesive solid sodium silicate and the balance of water.
Wherein the titanium dioxide powder is commercially available P25 titanium dioxide powder, the effective mass content of anatase is 79%, the content of rutile titanium dioxide is 21%, and the particle size is 20-50 nm; the fineness of the molecular sieve 13X is more than 300 meshes.
The preparation method of the titanium dioxide photocatalytic stock solution of the present example is the same as that of example 1.
Example 7
The titanium dioxide photocatalytic stock solution described in this embodiment is prepared from the following raw materials by mass:
0.1% of titanium dioxide powder, 13X 5.0% of porous adsorption material molecular sieve, 0.1% of dispersant sodium dodecyl sulfate, 1.0% of inorganic adhesive solid sodium silicate and the balance of water.
Wherein the titanium dioxide powder is commercially available P25 titanium dioxide powder, the effective mass content of anatase is 79%, the content of rutile titanium dioxide is 21%, and the particle size is 20-50 nm; the fineness of the molecular sieve 13X is more than 300 meshes.
The preparation method of the titanium dioxide photocatalytic stock solution of the present example is the same as that of example 1.
Example 8
The titanium dioxide photocatalytic stock solution described in this embodiment is prepared from the following raw materials by mass:
2.0 percent of titanium dioxide powder, 13X2.0 percent of porous adsorption material molecular sieve, 2.0 percent of dispersant sodium dodecyl sulfate, 4.0 percent of inorganic adhesive powdery calcium hydroxide and the balance of water.
Wherein the titanium dioxide powder is composed of anatase type titanium dioxide powder and rutile type titanium dioxide powder, the effective mass content of anatase type is more than 75%, and the primary particle size range is 25-50 nm; the fineness of the molecular sieve 13X is more than 300 meshes.
The preparation method of the titanium dioxide photocatalytic stock solution of the present example is the same as that of example 1.
Comparative example 1
The titanium dioxide photocatalytic stock solution of the comparative example is prepared from the following raw materials in percentage by mass:
2.0 percent of titanium dioxide powder, 13X2.0 percent of porous adsorption material molecular sieve, 2.0 percent of dispersant sodium dodecyl sulfate and the balance of water.
Wherein the titanium dioxide powder is commercially available P25 titanium dioxide powder, the effective mass content of anatase is 79%, the content of rutile titanium dioxide is 21%, and the particle size is 20-50 nm; the fineness of the molecular sieve 13X is more than 300 meshes.
The preparation method of the titanium dioxide photocatalytic stock solution comprises the following steps:
step one, slowly adding the selected titanium dioxide powder and the selected activated carbon powder into pure water for multiple times, and continuously and uniformly stirring by using a mechanical stirrer to finally obtain a suspension;
step two, adding the dispersant solid into the suspension liquid obtained in the step one, and keeping stirring until the suspension liquid is uniform;
and step three, homogenizing the turbid liquid by a homogenizer to obtain uniform grey slurry serving as a comparison sample.
Titanium dioxide photocatalytic digestion membrane performance test
The photocatalytic solutions obtained in the above examples and comparative examples were sprayed to a surface area of 5X 10cm using a spray gun2The test sample piece is made on the surface of the cement piece. The spraying conditions are as follows: air pressure of 2.5-3.0Mpa, spraying distance of 20-30cm, perpendicular to the surface of the cement sheet, and repeatedly spraying for 3 times.
And (3) carrying out photocatalytic performance test on the test sample piece obtained in each embodiment, specifically: and after the photocatalytic stock solution is dried for 48 hours, using acetaldehyde gas as a detected standard substance, and evaluating the photocatalytic performance of the test sample piece by using a gas chromatography. The test conditions were: zero-order air is used as carrier gas, the concentration of acetaldehyde is 1.67ppm, the humidity of the gas is 50 percent, the flow rate of the gas is 300mL/min, and the illumination intensity of ultraviolet light is 1mW/cm2。
The test sample piece obtained in each example was subjected to a continuous erosion wear test, specifically: the sample pieces were subjected to a continuous scour abrasion test using water droplets at a flow rate of 1 drop/s. And during washing, the sample slice forms an included angle of 60 degrees with the horizontal plane, and after continuous washing for 48 hours, the sample slice is naturally dried. The photocatalytic performance of the sample pieces was again tested using the conditions described above.
The friction test of the test sample piece obtained in each example is specifically as follows: and (3) carrying out friction test on the sample sheet by using a hard rubber ball, and continuously and repeatedly rubbing one side of the sample sheet sprayed with the titanium dioxide photocatalysis stock solution for 10000 times by using a 20kg balance weight. The photocatalytic performance of the sample pieces was again tested using the conditions described above.
The experimental results are shown in table 1 below. The amount of membrane shedding was resolved in the following data: slight shedding < significant shedding < massive shedding. As can be seen from the data in Table 1, compared with the data in the embodiment 1, the inorganic binder is not added in the comparative example 1, the initial photocatalytic performances of the comparative example 1 and the inorganic binder are close to each other, but after a scouring wear experiment and a counterweight wear experiment, the digestion film in the comparative example 1 falls off greatly, the acetaldehyde degradation rate is obviously reduced, while the digestion film in the embodiment 1 only slightly falls off in the counterweight wear experiment, and the acetaldehyde degradation rate is slightly reduced, so that the titanium dioxide photocatalytic stock solution disclosed by the invention enables the photocatalytic digestion film not to be easily subjected to mechanical friction wear by adding the inorganic binder, the photocatalytic effect time is prolonged, and the functionality of a construction surface is not influenced. Further, the specific selection of the inorganic binder can make the wear resistance of the digestion membrane have obvious difference, the rest components of the photocatalytic stock solutions in the embodiment 1 and the embodiment 8 are the same, only the inorganic binder is different in type, and the initial photocatalytic performances of the inorganic binder and the photocatalytic stock solutions are close to each other, but after the scouring wear experiment and the counterweight wear experiment, the digestion membrane in the embodiment 8 obviously falls off, the acetaldehyde degradation rate is obviously reduced, and the fact that the inorganic binder adopts the sodium silicate shows that the wear resistance of the digestion membrane is better. Further, because the components in the titanium dioxide photocatalytic stock solution have interaction, the percentage content of each component also has a significant influence on the performance of the digestion membrane, wherein examples 1 to 5 are in an optimal percentage content range, and the obtained digestion membrane has better photocatalytic performance and wear resistance; further, examples 1 and 2 are the most preferable examples, and have the best photocatalytic performance and abrasion resistance.
TABLE 1
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. The titanium dioxide photocatalysis stock solution is characterized by comprising the following preparation raw materials in percentage by mass:
0.1 to 10.0 percent of titanium dioxide powder, 0.1 to 6.0 percent of porous adsorption material, 0.1 to 10.0 percent of dispersant, 1.0 to 20.0 percent of inorganic adhesive and the balance of water.
2. The titanium dioxide photocatalysis stock solution as claimed in claim 1, which is prepared from the following raw materials in percentage by mass:
0.5 to 5.0 percent of titanium dioxide powder, 0.5 to 4.0 percent of porous adsorption material, 0.5 to 5.0 percent of dispersant, 2.0 to 10.0 percent of inorganic adhesive and the balance of water.
3. The titanium dioxide photocatalytic stock solution according to claim 1, characterized in that:
the titanium dioxide powder is a mixture of rutile titanium dioxide and anatase titanium dioxide, and the mass percent of the anatase titanium dioxide is 70-90%.
4. The titanium dioxide photocatalytic stock solution according to claim 1, characterized in that:
the particle size of the titanium dioxide powder is 20-50 nm.
5. The titanium dioxide photocatalytic stock solution according to claim 1, characterized in that:
the porous adsorption material is a material with micropores or mesopores, and the material is one or a mixture of more of silicate materials, aluminosilicate materials, porous carbon materials and metal-organic framework materials.
6. The titanium dioxide photocatalytic stock solution according to claim 1, characterized in that:
the dispersing agent is one or a mixture of sodium dodecyl sulfate, hydroxyalkyl cellulose containing alkyl of 1-5 carbon atoms and sodium alginate.
7. The titanium dioxide photocatalytic stock solution according to claim 1, characterized in that:
the inorganic adhesive is one or the mixture of solid sodium silicate and liquid sodium silicate.
8. A method for preparing a photocatalytic stock solution of titanium dioxide according to any one of claims 1 to 7, comprising the steps of:
and mixing the preparation raw materials of the titanium dioxide photocatalytic stock solution to obtain the titanium dioxide photocatalytic stock solution.
9. A titanium dioxide photocatalytic digestion film, which is prepared by using the titanium dioxide photocatalytic stock solution according to any one of claims 1 to 7.
10. A method of making the titanium dioxide photocatalytic digestion membrane according to claim 9, characterized by the steps of:
and coating the titanium dioxide photocatalytic stock solution on the surface, and then drying to obtain the titanium dioxide photocatalytic digestion film.
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