CN106607015A - Nano titanium dioxide photocatalyst with double-particle size distribution and preparation method thereof - Google Patents
Nano titanium dioxide photocatalyst with double-particle size distribution and preparation method thereof Download PDFInfo
- Publication number
- CN106607015A CN106607015A CN201611117008.1A CN201611117008A CN106607015A CN 106607015 A CN106607015 A CN 106607015A CN 201611117008 A CN201611117008 A CN 201611117008A CN 106607015 A CN106607015 A CN 106607015A
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- CN
- China
- Prior art keywords
- titanium dioxide
- nano titanium
- dioxide photocatalyst
- photocatalyst
- double
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- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 41
- 239000002245 particle Substances 0.000 title claims abstract description 38
- 238000009826 distribution Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 16
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 15
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 15
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 15
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 31
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 7
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 5
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 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 2
- 239000004743 Polypropylene Substances 0.000 claims 1
- 238000000889 atomisation Methods 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- -1 polypropylene Polymers 0.000 claims 1
- 229920001155 polypropylene Polymers 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 21
- 238000003756 stirring Methods 0.000 abstract description 21
- 230000000694 effects Effects 0.000 abstract description 18
- 230000015556 catabolic process Effects 0.000 abstract description 13
- 239000000084 colloidal system Substances 0.000 abstract description 13
- 238000006731 degradation reaction Methods 0.000 abstract description 13
- 239000002270 dispersing agent Substances 0.000 abstract description 9
- 239000007921 spray Substances 0.000 abstract description 7
- 239000004094 surface-active agent Substances 0.000 abstract description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract 1
- 238000001694 spray drying Methods 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 description 18
- 230000001699 photocatalysis Effects 0.000 description 10
- 238000005507 spraying Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 230000007613 environmental effect Effects 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 6
- 229940012189 methyl orange Drugs 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 235000013339 cereals Nutrition 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 210000000476 body water Anatomy 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- JHJUUEHSAZXEEO-UHFFFAOYSA-M sodium;4-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 JHJUUEHSAZXEEO-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- 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
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention provides a nano titanium dioxide photocatalyst with double-particle size distribution and a preparation method thereof. The method includes: dissolving an organic titanate in an alcohol solution, adding an aqueous solution of polyacrylic acid and polyvinylpyrrolidone dropwise under stirring to prepare a transparent titanium dioxide sol; then adding a commodity nano titanium dioxide powder and carrying out ultrasonic stirring to obtain titanium dioxide colloids from transparent to translucent; and finally conducting spray drying, thus obtaining the nano titanium dioxide photocatalyst with double-particle size distribution. The titanium dioxide photocatalyst prepared by the method provided by the invention has no need for adding any surfactant or dispersant during use, by water adding and stirring, a high-stability nano titanium dioxide photocatalyst spray solution can be prepared, and can be placed stably for more than 6 months. The catalyst provided by the invention has high activity on photocatalytic degradation of organic matters under sunlight, and the degradation rate is 40% higher than that the existing commodity nano titanium dioxide P25.
Description
Technical field
The present invention relates to nano titanium dioxide photocatalyst of a kind of pair of particle diameter distribution and preparation method thereof, the photocatalyst
The nano titanium oxide spray coating liquor of stable dispersion directly can be configured in the application with water, and stably can be preserved more than 6 months,
The photocatalytic activity of nano titanium oxide more existing than existing market is high simultaneously.Photocatalyst prepared by the method is in environmental improvement
It is middle to promote expected by the economic benefit for having produced and environmental benefit, belong to environmentally conscious materials field.
Background technology
So-called photocatalyst, is exactly the irradiation through light, can promote the material of chemical reaction.As photocatalyst can be with
Process air in or water in extremely low concentration harmful chemical, harmful organic substance can be completely decomposed into water and carbon dioxide,
And itself will not decompose release harmful substance, therefore it is extremely excellent surrounding purifying material.With the development of modern economy, environment
Also more and more higher is required, photocatalyst is received more and more attention, in smelly eliminating, sterilization, antibacterial, antifouling and removing harmful substance
Etc. the application prospect that shows of aspect.At present, the material that can be used as photocatalyst has many kinds, wherein nanometer titanium dioxide
Titanium, due to stable in properties, nontoxic, and efficient photocatalytic activity, is photocatalyst the most frequently used at present, and existing market
On the photocatalyst that commonly gets the nod.
The nano titanium dioxide photocatalyst sold in the market mainly has two types, a kind of pressed powder, performance
The Nano titanium dioxide P25 that most preferably goldschmidt chemical corporation of common accreditation is produced on market, another is nano-silica
Change titanium dispersion liquid.For nano titanium oxide pressed powder product, to be disperseed in the application, and it is a crucial skill to disperse
Art, and be most difficult at present, various dispersants will be added, and applicable dispersion be obtained using various dispersing apparatus, typically
User, the technical formula and special equipment for not having specialty are extremely difficult to stable dispersion liquid, so domestic consumer is rarely employed,
Sell after the environmental protection company dispersion for being all specialty, but long-time stability still do not solved (can be layered within 1 month) after disperseing at present,
Can not keep for a long time and transport.For nano titanium oxide dispersion product, except above-mentioned employing nanoscale titanium dioxide
Outside the dispersion liquid that titanium is processed into, also one kind is Nano titanium dioxide colloidal sol, and its stability can be solved, but concentration is low (big
It is many below 1%), content has substantial amounts of organic solvent, and cost of transportation is high, it is often more important that due to colloidal sol crystallinity it is poor, without
Overheating Treatment is directly using the photocatalysis performance of the product than relatively low.
In order to solve these problems, both at home and abroad in terms of nano titanium oxide dispersant and Nano titanium dioxide colloidal sol all
Exploitation is conducted extensive research, the Chinese patent containing titanium dioxide in title there are 508 disclosed in 2014,2015
579 are reached disclosed in year.As Chinese invention patent (publication number CN200310112124.0) discloses a kind of nanometer titanium dioxide
The process for dispersing of titanium valve body, it is characterised in that nano-titanium dioxide powder is dissolved in and with the addition of the molten of surfactant and dispersant
In agent, surfactant is cationic cellulose, sodium hexameta phosphate, dodecylbenzene sodium sulfonate, isobutyl group sodium sulfonate or double hard
Ester acid PVOH ether；Dispersant is Disperbyk-034, Disperbyk-190, Disperbyk-183, ROHM AND HAAS 890, sieve
Door Haas 1124, ROHM AND HAAS 1288, ROHM AND HAAS 731A, NC890 and LOPON895；This be by solvent, surfactant and
The dispersion that dispersant is constituted.It is adapted to carry out dispersion use to nano-titanium dioxide powder material, its formula is all compared with technique
It is more complicated.For example, Chinese invention patent (publication number CN201510974495.2) discloses a kind of inorganic water white transparency nanometer two
The preparation method of titania photocatalyst, using titanium tetrachloride by low temperature hydrolysis, with prepared slurry in low temperature ammonia, then passes through
High speed centrifuge carries out solid-liquid separation, and deionized water repeated washing, centrifugation；It is molten by hydrogen peroxide low-temperature oxidation
Solution, (170-190 DEG C) of high temperature circulate complexation, water white transparency nanometer titanium dioxide are obtained using high intensity (254nm) ultraviolet catalytic
Titanium photocatalyst (colloidal sol), the catalyst energy catalytic degradation Organic substance, purifies the air of a room, and improves IAQ (indoor air quality).The party
Method prepares complexity, and product remains the colloidal sol of low concentration.Chinese invention patent (publication number CN201510036659.7) is also disclosed
A kind of preparation method of monodisperse nano-titanium dioxide colloidal sol, using titanium tetrachloride and butyl titanate simultaneously as titanium source, with four
The hydrochloric acid that titanium chloride hydrolysis is obtained is used as catalyst, and the product that hydrolysis is obtained is anti-as nucleus induction butyl titanate hydrolysis
Should, solid content is obtained by the time of the ratio for controlling titanium tetrachloride, butyl titanate and deionized water, stirring and heating adjustable
Stable titanium colloidal sol.The method product remains the colloidal sol of low concentration, does not prepare redispersible pressed powder.
It is an object of the invention to adopt condition relatively mild, the industrial method easily realized is prepared a kind of easily steady
Fixed scattered nano titanium dioxide photocatalyst, the nano titanium oxide is a kind of pressed powder with collosol property, is being answered
The nano titanium oxide spray coating liquor of stable dispersion directly can be configured with water, and stably can be preserved more than 6 months；Simultaneously
Under sunlight, the activity of its photocatalytic activity nano titanium oxide P25 more best than existing market increases, based on this,
We design the nano titanium oxide of a kind of pair of particle diameter distribution, expand absorption of the titanium dioxide to solar spectrum, strengthen activity, full
The requirement of sufficient field of environmental improvement application.Up till now for this purpose, not reporting that this high activity with collosol property is received both at home and abroad
Rice titanium dioxide solids powder.
The photocatalyst of the invention, with storage than colloidal sol conveniently, low cost, no solvent, long shelf-life are safe for its transport
Property is good；The not only nano titanium dioxide photocatalyst of the related all commercially available invention of company but also domestic consumer of environmental area,
Convenient configuration is used, and the catalyst is promoted the use of expected by the economic benefit for having produced and environmental benefit in environmental area.
The content of the invention
It is an object of the invention to adopt condition relatively mild, the industrial method easily realized is prepared a kind of easily steady
Fixed dispersion and activity are got back the nano titanium dioxide photocatalyst of raising, and the nano titanium oxide in the application can be straight
The nano titanium oxide spray coating liquor that stable dispersion is configured with water is connect, and stably can be preserved more than 6 months, while comparing existing market
The activity of existing nano titanium oxide is high, meets the requirement of field of environmental improvement application.
Nano titanium dioxide photocatalyst of double particle diameter distributions of the present invention and preparation method thereof, it is characterised in that include
Following steps：
(1) organic titanate of certain mass is dissolved in alcoholic solution, unlatching is stirred and is added dropwise over a certain amount of poly-
The aqueous solution of acrylic acid and polyvinylpyrrolidone, be hydrolyzed at 30～60 DEG C 2～6h of reaction, obtains transparent titanium dioxide
Titanium colloidal sol；
(2) given commodity nano titanium dioxide powder is added to into (1) described colloidal sol, 0.5～3h of ultrasonic agitation is obtained
To transparent to translucent colloidal tio 2；
(3) complex that (2) obtain is spray-dried, the nano titanium dioxide photocatalyst of double particle diameter distributions is obtained
Powder.
In the step (1), it is characterised in that organic titanate：Alcohol：Polyacrylic acid：Polyvinylpyrrolidone：The matter of water
Measuring ratio is：100：100～800：1～10：0.1～5：100～1000.Wherein, organic titanate is butyl titanate or titanium
Sour four isopropyl esters；Alcohol is ethanol, propanol, ethylene glycol.
In the step (2), it is characterised in that commodity nano titanium oxide addition with the mass ratio of organic titanate is
10～100：100；Preferred commodity nano titanium oxide is market flow-through P25 titanium dioxide.
In the step (3), it is characterised in that be dried using conventional pressure spray dryer device, pressure 1-10Mpa, heat
Air is dried medium, temperature 150-250 DEG C.
Compared with prior art, the present invention has the advantage that and effect：
1st, preparation condition of the present invention is relatively mild, industrial easily to realize, its preparation method have obvious novelty with
Advance, shows in terms of three, and one is in prepared by colloidal sol to substitute general mineral acid (hydrochloric acid, nitric acid) using polyacrylic acid,
Not only prevent corrosivity and the hazardness of subsequent product, at the same polyacrylic acid coordinate together with polyvinylpyrrolidone can conduct
Good stable dispersant；Two is the addition commodity nano titanium oxide in colloidal sol, can induce the crystallization of colloidal sol, increases in colloidal sol
The concentration of nano titanium oxide, while further with the stable dispersant cladding commodity nano titanium oxide in colloidal sol；Three are
To colloid using being spray-dried, it is to avoid reunion of the general heat treatment to material, the method not only be easy to reclaim by solvent, Er Qiebao
Dispersion and the cladding of nano titanium oxide in colloid have been demonstrate,proved, and guarantee have been provided for the follow-up application of dispersion again.
2nd, titanium dioxide optical catalyst prepared by the present invention has special application advantage, no longer needs addition in use
Any surfactant and dispersant, add water and the nano titanium dioxide photocatalyst spray coating liquor of high stable are prepared by stirring, and two
The mass concentration of titanium oxide can regulate and control in 0.1～5% scope, and stably can place more than 6 months with good stability.
3rd, the application effect that titanium dioxide optical catalyst prepared by the present invention has had, due to mean diameter 5-10nm
With double particle diameter distributions of 25-30nm, such as Fig. 1-5, the Photocatalytic activity improved under sunlight to Organic substance that can be maximum, its
Degradation rate improves more than 40% than existing goods P25 nano titanium oxides.
Description of the drawings
Fig. 1 is the high resolution scanning of the nano titanium dioxide photocatalyst of double particle diameter distributions prepared by present example 1
Electromicroscopic photograph (SEM) figure.As illustrated, small particle average out to 6nm, big particle diameter average out to 25nm.
Fig. 2 is the high resolution scanning of the nano titanium dioxide photocatalyst of double particle diameter distributions prepared by present example 2
Electromicroscopic photograph (SEM) figure.As illustrated, small particle average out to 8nm, big particle diameter average out to 28nm.
Fig. 3 is the particle statistic result of the nano titanium dioxide photocatalyst of double particle diameter distributions prepared by present example 4
Figure, little particle mean diameter are 10nm, and bulky grain mean diameter is 30nm.
Fig. 4 is the particle statistic result of the nano titanium dioxide photocatalyst of double particle diameter distributions prepared by present example 5
Figure, little particle mean diameter are 5nm, and bulky grain mean diameter is 25nm.
Specific embodiment
Invention is described in further detail below by way of specific embodiment, but the invention is not restricted to following examples.
Embodiment 1
Add 100g butyl titanates, 100g ethanol to stir in the reactor, control temperature 50 C, low whipping speed
Under the conditions of 500-1000 rev/min, 1g polyacrylic acid, 1g polyvinylpyrrolidones, the mixed solution of 500g water, body are slowly added into
Four ester of metatitanic acid in system：Ethanol：Polyacrylic acid：Polyvinylpyrrolidone：Mass ratio=100 of water：100：1：1：500；Constant temperature is stirred
Vitreosol is formed after mixing reaction 3h, 30g commodity nano titanium oxide P25 are added, starts ultrasonic agitation, continue 1h, formed
Transparent colloid；The colloid for obtaining is obtained at pressure 1MPa, 250 DEG C of hot-air using conventional pressure spray dryer device
The nano titanium dioxide photocatalyst of double particle diameter distributions, as shown in figure 1, small particle average out to 6nm, big particle diameter average out to 25nm.
Application effect：Catalyst obtained in 10g is taken, plus 990g pure water stirring 0.5h can be prepared by the 1% of stable dispersion
Nano titanium dioxide photocatalyst spray coating liquor, placement will not be layered for 8 months.The catalyst of preparation photocatalysis drop under sunlight
Organic methyl orange in Xie Shui, under the conditions of catalyst amount 1g/L, methyl orange concentration 20mg/L, reacts 3h, and degradation rate is
88.5%；The degradation rate of commodity nano titanium oxide P25 is 54.2% under the same conditions, and activity improves 63.3%.
Embodiment 2
Add 100g tetraisopropyl titanates, 400g propanol to stir in the reactor, control 30 DEG C of temperature, in stirring speed
Under the conditions of 500-1000 rev/min of degree, 10g polyacrylic acid is slowly added into, 0.1g polyvinylpyrrolidones, the mixing of 400g water are molten
Liquid, four ester of metatitanic acid in system：Ethanol：Polyacrylic acid：Polyvinylpyrrolidone：Mass ratio=100 of water：400：10：0.1：
400；Vitreosol is formed after constant temperature stirring reaction 5h, 10g commodity nano titanium oxide P25 are added, is started ultrasonic agitation, is held
Continuous 3h, forms transparent colloid；Pressure spray dryer device of the colloid for obtaining using routine, in pressure 5MPa, hot-air 200
The nano titanium dioxide photocatalyst of double particle diameter distributions is obtained at DEG C, as shown in Fig. 2 small particle average out to 8nm, big particle diameter is average
For 28nm.
Application effect：Catalyst obtained in 50g is taken, plus 950g pure water stirring 0.5h can be prepared by the 5% of stable dispersion
Nano titanium dioxide photocatalyst spray coating liquor, placement will not be layered for 6 months.The catalyst of preparation photocatalysis drop under sunlight
Solution air Organic substance formaldehyde, in catalyst amount 0.1g/M3, concentration of formaldehyde 10mg/M3Under the conditions of, 2h is reacted, degradation rate is
95.8%；The degradation rate of commodity nano titanium oxide P25 is 68.4% under the same conditions, and activity improves 40.1%.
Embodiment 3
Add 100g butyl titanates, 800g ethanol to stir in the reactor, control 40 DEG C of temperature, low whipping speed
Under the conditions of 500-1000 rev/min, 10g polyacrylic acid is slowly added into, 1g polyvinylpyrrolidones, the mixed solution of 100g water,
Four ester of metatitanic acid in system：Ethanol：Polyacrylic acid：Polyvinylpyrrolidone：Mass ratio=100 of water：800：10：1：100；Constant temperature
Vitreosol is formed after stirring reaction 2h, 50g commodity nano titanium oxide P25 are added, starts ultrasonic agitation, continue 1h, shape
Into translucent colloid；Pressure spray dryer device of the colloid for obtaining using routine, at pressure 10MPa, 150 DEG C of hot-air
The nano titanium dioxide photocatalyst of double particle diameter distributions is obtained.As a result similar to Fig. 1, small particle average out to 6nm, big particle diameter are average
For 26nm.
Application effect：Catalyst obtained in 1g is taken, plus 999g pure water stirring 0.5h can be prepared by the 0.1% of stable dispersion
Nano titanium dioxide photocatalyst spray coating liquor, placement will not be layered for 8 months.The catalyst of preparation photocatalysis drop under sunlight
Organic methyl orange in Xie Shui, under the conditions of catalyst amount 1g/L, methyl orange concentration 20mg/L, reacts 3h, and degradation rate is
95.6%；The degradation rate of commodity nano titanium oxide P25 is 54.2% under the same conditions, and activity improves 76.4%.
Embodiment 4
Add 100g butyl titanates, 300g ethanol to stir in the reactor, control temperature 60 C, low whipping speed
Under the conditions of 500-1000 rev/min, 5g polyacrylic acid is slowly added into, 5g polyvinylpyrrolidones, the mixed solution of 1000g water,
Four ester of metatitanic acid in system：Ethanol：Polyacrylic acid：Polyvinylpyrrolidone：Mass ratio=100 of water：300：5：5：1000；Constant temperature
Vitreosol is formed after stirring reaction 4h, 100g commodity nano titanium oxide P25 are added, starts ultrasonic agitation, continue 3h, shape
Into translucent colloid；Pressure spray dryer device of the colloid for obtaining using routine, at pressure 8MPa, 250 DEG C of hot-air
The nano titanium dioxide photocatalyst of double particle diameter distributions is obtained.As a result similar to Fig. 2, Fig. 3, small particle average out to are shown in statistical result
10nm, big particle diameter average out to 30nm.
Application effect：Catalyst obtained in 5g is taken, plus 995g pure water stirring 0.5h can be prepared by the 0.5% of stable dispersion
Nano titanium dioxide photocatalyst spray coating liquor, placement will not be layered for 6 months.The catalyst of preparation photocatalysis drop under sunlight
Solution air Organic substance formaldehyde, in catalyst amount 0.1g/M3, concentration of formaldehyde 10mg/M3Under the conditions of, 2h is reacted, degradation rate is
97.6%；The degradation rate of commodity nano titanium oxide P25 is 68.4% under the same conditions, and activity improves 42.7%.
Embodiment 5
Add 100g tetraisopropyl titanates, 100g ethylene glycol to stir in the reactor, control temperature 50 C, in stirring
Under the conditions of speed 500-1000 rev/min, 2g polyacrylic acid is slowly added into, 1g polyvinylpyrrolidones, the mixing of 800g water are molten
Liquid, four ester of metatitanic acid in system：Ethanol：Polyacrylic acid：Polyvinylpyrrolidone：Mass ratio=100 of water：100：2：1：800；It is permanent
Vitreosol is formed after warm stirring reaction 3h, 80g commodity nano titanium oxide P25 are added, starts ultrasonic agitation, continue 2h,
Form translucent colloid；Pressure spray dryer device of the colloid for obtaining using routine, in pressure 5MPa, 250 DEG C of hot-air
The lower nano titanium dioxide photocatalyst that double particle diameter distributions are obtained.As a result similar to Fig. 1, Fig. 4 is shown in statistical result, and little particle is average
Particle diameter is 5nm, and bulky grain mean diameter is 25nm.
Application effect：Catalyst obtained in 20g is taken, plus 980g pure water stirring 0.5h can be prepared by the 2% of stable dispersion
Nano titanium dioxide photocatalyst spray coating liquor, placement will not be layered for 6 months.The catalyst of preparation photocatalysis drop under sunlight
Organic methyl orange in Xie Shui, under the conditions of catalyst concn 1g/L, methyl orange concentration 20mg/L, reacts 3h, and degradation rate is
86.7%；The degradation rate of commodity nano titanium oxide P25 is 54.2% under the same conditions, and activity improves 60.0%.
Claims (4)
1. nano titanium dioxide photocatalyst of a kind of pair of particle diameter distribution and preparation method thereof, it is characterised in that including following step
Suddenly：
(1) organic titanate of certain mass is dissolved in alcoholic solution, unlatching is stirred and is slowly added into a certain amount of polypropylene
Acid and the aqueous solution of polyvinylpyrrolidone, be hydrolyzed at 30～60 DEG C 2～6h of reaction, obtains transparent titanium dioxide molten
Glue；
(2) given commodity nano titanium dioxide powder is added to into (1) described colloidal sol, 0.5～3h of ultrasonic agitation is obtained
It is bright to translucent colloidal tio 2；
(3) complex that (2) obtain is spray-dried, the nano titanium dioxide photocatalyst of double particle diameter distributions is obtained.
2. method according to claim 1, it is characterised in that in step (1), organic titanate：Alcohol：Polyacrylic acid：It is poly-
Vinylpyrrolidone：The mass ratio of water is：100：100～800：1～10：0.1～5：100～1000.Wherein, organic titanate
For butyl titanate or tetraisopropyl titanate；Alcohol is ethanol, propanol, ethylene glycol.
3. method according to claim 1, it is characterised in that in step (2), commodity nano titanium oxide addition with have
The mass ratio of machine titanate is 10～100：100；Preferred commodity nano titanium oxide is market plain edition P25 nanometer titanium dioxide
Titanium.
4. method according to claim 1, it is characterised in that in step (3), is spray-dried using conventional press atomization
Drying device, pressure 1-10Mpa；Hot-air is dried medium, temperature 150-250 DEG C.
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