CN103408068A - Method for preparing nanometer titanium dioxide through low temperature water steaming treatment - Google Patents
Method for preparing nanometer titanium dioxide through low temperature water steaming treatment Download PDFInfo
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- CN103408068A CN103408068A CN2013103009234A CN201310300923A CN103408068A CN 103408068 A CN103408068 A CN 103408068A CN 2013103009234 A CN2013103009234 A CN 2013103009234A CN 201310300923 A CN201310300923 A CN 201310300923A CN 103408068 A CN103408068 A CN 103408068A
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- 238000010025 steaming Methods 0.000 title abstract description 10
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 39
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- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 12
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- 230000007613 environmental effect Effects 0.000 claims description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 4
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- 239000010935 stainless steel Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 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 description 2
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Abstract
The present invention relates to a method for preparing nanometer titanium dioxide through a low temperature water steaming treatment. The method comprises: mixing a titanium source and a chelating agent, and completely and uniformly stirring to obtain a homogeneous yellow solution; completely and uniformly mixing deionized water and a catalyst, and adjusting the pH value of the solution to 2-3; under the state of a water bath and vigorous stirring, slowly adding the yellow solution to the deionized water and catalyst mixed solution in a dropwise manner, continuously and vigorously stirring for 2-6 h after completing the addition, and aging for 24-72 h to obtain the transparent Ti02 hydrosol with blue light; and placing the TiO2 hydrosol on different substrate materials, and placing into a water steaming environment to steam for 6-10 h to obtain nanometer TiO2 with different forms. According to the present invention, the conventional high temperature powder preparation method is broken through; and high catalysis activity nanometer TiO2 with a good dispersion performance can be obtained without addition of any dispersing agents, industrial production is easily achieved, and an application of the nanometer TiO2 in materials with a characteristic of no high temperature resistance is broadened.
Description
Technical field
The present invention relates to the nanometer material science field, especially relate to a kind of water at low temperature and steam the method that processing prepares nano titanium oxide, for non-refractory base material (as textiles, plastics).
Background technology
Nano titanium oxide is because it is nontoxic, stable performance, and have that photocatalytic activity is high, resistance to chemical corrosion is strong, to the advantages such as organic matter degradation non-selectivity, non-secondary pollution in water pollutant, become the photocatalyst that gains great popularity now and have broad prospect of application.In gas sweetening, process the field of Environment Protections such as organic pollutant, antibacterial and deodouring, antifog and automatic cleaning coating and be used widely.
The preparation method of nano titanium oxide can be summarized as solid phase method, vapor phase process and liquid phase method three major types.Various preparation methods all have its relative merits.Solid phase method is by solid phase, to arrive the variation of solid phase, namely relies on mechanical force to grind and shatter to prepare nano level TiO solid material
2Powder, solid phase method comprises high-energy ball milling method, spark-discharge method, thermal decomposition method, solid reaction process etc.The technological operation used of these methods is simple, easily realize producing continuously, but shortcoming is that gained titanium dioxide size distribution is wide, and photocatalytic activity is lower, and easily introduces impurity.Vapor phase process is directly to utilize the whole bag of tricks such as gas or employing laser that the titanium source is become to gas, then at gaseous phase, issues biological reason or chemical transformation, finally through the overcooling condensation growth, forms the method for nano particle.Vapor phase process comprises TiCl
4Vapour phase oxidation process, TiCl
4Oxyhydrogen flame hydrolysis method, pure titanium salt gas phase hydrolysis method, rare gas element add in-place platen press, induced with laser pyrolysis method etc.Though vapor phase process can make the nano oxidized ti powder with better quality, gas-phase reaction need to make the material gasification, and energy consumption is higher.In addition, at high temperature moment the gas phase reaction process that completes, the form of reactor, material, material import and export mode etc. are all had to higher requirement, thereby bring a series of technical problems.
As TiO
2The preparation method of nano-powder, it is the most extensive that liquid phase method is studied.Liquid phase method is generally with TiCl
4, Ti (SO
4)
2, titanium alkoxide etc. be that the raw material hydrolysis generates TiO
2Hydrate, obtain nano-TiO after drying, high-temperature roasting
2Powder.Liquid phase method has the advantages such as raw material sources are extensive, simple to operate, equipment requirements is low.Sol-gel (sol-gel) method of take in liquid phase method is Typical Representative, also one of more ripe preparation method, become the method that the various functional materialss of preparation generally adopt, show wide application prospect in fields such as polycomponent function ceramics, functional paint, glass, plastics, makeup.But liquid phase method generally need to, through pyroprocessing more than 500 ℃, could obtain the nano-TiO of different crystal forms
2, there are the defects such as the preparation process temperature is high, energy consumption is large, agglomeration easily occurs in the nanoparticle made, and pyroprocessing has also affected nano-TiO
2The application of filming on the non-refractory material.For the bottleneck of the shortcomings such as the preparation process temperature that breaks traditions is high, energy consumption is large, find under low temperature or normal temperature and prepare the high catalytic activity nano-TiO
2Method become the most popular direction of photocatalysis field, to TiO
2The preparation industry of nano material will produce revolutionary impact.
Low temperature prepares nano-TiO in recent years
2Obtain certain progress, both at home and abroad existing many reports.Melghit etc. at normal temperatures and pressures, by the TiCl diluted
4Solution stirring at room 7h, add ammoniacal liquor and hydrogen peroxide subsequently, obtains pure anatase octahedrite TiO 300 ℃ of lower thermal treatments
2.Zhao Xiaohong etc. are with TiCl
4And distilled water is main raw material, constant temperature ageing 11～144h in stainless steel water thermal reactor (65～120 ℃), more centrifugal through precipitation, wash, 80 ℃ of dryings can obtain TiO
2Powder.Can find out, above method mainly be take inorganic ti sources and is raw material, has the preparation process complexity, length consuming time, is unfavorable for the problems such as batch production; And TiCl
4In hydrolytic process, can produce a large amount of severe corrosive gas chlorination hydrogen, not environmental protection also causes damage to HUMAN HEALTH.Application number is in 200510039171.6 Chinese patent, the organic titanium source is fully mixed with organic alcohol solvent, obtain the titanium compound alcoholic solution, be added drop-wise in acidic aqueous solution and be hydrolyzed again, after the 6～48h that refluxes at 65～85 ℃ of temperature, alcohols is removed in evaporation under 50～55 ℃, obtains Detitanium-ore-type TiO
2Colloidal sol, this process need carry out reflow treatment under comparatively high temps, also be unfavorable for batch production, but also need by the evaporative removal organic solvent, environment is had to certain pollution.
In sum, the low-temperature nano TiO reported at present
2Although the preparation method is existing a variety of, from the industrial production angle with consider environmental problem, all there is deficiency in various degree.
Summary of the invention
Purpose of the present invention is exactly that a kind of method that high temperature in the past prepares powder that broken through is provided in order to overcome the defect that above-mentioned prior art exists; And just can obtain without adding any dispersion agent the high catalytic activity nano-TiO that dispersing property is good
2.And this nano-TiO
2The preparation method be convenient to suitability for industrialized production, and widened nano-TiO
2Application on non-refractory material (as textiles, plastics etc.).
Purpose of the present invention can be achieved through the following technical solutions:
A kind of water at low temperature is steamed and is processed the method for preparing nano titanium oxide, comprises the following steps:
(1) the titanium source is mixed with sequestrant, stir, obtain the yellow solution of homogeneous phase;
(2) deionized water and catalyzer are fully mixed to regulator solution pH value to 2～3;
(3) under water-bath and vigorous stirring state, the solution that step (1) is obtained slowly splashes in the solution that step (2) obtains, controlling rate of addition dropwises in 0.5～2h, then continue violent stirring 2～6h, ageing 24h～72h, obtain the transparent TiO with blue light again
2The water-sol;
(4) TiO that ageing is good
2The water-sol is placed on the different base material, then puts in water and steams under environment and steam 6h～10h, obtains the nano-TiO of different shape
2.
The mol ratio of described titanium source, deionized water, sequestrant, catalyzer is 1: (4～200): (1～5): (1～7).
As preferred embodiment, the titanium source is selected from a kind of in tetraethyl titanate, tetrabutyl titanate or isopropyl titanate.
As preferred embodiment, sequestrant is selected from a kind of in Glacial acetic acid, quadrol or methyl ethyl diketone.
As preferred embodiment, catalyzer is selected from a kind of in Glacial acetic acid, hydrochloric acid or nitric acid.
The temperature of described water-bath is 30 ℃～60 ℃.
It is that saturated vapour pressure is 0.0～0.38MPa that described water steams environment, and temperature is that the water of 99～150 ℃ steams environmental system.
Described base material is high temperature material or soft base material.
As preferred embodiment, high temperature material is glass, pottery or stainless steel.
As preferred embodiment, soft base material is plastics, timber or textiles.
The nano-TiO prepared
2The form difference can be powder shaped or be attached to the nano-TiO on base material
2Film.
Compared with prior art, the present invention is directed to general liquid phase method needs high-temperature calcination just can obtain the nano titanium oxide that crystal formation is good in the process for preparing titanium dioxide, and the powder made is easily reunited, bad dispersibility in water, be unfavorable for the problem of filming on the non-refractory base material, as the restriction of the Application Areass such as textiles, plastics, timber.The present invention has the following advantages:
1. nano-TiO of the present invention
2To choose the cheap water be easy to get to make solvent, Glacial acetic acid is stablizer, synthetic and technique is simple to operation under the atmospheric low-temperature condition, in preparation process, not relating to throw out produces, without steps such as filtration, washing, high-temperature calcinations, the present invention has replaced tradition as solvent, to prepare nano-TiO with organic solvents such as ethanol
2, this has not only reduced cost, has also reduced disaster hidden-trouble;
2. the nano-TiO for preparing of the present invention
2Through water at low temperature steaming system, process, allow Nano sol particle nucleation and growth slowly, crystallization is constantly perfect, the TiO made
2Have the advantages that degree of crystallinity is high, dispersing property good, particle diameter is little, catalytic activity is high, the crystal grain that while having avoided the high-temperature calcination crystallization, phase transformation causes is grown up rapidly, and catalytic activity is low, the phenomenon of easy reunion.
3. nano-TiO of the present invention
2Through water steaming system, process the TiO that can obtain different shape
2, can be powder, also can on base material, prepare nano-TiO
2Film.Because the present invention steams under environment and carries out in water at low temperature, so this method can be for the application on the flexible substrate of non-refractory, as the Application Areas on plastics, timber, textiles.
4. water at low temperature of the present invention is steamed the standby nano-TiO of legal system
2Huge for prospect on the non-refractory material, the especially application on textiles, if applied the nano-TiO of thin layer on textiles
2Film, give fabric and have the multifunctional textile product such as antibacterial and deodouring, uvioresistant, decontamination automatically cleaning, degradable organic pollutant, meets the diversified demand of modern people.Such as having the demands such as antibiotic medical clothing of nurses, bedclothes, gloves, shoe-pad, socks, have the demands such as anti-ultraviolet parasols, summer clothes.The purposes such as curtain, wall paper, carpet with photocatalytic self-cleaning.
As can be seen here, this nano-TiO of the present invention
2Application on the non-refractory material is extensively, is nano-TiO
2The application of photocatalyst in the finishing functions of textile fabrics field brings an important breakthrough and commercial value.
The accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention;
Fig. 2 is the nano-TiO that Comparative Examples is made
2Powder XRD figure spectrum;
Fig. 3 is the nano-TiO that embodiment 1 makes
2Powder XRD figure spectrum;
Fig. 4 is the nano-TiO that embodiment 2 makes
2Powder XRD figure spectrum.
Embodiment
The present invention is described in detail below in conjunction with the drawings and specific embodiments.
Comparative Examples
Under 30 ℃ of water-bath vigorous stirring states of normal pressure, tetrabutyl titanate and Glacial acetic acid mixing solutions are dropwise joined in aqueous acetic acid, control PH=2～3 in the aqueous solution.Wherein the mol ratio of tetrabutyl titanate, deionized water, sequestrant, catalyzer is 1: 180: 5: 4.Dropwise rear continuation and stir 2h.Quiet to ageing 48h, obtain the TiO with blue light
2Vitreosol.Then the nano-TiO that ageing is good
2Colloidal sol is put into the glass surface ware, in 150 ℃ of dry 10h of normal pressure baking oven, obtains nano-TiO
2Powder, its XRD figure spectrum and performance index are shown in Fig. 2 and table 1.
Table 1 bakes the TiO made under condition
2Powder characteristic
Embodiment 1
Under 30 ℃ of water-bath vigorous stirring states of normal pressure, tetrabutyl titanate and Glacial acetic acid mixing solutions are dropwise joined in aqueous acetic acid, control PH=2～3 in the aqueous solution.Wherein the mol ratio of tetrabutyl titanate, deionized water, sequestrant, catalyzer is 1: 200: 5: 3.Dropwise rear continuation and stir 2h.Quiet to ageing 48h, obtain the TiO with blue light
2Vitreosol.Then the nano-TiO that ageing is good
2Colloidal sol is put into the glass surface ware, and the dry 8h of water steaming system in 100 ℃ of normal pressures, obtain nano-TiO
2Powder.
Its XRD figure spectrum and performance index are shown in Fig. 3 and table 2.
The TiO made under table 2 water at atmospheric pressure steaming system
2Powder characteristic
Embodiment 3
Under 30 ℃ of water-bath vigorous stirring states of normal pressure, tetrabutyl titanate and Glacial acetic acid mixing solutions are dropwise joined in aqueous acetic acid, control PH=2～3 in the aqueous solution.Wherein the mol ratio of tetrabutyl titanate, deionized water, sequestrant, catalyzer is 1: 190: 5: 5.Dropwise rear continuation and stir 2h.Quiet to ageing 48h, obtain the TiO with blue light
2Vitreosol.Then the nano-TiO that ageing is good
2Colloidal sol is put into the glass surface ware, and in 0.18MPa, the water of 130 ℃ steams the dry 6h of system, obtains TiO
2Powder.Its XRD is shown in Fig. 4, show that performance is as shown in table 3 below.
The TiO made under table 3 high pressure water steaming system
2Powder characteristic
Can find out the nano-TiO that the dry system of high pressure water evaporate to dryness obtains
2Powder has good photocatalytic activity, and after uv irradiating 1.5h, the 5mg/L methylene blue solution almost is degraded to white solution.
Embodiment 4
A kind of water at low temperature is steamed and is processed the method for preparing nano titanium oxide, and its technical process as shown in Figure 1, comprises the following steps:
(1) tetrabutyl titanate is mixed with Glacial acetic acid, obtain yellow solution.
(2) deionized water and Glacial acetic acid are mixed, pour in there-necked flask, be placed in 30 ℃ of constant temperature water baths, in under the electric mixer whipped state, the yellow solution in step (1) slowly being added drop-wise to aqueous acetic acid, drip Bi Jixu violent stirring 2h, after ageing 48h, obtain with the transparent nano TiO 2 water-sol of blue light.The mol ratio of above-mentioned tetrabutyl titanate, deionized water, sequestrant, catalyzer is 1: 200: 5: 3.
(3) choosing the flexible substrate cotton fabric is base material, immerses the good nano-TiO of ageing
2In the water-sol, soak and steam 8h in the water steaming system of 100 ℃ of normal pressures, clean and dry, obtain area load one deck and be uniformly distributed nano-TiO
2Cotton fabric, the dirt (as coffee, red wine etc.) that its fabric face stains, can be removed after 8 hours fully through illumination.Thereby nano titanium oxide of the present invention is processed on fabric has good automatically cleaning effect, can be used on the Application Areass such as tablecloth, wall paper, carpet.
Embodiment 5
A kind of water at low temperature is steamed and is processed the method for preparing nano titanium oxide, and its technical process as shown in Figure 1, comprises the following steps:
(1) tetrabutyl titanate is mixed with Glacial acetic acid, obtain yellow solution.
(2) deionized water and Glacial acetic acid are mixed, pour in there-necked flask, be placed in 30 ℃ of constant temperature water baths, in under the electric mixer whipped state, the yellow solution in step (1) slowly being added drop-wise to aqueous acetic acid, drip Bi Jixu violent stirring 3h, after ageing 36h, obtain with the transparent nano-TiO of blue light
2The water-sol.The mol ratio of above-mentioned tetrabutyl titanate, deionized water, sequestrant, catalyzer is 1: 190: 5: 5.
(3) choosing the flexible substrate cotton fabric is base material, immerses the good nano-TiO of ageing
2In the water-sol, in 0.18MPa, the water steaming system of 130 ℃ is soaked and is steamed 6h, cleans and dries, and obtains area load one deck and is uniformly distributed nano-TiO
2Cotton fabric.Its cotton fabric uvioresistant performance is as shown in table 4 below.
Table 4 cotton fabric anti-ultraviolet property
| Cloth specimen | UPF | T(UVA) | T(UVB) |
| Former cloth | 8.17 | 18.93％ | 9.48％ |
| Sample cloth after arrangement | 194.9 | 3.00％ | 0.32％ |
By as seen from Table 4, nano titanium oxide of the present invention is processed on fabric has good shielding ultraviolet rays effect.Can be used on the Application Areass such as curtain, parasols.
Claims (10)
1. a water at low temperature is steamed and is processed the method for preparing nano titanium oxide, it is characterized in that, the method adopts water at low temperature to steam and processes and prepares nano titanium oxide, specifically comprises the following steps:
(1) the titanium source is mixed with sequestrant, stir, obtain the yellow solution of homogeneous phase;
(2) deionized water and catalyzer are fully mixed to regulator solution pH value to 2～3;
(3) under water-bath and vigorous stirring state, the solution that step (1) is obtained slowly splashes in the solution that step (2) obtains, controlling rate of addition dropwises in 0.5～2h, then continue violent stirring 2～6h, ageing 24h～72h, obtain the transparent TiO with blue light again
2The water-sol;
(4) TiO that ageing is good
2The water-sol is placed on the different base material, then puts in water and steams under environment and steam 6h～10h, obtains the nano-TiO of different shape
2.
2. a kind of water at low temperature according to claim 1 is steamed the method for preparing nano titanium oxide of processing, it is characterized in that, the mol ratio of described titanium source, deionized water, sequestrant, catalyzer is 1: (4～200): (1～5): (1～7).
3. a kind of water at low temperature according to claim 1 and 2 is steamed and is processed the method for preparing nano titanium oxide, it is characterized in that, described titanium source is selected from a kind of in tetraethyl titanate, tetrabutyl titanate or isopropyl titanate.
4. a kind of water at low temperature according to claim 1 and 2 is steamed and is processed the method for preparing nano titanium oxide, it is characterized in that, described sequestrant is selected from a kind of in Glacial acetic acid, quadrol or methyl ethyl diketone.
5. a kind of water at low temperature according to claim 1 and 2 is steamed and is processed the method for preparing nano titanium oxide, it is characterized in that, described catalyzer is selected from a kind of in Glacial acetic acid, hydrochloric acid or nitric acid.
6. a kind of water at low temperature according to claim 1 is steamed and is processed the method for preparing nano titanium oxide, it is characterized in that, the temperature of described water-bath is 30 ℃～60 ℃.
7. a kind of water at low temperature according to claim 1 is steamed and is processed the method for preparing nano titanium oxide, it is characterized in that, it is that saturated vapour pressure is 0.0～0.38MPa that described water steams environment, and temperature is that the water of 99～150 ℃ steams environmental system.
8. a kind of water at low temperature according to claim 1 is steamed and is processed the method for preparing nano titanium oxide, it is characterized in that, described base material is high temperature material or soft base material.
9. a kind of water at low temperature according to claim 8 is steamed and is processed the method for preparing nano titanium oxide, it is characterized in that, described high temperature material is glass, pottery or stainless steel, and described soft base material is plastics, timber or textiles.
10. a kind of water at low temperature according to claim 1 is steamed and is processed the method for preparing nano titanium oxide, it is characterized in that the nano-TiO prepared
2For powder shaped or be attached to the nano-TiO on base material
2Film.
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