CN104556219A - Method for preparing nano-TiO2 - Google Patents
Method for preparing nano-TiO2 Download PDFInfo
- Publication number
- CN104556219A CN104556219A CN201310521975.4A CN201310521975A CN104556219A CN 104556219 A CN104556219 A CN 104556219A CN 201310521975 A CN201310521975 A CN 201310521975A CN 104556219 A CN104556219 A CN 104556219A
- Authority
- CN
- China
- Prior art keywords
- titanium
- titanium source
- present
- water soluble
- soluble alkaline
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a method for preparing nano-TiO2. The method comprises the following steps: contacting a titanium source and a water-soluble alkaline substance in the presence of an aqueous solvent under a hydrolysis condition, wherein the titanium source is a titanium compound having the following structure [TiClx(OR)(4-x)][R'OH]y, x is 1, 2 or 3, y is 0, 1, 2, 3, 4 or 5, and R and R' are same or different alkyls. According to the method, hydrolysis can be carried out at a relatively low temperature. Compared with methods in the prior art of using titanium tetrachloride or titanium tetraol as a titanium source, the method has the advantages of greatly reducing water consumption and effectively reducing wastewater drainage.
Description
Technical field
The present invention relates to one and prepare nano-TiO
2method.
Background technology
Current world wide is for nano-TiO
2research mainly concentrate on the nano-TiO of size tunable
2the preparation of particle and the utilization to its photocatalysis performance.Nano-TiO
2particle refers generally to the TiO that particle diameter is less than 100 nanometers
2particle.There is the TiO of aforementioned particle size
2particle has larger specific area and good dispersive property, therefore has fabulous photocatalysis performance and special optical property.
TiO
2crystal formation be mainly divided into rutile-type, Detitanium-ore-type and brookite type, wherein, comparatively common with the above two.Nm-class rutile-type TiO
2particle has good optical property, is mainly used in as ultra-violet absorber, high grade paint and cosmetic additive agent etc., in addition, when this type nano-TiO
2when grain diameter is less than 20 nanometer, also show stronger photocatalysis performance.Nano-sized anatase type TiO
2particle has stronger photocatalysis performance, is therefore mainly used in the photocatalysis Decomposition of organic pollution as water purification and purification of air etc.
At present, nano-TiO is prepared
2the main method of particle be all with the alkoxide (as: four titanium propanolates and four butanols titaniums) of the inorganic salts of titanium (as: titanium tetrachloride and titanium sulfate) or titanium for initiation material, finally obtain nano-TiO through different hydrolysis methods (as: direct hydrolysis method, water (solvent) hot method, sluggish precipitation, sol-gel process, microemulsion phase method and gas phase hydrolysis method etc.)
2particle.
CN1530327A discloses the preparation method of a kind of crystal formation and the controlled nanometer titanic oxide material of size, comprises following steps:
(1) polymer Ao mixture be dissolved in alcoholic solution close agent solution to obtain polymer Ao:
(2) by titanium tetrachloride (TiC1
4) or TiC1
4the aqueous solution and polymer Ao close agent solution and are uniformly mixed in the reactor, thus obtain homodisperse mixed solution, wherein by percentage to the quality, and TiC1
4, polymer Ao mixture, water and alcohol ratio be respectively 5-50%, 0.3-30%, 50-90% and 5-60%;
(3) to step 2) mixed solution that obtains adds aqueous alkali, and adds thermal response under agitation, and wherein, heating-up temperature is between 50-110 DEG C, and the heat time is between 0.5-5 hour: and
(4) solvent after removing reaction in mixed solution also obtains nanometer titanic oxide material by drying.
Although the method can form stable titanium ion gel rubber system, it introduces polymeric chelant carboxylic acid etc., causes component of effluent complicated difficult with process or recycles.
Comprehensive analysis, prior art prepare nano-TiO
2there is following major defect in the method for particle:
1, employing titanium tetrachloride is the direct hydrolysis technique of initiation material, owing to needing to add alkali and dispersant simultaneously, causes component of effluent complicated difficult with process or recycles;
2, employing titanium tetrachloride is the direct hydrolysis technique of initiation material, and the comparatively large general water consumption of water requirement is 10 times of initiation material to 50 times, causes waste liquid amount to be discharged larger;
3, adopt titanium tetrachloride be initiation material direct hydrolysis technique use inorganic base as pH adjusting agent, reaction speed be difficult to control, therefore size controlling is more difficult;
4, employing Titanium alkoxides is the technique (comprising Hydrolyze method and sol-gel process) of initiation material, and its cost of material is higher, and in raw material, Ti content is lower simultaneously, and therefore economy is poor;
5, titanium tetrachloride is adopted to be the vapor phase hydrolysis technique of initiation material, higher to the requirement of equipment, and produce a large amount of seriously corroded of hydrochloric acid smog to equipment in process and cause equipment investment higher;
6, hydro-thermal method or vapor phase method is adopted to prepare TiO
2nano particle, need use acidproof high voltage bearing equipment, therefore operational danger is higher, and equipment investment and maintenance cost are all higher.
Summary of the invention
The object of the invention is the aforementioned techniques defect for overcoming prior art, providing one to be hydrolyzed in a mild condition, and can greatly reduce the consumption of water prepare nano-TiO
2method.
Supported Ziegler-Natta catalyst is that propylene polymerization produces in polyacrylic process a kind of catalyst used.Can produce a certain amount of waste residue in the production of this catalyst, analyze and find, its main component is [TiCl
3oEt] EtOH
x(x=1), Ti content is up to 19%(mass fraction).This waste residue can react with water and generate hydrochloric acid and therefore have stronger corrosivity, also can discharge hydrochloric acid smog in addition in atmosphere and pollute.At present, for this waste residue not cost-effective processing method.
The present inventor prepares in the method for nano titanium oxide find in research, use the hydrolysis of the titanium source of prior art to prepare nano titanium oxide, not only required hydrolysis temperature is high, and in hydrolytic process, water consumption is large, therefore, can the present inventor attempts imagination be [TiCl by main component
3oEt] [EtOH]
x(x=1) waste residue for the preparation of nano titanium oxide, using as improvement titanium source, through verification experimental verification, find, adopt this waste residue to prepare nano titanium oxide as titanium source, can be hydrolyzed under lower hydrolysis temperature and prepare nano titanium oxide, and in process, water consumption is low.
The present inventor also finds, (the similar compound of structure comprises [TiCl for compound that in this waste residue, main component structure is similar
x(OR)
(4-x)] [R ' OH]
y, wherein x=1,2,3; Y=0,1,2,3,4,5, R and R ' is identical or different alkyl, for initiation material prepares TiO
2nano particle, has aforementioned same effect.Based on aforementioned discovery and verification experimental verification, complete the present invention.
For realizing aforementioned object, the invention provides one and preparing nano-TiO
2method, the method comprises: under hydrolysising condition, is contacted in titanium source with water soluble alkaline material under aqueous solvent exists, and wherein, described titanium source is the titanium compound with following structure: [TiCl
x(OR)
(4-x)] [R ' OH]
y, wherein, x be 1,2 or 3, y be 0,1,2,3,4 or 5, R and R ' be identical or different alkyl.
The present invention has the titanium compound ([TiCl of following structure by using
x(OR)
(4-x)] R ' OH
y, wherein x=1,2 or 3; Y=0,1,2,3,4 or 5, R and R ' is identical or different alkyl) as titanium source, method of the present invention can be hydrolyzed at a lower temperature, and use titanium tetrachloride, the tetrol of titanium and thing as the method in titanium source compared to prior art, method water consumption of the present invention reduces greatly, effectively can reduce the discharge of waste water.
In a preferred embodiment of the invention, the waste residue that effectively make use of supported Ziegler-Natta catalyst is titanium material, and hydrolysis temperature and hydrolysis water consumption (water requirement is only initiation material quality 4 to 10 times) can be reduced, there is extraordinary economy, without strong acid and strong base or high-temperature and high-pressure conditions in whole course of reaction, lower to equipment requirement, and waste liquid amount is easy to reclaim less.
The present invention uses the Hydrolyze method of improvement, and the waste residue produced in catalyst production process is converted into nano-TiO
2particle, thus realize the innoxious of waste residue and resource, achieves the anatase titanium dioxide or or the TiO of mixed type that prepare particle diameter 1 to 100 nanometer with the raw material of cheapness and lower technological requirement
2nano particle.
Other features and advantages of the present invention are described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Below the specific embodiment of the present invention is described in detail.Should be understood that, detailed description of the invention described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides one and prepare nano-TiO
2method, the method comprises: under hydrolysising condition, is contacted in titanium source with water soluble alkaline material under aqueous solvent exists, and wherein, described titanium source is the titanium compound with following structure:
[TiCl
x(OR)
(4-x)] [R ' OH]
y, wherein, x be 1,2 or 3, y be 0,1,2,3,4 or 5, y be preferably 0,1,2,3; R and R ' is identical or different alkyl.
According to method of the present invention, preferred described x is 3.
According to method of the present invention, preferred described y is 1.
According to method of the present invention, preferred described R and R ' is the alkyl of C1-C5 separately, and be preferably the alkyl of C1-C4, more preferably R and R ' is one or more in methyl, ethyl, propyl group and butyl separately, and preferably R with R ' is identical alkyl.
According to method of the present invention, aforementioned preferred titanium source can be commercially available, and also can prepare, when y is not equal to 0, and can by alcohol R ' OH and TiCl
x(OR)
(4-x)be mixed to get, also can prepare as follows: at low temperatures, titanium tetrachloride is carried out in the organic solution of alcohol alcoholysis and obtain, wherein, low temperature is lower than subzero 20 DEG C, and organic solvent can be such as hexane.
According to method of the present invention, in order to reasonably utilize resource, preferred described titanium source derives from the waste residue produced supported Ziegler-Natta catalyst and produce, and wherein, described waste residue is mainly containing [TiCl
3(OEt)] [EtOH], wherein Et is ethyl, [TiCl
3(OEt)] [EtOH] purity more than 95%, all the other are other foreign ions such as Fe
3+and Mg
2+.
According to method of the present invention, preferably titanium source and mixed in hydrochloric acid are formed solution, then contact under aqueous solvent exists with water soluble alkaline material, the concentration of preferred described hydrochloric acid is 0.01-0.1mol/L.
According to method of the present invention, the range of choices of the kind of described water soluble alkaline material is wider, the water soluble alkaline material that this area routine uses all can realize the goal of the invention of the application, for the present invention, preferred described water soluble alkaline material is one or more in ammonia, alkali-metal hydroxide and organic amine compound, be more preferably ammonia and/or organic amine compound, most preferably be organic amine compound.
According to method of the present invention, the goal of the invention of the application can be realized according to preceding solution, for the present invention, consider from economy point, preferred described water-soluble organic amine is hydramine and/or enamine, more preferably described water-soluble organic amine is the mixture of hydramine and enamine, and more preferably the weight ratio of enamine and hydramine is 5-100:100, preferred 10-50:100.
According to method of the present invention, the range of choices meeting the hydramine of application claims is wider, as long as water-soluble hydramine can realize the goal of the invention of the application, for the present invention, preferred described hydramine is the hydramine of C1-C10, can be that single methanol amine also can for many hydramine, for the present invention, preferred described hydramine be one or more in triethanolamine, diethanol amine and MEA.
According to method of the present invention, the range of choices meeting the enamine of application claims is wider, as long as water-soluble enamine can realize the goal of the invention of the application, for the present invention, preferred described enamine is the enamine of C2-C10, more preferably described enamine is one or more in ethylenediamine, triethylene diamine, diethylenetriamine, triethylene tetramine, TEPA, five ethene hexamines, and particularly preferably described enamine is at least two kinds of mixtures in triethylene tetramine, TEPA and five ethene hexamines.
According to method of the present invention, the organic amine of the present invention titanium source that is hydrolyzed is adopted to prepare titanium dioxide, not only without the need to introducing dispersant or surfactant, and can effectively control reaction speed and product cut size, the severity of hydrolysising condition can be reduced simultaneously, the temperature of prior art is generally (direct hydrolysis method 80-100 DEG C, hydro-thermal method 150-200 DEG C), and the present invention can be hydrolyzed at a lower temperature, can be generally 0-80 DEG C, be more preferably 50-65 DEG C, and prior art generally needs to carry out under strongly acidic conditions, and the present invention only carries out getting final product (whole process pH value is 5-12) under mild conditions, even if prior art uses ammoniacal liquor to be hydrolyzed as inorganic base, also produce in hydrolytic process highly acid (reaction start rear pH value of solution rapidly by be greater than 12 drop to be less than 1), cause easy etching apparatus.As can be seen here, compared to the method for prior art, method energy consumption of the present invention is lower, thus can save production cost.
Titanium source of the present invention can be hydrolyzed at a lower temperature, and hydrolysis temperature is 0-80 DEG C, is preferably 50-65 DEG C.
According to the preferred embodiment of the present invention, it is 5-12 that the condition be more preferably hydrolyzed also comprises pH, is more preferably 8-12.
According to more preferably embodiment of the present invention, more preferably the condition be hydrolyzed also comprises: the mol ratio of titanium source and water soluble alkaline material is that 1:1.05-1.2x(is in amido), during with aforementioned waste residue for raw material, the mol ratio of titanium source and water soluble alkaline material is 1:3.2-3.6.
Generally speaking, use the titanium source of prior art if titanium tetrachloride etc. is as titanium source of the present invention, the mass ratio in aqueous solvent and titanium source is 10-50:1.And use aforementioned titanium source [TiCl of the present invention
x(OR)
(4-x)] [R ' OH]
ybe hydrolyzed, the mass ratio in aqueous solvent and titanium source is preferably 4-10:1.
According to one of the present invention preferred embodiment, the condition of hydrolysis comprises: temperature is 0-80 DEG C, and being preferably 50-65 DEG C, pH is 5-12, and the mol ratio of titanium source and water soluble alkaline material is 1:1.05-1.2x, and the mass ratio in reaction dissolvent and titanium source is 4-10:1.
According to method of the present invention, preferred method of the present invention also comprises: from the mixture after contact, isolate solid material, then dry.
In the present invention, dry temperature can be that the routine of this area is selected, and is generally 80-120 DEG C.
In the present invention, the method isolating solid material from the mixture after contact can be carried out with reference to prior art, and the step generally comprise filtration, wash, refiltering, the present invention is not described in detail at this.
In the present invention, crystalline phase figure adopts XRD diffraction approach to obtain, and particle diameter adopts transmission electron microscope to record.
Describe the present invention in detail below by embodiment, but the present invention is not limited to this.
Embodiment 1
Under condition of ice bath, the waste residue producing supported Ziegler-Natta catalyst generation (is consisted of (TiCl
3oEt) EtOH, wherein Et is ethyl) be mixed to get waste residue solution as titanium source and watery hydrochloric acid (concentration is 0.1mol/L), the mass ratio of waste residue and hydrochloric acid is 1:1, then (organic amine is the mixture of triethylene diamine and diethanol amine with the aqueous solution of 20 quality % organic amines, the two weight ratio is 10:100), the mol ratio of titanium source and organic amine (in amido) is 1:3.3, pH value is 11, after being heated to 55 DEG C of insulation 180min, titanium source is all hydrolyzed, filter, washing, refilter separation and obtain solid, then at 100 DEG C, drying obtains pure nanometer anatase titania, particle diameter is about 12nm.
Embodiment 2
Titanium dioxide is prepared according to the method for embodiment 1, unlike, triethylene diamine and diethanol amine weight ratio are 5:100, and other conditions are constant, obtain pure nanometer anatase titania, and particle diameter is about 14nm.
Embodiment 3
Titanium dioxide is prepared according to the method for embodiment 1, unlike, the By Amine Solutions of use is triethanolamine solution, and all the other conditions are constant, and obtain nanometer anatase titania (containing 5% Rutile Type of having an appointment), particle diameter is about 30nm.
Embodiment 4
Titanium dioxide is prepared according to the method for embodiment 1, unlike, the mol ratio of titanium source and organic amine is 1:4, and all the other conditions are constant, obtain nanometer anatase titania, particle diameter about 50nm.
Embodiment 5
Titanium dioxide is prepared according to the method for embodiment 1, unlike, the titanium source of use is trichloromethoxy titanium, organic amine is the mixture of ethylenediamine and MEA, and the two weight ratio is 30:100, and temperature is 60 DEG C, obtain sharp pure titanium-type nano titanium oxide, particle diameter about 12nm.
Embodiment 6
Titanium dioxide is prepared according to the method for embodiment 1, unlike, the titanium source of use is trichlorine titanium butoxide, organic amine is the mixture of triethylene tetramine and triethanolamine, and the two weight ratio is 50:100, and temperature is 65 DEG C, obtain pure nanometer anatase titania, particle diameter about 18nm.
Embodiment 7
Titanium dioxide is prepared according to the method for embodiment 1, unlike, the triethylene diamine of use is replaced by the mixture of TEPA and five ethene hexamines, and wherein the weight ratio of TEPA and five ethene hexamines is 1:1, obtain pure nanometer anatase titania, particle diameter about 8nm.
Embodiment 8
In flask, add deionized water 100ml, after 20ml isopropyl alcohol and 5g polyethylene glycol stir, under ice bath, in solution, add the dilute hydrochloric acid solution (concentration of hydrochloric acid is 0.01mol/L) that 20ml concentration is the waste residue of 0.5mol/L.Drip ammoniacal liquor and regulate pH value of solution to 12, solution is heated to 90 DEG C, be incubated 3 hours, solution filters after ageing in 24 hours, washs 3 times respectively, obtain nano-TiO with deionized water and absolute ethyl alcohol
2grain diameter 20nm, wherein, rutile makes an appointment 35%, and anatase makes an appointment 65%.
Comparative example 1
This comparative example prepares nano titanium oxide for illustration of method conventionally.
In flask, add deionized water 100ml, after 20ml isopropyl alcohol and 5g polyethylene glycol stir, under ice bath, in solution, add the TiCl that 20ml concentration is 0.5mol/L
4solution, drip ammoniacal liquor and regulate pH value of solution to 12, solution is heated to 90 DEG C, be incubated 3 hours, solution filters after ageing in 24 hours, washs 3 times respectively, obtain nano-TiO with deionized water and absolute ethyl alcohol
2, grain diameter is 15nm, and wherein rutile makes an appointment 75%, and anatase makes an appointment 25%.
Comparative example 2
Titanium dioxide is prepared according to the method for embodiment 1, unlike, the titanium source of use is titanium tetrachloride, and all the other conditions are constant, and obtain nanometer anatase titania (containing 5% Rutile Type of having an appointment), particle diameter is about 25nm.
As can be seen from the result of comparative example and embodiment, can be hydrolyzed the nano titanium oxide obtaining pure crystalline phase at a lower temperature according to method of the present invention, and size tunable is better, and whole process produces without strong acid and strong base condition, without equipment pollution, and method water consumption of the present invention is lower.
More than describe the preferred embodiment of the present invention in detail, but, the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention, can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to demetalization scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, can be combined by any suitable mode.
In addition, also can be combined between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (9)
1. prepare nano-TiO for one kind
2method, the method comprises: under hydrolysising condition, is contacted in titanium source, it is characterized in that with water soluble alkaline material under aqueous solvent exists, and described titanium source is the titanium compound with following structure:
[TiCl
x(OR)
(4-x)] [R ' OH]
y, wherein, x be 1,2 or 3, y be 0,1,2 or 3, R and R ' be identical or different alkyl.
2. method according to claim 1, wherein, x is 3, y is 1, R and R ' be the alkyl of C1-C10.
3. method according to claim 2, wherein, described R and R ' is one or more in methyl, ethyl, butyl and propyl group separately.
4. according to the method in claim 1-3 described in any one, wherein, described titanium source is the product of the incomplete alcoholysis of titanium tetrachloride.
5. according to the method in claim 1-4 described in any one, wherein, described titanium source is prepared as follows: at low temperatures, and titanium tetrachloride is carried out alcoholysis in the organic solution of alcohol, and wherein, low temperature is lower than subzero 20 DEG C, and the solvent of organic solution is hexane.
6. according to the method in claim 1-5 described in any one, wherein, titanium source and mixed in hydrochloric acid are formed solution, then contacts under aqueous solvent exists with water soluble alkaline material.
7. according to the method in claim 1-6 described in any one, wherein, described water soluble alkaline material is one or more in ammonia, alkali-metal hydroxide and organic amine compound.
8. according to the method in claim 1-7 described in any one, wherein, the condition of hydrolysis comprises: temperature is 0-80 DEG C, pH is 5-12, and the mol ratio of titanium source and water soluble alkaline material is 1:1.05-1.2x, and the mass ratio in aqueous solvent and titanium source is 4-10:1.
9. according to the method in claim 1-8 described in any one, wherein, the method also comprises: from the mixture after contact, isolate solid material, then dry.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310521975.4A CN104556219B (en) | 2013-10-29 | 2013-10-29 | One prepares nano-TiO2Method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310521975.4A CN104556219B (en) | 2013-10-29 | 2013-10-29 | One prepares nano-TiO2Method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104556219A true CN104556219A (en) | 2015-04-29 |
| CN104556219B CN104556219B (en) | 2016-06-01 |
Family
ID=53073424
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310521975.4A Active CN104556219B (en) | 2013-10-29 | 2013-10-29 | One prepares nano-TiO2Method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104556219B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107012524A (en) * | 2017-05-10 | 2017-08-04 | 浙江银瑜新材料股份有限公司 | One kind is based on the high uvioresistant function fiber producing processes of organic synthesis |
| CN112126100A (en) * | 2020-10-13 | 2020-12-25 | 绍兴高卓新材料科技有限公司 | Long-acting nano antibacterial composite material and preparation method thereof |
| CN112708782A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Titanium-containing waste liquid treatment method and titanium-containing dry powder |
| CN112707449A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Method for treating titanium-containing waste liquid |
| CN112707561A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Treatment method of titanium-containing waste liquid |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101028937A (en) * | 2007-02-06 | 2007-09-05 | 云南大学 | Method for producing nano-anatase mine-titanium oxide water sol |
| CN101352675A (en) * | 2008-03-03 | 2009-01-28 | 广东海洋大学 | Method for preparing shell powder supported active nano titanic oxide |
| US20090209665A1 (en) * | 2008-02-14 | 2009-08-20 | Guoyi Fu | Colloidal titanium dioxide sols |
| CN101519213A (en) * | 2008-02-28 | 2009-09-02 | 中国石油化工股份有限公司 | Synthetic method of titanium-containing mesoporous materials |
| CN103086426A (en) * | 2013-01-14 | 2013-05-08 | 浙江大学 | Preparation method of titanium dioxide aerogel |
-
2013
- 2013-10-29 CN CN201310521975.4A patent/CN104556219B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101028937A (en) * | 2007-02-06 | 2007-09-05 | 云南大学 | Method for producing nano-anatase mine-titanium oxide water sol |
| US20090209665A1 (en) * | 2008-02-14 | 2009-08-20 | Guoyi Fu | Colloidal titanium dioxide sols |
| CN101519213A (en) * | 2008-02-28 | 2009-09-02 | 中国石油化工股份有限公司 | Synthetic method of titanium-containing mesoporous materials |
| CN101352675A (en) * | 2008-03-03 | 2009-01-28 | 广东海洋大学 | Method for preparing shell powder supported active nano titanic oxide |
| CN103086426A (en) * | 2013-01-14 | 2013-05-08 | 浙江大学 | Preparation method of titanium dioxide aerogel |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107012524A (en) * | 2017-05-10 | 2017-08-04 | 浙江银瑜新材料股份有限公司 | One kind is based on the high uvioresistant function fiber producing processes of organic synthesis |
| CN107012524B (en) * | 2017-05-10 | 2018-08-10 | 浙江银瑜新材料股份有限公司 | A kind of uvioresistant function fiber producing processes based on organic synthesis |
| CN112708782A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Titanium-containing waste liquid treatment method and titanium-containing dry powder |
| CN112707449A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Method for treating titanium-containing waste liquid |
| CN112707561A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Treatment method of titanium-containing waste liquid |
| CN112707561B (en) * | 2019-10-25 | 2023-05-12 | 中国石油化工股份有限公司 | Treatment method of titanium-containing waste liquid |
| CN112126100A (en) * | 2020-10-13 | 2020-12-25 | 绍兴高卓新材料科技有限公司 | Long-acting nano antibacterial composite material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104556219B (en) | 2016-06-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104556219B (en) | One prepares nano-TiO2Method | |
| CN104556220B (en) | One prepares nano-TiO2Method | |
| CN101318698B (en) | Method for preparing anatase type nano-titanium dioxide | |
| CN103523824B (en) | The preparation method of nano-sheet ferroelectric material for a kind of photocatalysis | |
| CN104209136A (en) | Preparation method of TiO2/porous g-C3N4 composite material | |
| CN103318956A (en) | Titanium dioxide nanowire preparation method | |
| CN107522169A (en) | A kind of normal temperature prepares pure organic homogeneous precipitation method of nano-oxide | |
| CN105363400A (en) | Photocatalyst nano TiO2 hydrosol production apparatus | |
| CN105540640A (en) | Preparation method of flower-shaped nanometer zinc oxide | |
| CN110143613A (en) | A kind of Nano titanium dioxide powder preparation method | |
| CN103613117B (en) | A kind of method adjusting the ratio regulation and control zinc sulfide nano pattern of mixed solvent | |
| CN103111295B (en) | Photocatalytic nano composite material having magnetic response property and preparation method thereof | |
| CN100519418C (en) | High purity nano polyaluminum sol industrialized preparation method | |
| CN104445221B (en) | A kind of microwave-assisted rice hull ash prepares the new method of white carbon | |
| CN101928484B (en) | Method for preparing sulfate/titanium dioxide composite powder from titanyl sulfate | |
| CN103464130A (en) | Method of preparing titanium dioxide meso-pore material with adjustable pore diameter | |
| CN104098125B (en) | A kind of preparation method of strontium titanates nano cubic block | |
| CN104556116A (en) | Method for assisted synthesis of TS-1 molecular sieve by using aerosol | |
| CN107486171A (en) | A kind of preparation method of titanium dioxide and Chitosan Composites | |
| CN103601237A (en) | Charged anatase titania nanoparticles and low-temperature preparation method thereof | |
| CN205146223U (en) | Photocatalyst nanometer tiO2 hydrosol apparatus for producing | |
| CN105126809A (en) | Preparation method for lead titanate/titanium dioxide two-dimension monocrystal heterostructure photocatalyst | |
| CN104609469A (en) | Preparation method for mono-dispersed nano titanium dioxide sol | |
| CN101704544B (en) | Method for preparing zinc oxide nano rod applied to sewage treatment | |
| CN105000596B (en) | Method for preparing nano-TiO2 gel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |