CN104098133B - Preparation method for high-efficient photocatalyst-nanometer titanium dioxide water-based colloid - Google Patents
Preparation method for high-efficient photocatalyst-nanometer titanium dioxide water-based colloid Download PDFInfo
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Abstract
The invention discloses a preparation method for a high-efficient photocatalyst-nanometer titanium dioxide water-based colloid. The preparation method comprises the following steps: adopting metal titanium as titanium source; adopting hydrogen peroxide to oxidize nulvalent metal Ti into quadrivalent TiO＜2+＞; further conducting complexing on the TiO＜2+＞ and the hydrogen peroxide to obtain water-soluble TiO[H2O2]＜2+＞ yellow complex; obtaining yellow complex colloid after evaporating and removing excess hydrogen peroxide and ammonia; conducting hydrothermal reaction by high pressure water of 150-200 DEG C; transporting the TiO[H2O2]＜2+＞ yellow complex into pure white Ti(OH)4 water-based emulsion; adding mineral acid to adjust the pH value of the emulsion to the range of 2-4; conducting temperature control to enable the temperature of water bath to be 60-80 DEG C; continually stirring for 3-6 hours to enable the Ti(OH)4 water-based emulsion to gradually gel into nanometer titanium dioxide water-based colloid. The preparation method uses no organic solvent; no waste water or waste gas generates in the reaction process; particle diameters of colloid granular are less than 10 nanometers; degree of crystallinity is high; high photocatalytic activity is provided; coating property and film forming property on porous base material are extremely good.
Description
Technical field
The present invention relates to the preparation method of a kind of high efficiency photocatalyst, belong to nano titanium dioxide photocatalysis Environment control dirty
The application of dye.
Background technology
Optically catalytic TiO 2 technology is applied to the control of environmental pollution, be particularly used for thoroughly decomposing various poisonous, have
The organic pollution of evil has become one of generally acknowledged most effective means in countries in the world.
863 country's major scientific and technological project industrialization biddings documents are pointed out: the practical mark of photocatalysis technology is that " two is high by one
Low, " high efficiency photocatalyst to be solved and highly effective photocatalytic reactor develop in a difficult problem, to reach economically
Requirement to low cost movement.
Nanotechnology is the one preferred technique obtaining high efficiency photocatalyst.
Over nearly 20 years, experts and scholars both domestic and external have done substantial amounts of research and development in terms of preparing nano titanium dioxide photocatalyst
Work, also occurs in that many patents, including nano titanium oxide solid state powder, nano titanium oxide solvent-borne type colloid, nanometer
The patented technology of the preparation methoies such as titanium dioxide water colloid.It is known that nano titanium oxide solid state powder difficulty is disperseed, is easily rolled into a ball
Poly-；In nano titanium oxide solvent-borne type colloid, organic solvent is volatile, be difficult to preservation；Therefore the nano titanium oxide of highly dispersed state
Aqueous colloidal most actual application prospect.
But, in patented technology prepared by numerous nanometer titanium dioxide water colloids, it is main former for mostly using organic titanium
Material (such as titanate esters or claim Titanium alkoxides, alkoxytitanium etc.), also needs to add organic solvent (such as ethanol, propanol, different in building-up process
Propanol etc.), hydrolysis inhibitor (such as diethanolamine, triethanolamine etc.), chelating agen (such as ethylenediamine, acetylacetone,2,4-pentanedione etc.), the most former
Material cost is high, and can cause environmental pollution.
Summary of the invention
It is an object of the present invention to provide the preparation method of a kind of high efficiency photocatalyst-nanometer titanium dioxide water colloid, this system
Preparation Method is to be entirely Inorganic synthese, does not use any organic solvent, produces without waste water, waste gas in course of reaction, is a kind of
Clean preparation technology；The theoretical earning rate of titanium dioxide is up to 166%, and cost of material drops significantly compared with other patent technique
Low；Using nanometer titanium dioxide water colloidal solid particle diameter prepared by the present invention less than 10 nanometers, degree of crystallinity is high, has the strongest
Photocatalytic activity；And paintability and filming performance on porous substrate is the best, high efficiency photocatalysis agent film can be made
Apply in air and water purification field, can be with various poisonous, the harmful organic contamination of oxidation Decomposition under the irradiation of ultraviolet light
Thing, formaldehyde clearance is high and the removal time is greatly shortened, and sterilizing rate is high and the time is short simultaneously.
For reaching above-mentioned purpose, the technical solution used in the present invention comprises the following steps: a kind of high efficiency photocatalyst-nanometer
The preparation method of titanium dioxide water colloid, comprises the following steps:
Step one, Titanium is put in glass beaker, add aqueous hydrogen peroxide solution and form mixed liquor, Titanium and mistake
The mol ratio of hydrogen oxide is 1:8 ~ 12, and described Titanium is participated sponge titanium；
Step 2, being placed in ice-water bath by glass beaker, ice-water bath temperature controls between 5～15 DEG C, moderate-speed mixer institute
State mixed liquor thing and form intermediate reaction thing；
Step 3, a certain amount of ammonia is poured in the flask of band arm and piston, flask is placed in hot bath, water-bath
Temperature controls at about 60 DEG C, and heating makes ammonia volatilization form ammonia steam, and this ammonia steam enters in intermediate reaction thing by arm, adjusts
The pH value of joint intermediate reaction thing is to obtaining intermediate reaction thing after regulation in the range of 8 ~ 11, and now Titanium is 1 with the mol ratio of ammonia:
9~15；
Intermediate reaction thing 3 ~ 8 hours after step 4, continuously stirred regulation, until it is water-soluble to obtain transparent yellow complex
Liquid；
Step 5, yellow complex aqueous solution is transferred in the flask of band arm, puts in the hot bath of about 60 DEG C,
Evaporation removes hydrogen peroxide and the ammonia of excess, obtains yellow complex colloid；
Step 6, yellow complex colloid is poured in autoclave, 150 DEG C ~ 200 DEG C hydro-thermal reactions 4 ~ 8 hours, obtain
Obtain pure white water-based emulsion；
Step 7, pure white water-based emulsion is refunded in glass beaker, under room temperature, add mineral acid, regulation breast while stirring
The pH value of liquid obtains water-based emulsion after being acidified to 2 ~ 4；
Step 8, glass beaker is put in 60～80 DEG C of water bath devices, water after making acidifying at continuously stirred 3～6 hours
Property emulsion gel gradually becomes nanometer titanium dioxide water colloid.
In technique scheme, further improved plan is as follows:
1., in such scheme, in described aqueous hydrogen peroxide solution, content of hydrogen peroxide is 30%, proportion 1.1g/ml.
2., in such scheme, described moderate-speed mixer speed is 300 ~ 600 revs/min.
3. in such scheme, described ammonia content 26%, proportion 0.9g/ml.
4. in such scheme, the ammonia evaporated in described step 5 is passed through in pure water, recyclable uses again.
5., in such scheme, described mineral acid is any one in dilute hydrochloric acid, dilute sulfuric acid or dust technology.
Owing to technique scheme is used, the present invention compared with prior art has following advantages and an effect:
The preparation method of high efficiency photocatalyst of the present invention-nanometer titanium dioxide water colloid, it is to be entirely inorganic conjunction
Become, do not use any organic solvent, course of reaction produces without waste water, waste gas, be a kind of clean preparation technology；Secondly, use
High-purity titanium sponge, aqueous hydrogen peroxide solution are as main material and combine specific processing step and parameter, can make titanium dioxide
Theoretical earning rate is up to 166%, and cost of material is substantially reduced compared with other patent technique, greatly reduces raw material impurity
The probability introduced, thus improve the stability of product and purity and performance；Again, nano titanium oxide prepared by the present invention is used
Aqueous colloidal grain diameter is good less than 10 nanometers and particle uniformity, and degree of crystallinity is high, has the strongest photocatalytic activity；And many
Paintability and filming performance on the base material of hole are the best, can make high efficiency photocatalysis agent film, apply at air and water
Field of purification, under the irradiation of ultraviolet light can high with various poisonous, the harmful organic pollution of oxidation Decomposition, formaldehyde clearance and
The removal time is greatly shortened, and sterilizing rate is high and the time is short simultaneously.
Accompanying drawing explanation
Accompanying drawing 1 amplifies 140,000 times of nano-TiOs for the present invention2Aqueous colloidal transmission electron microscope shape appearance figure；
Accompanying drawing 2 is nano-TiO of the present invention2Aqueous colloidal particle size distribution figure；
Accompanying drawing 3 is the application example of high efficiency photocatalyst of the present invention--Formaldehyde decomposition curve；
Accompanying drawing 4 is the application example of high efficiency photocatalyst of the present invention--bactericidal effect curve.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described:
Embodiment 1: the preparation method of a kind of high efficiency photocatalyst-nanometer titanium dioxide water colloid, comprises the following steps:
Step one, 5 grams of Titaniums are put in 500 milliliters of glass beakers, add 85 milliliters of aqueous hydrogen peroxide solutions, metal
Titanium is 1:8 with the mol ratio of hydrogen peroxide, and described Titanium is participated sponge titanium；
Step 2, being placed in ice-water bath by glass beaker, ice-water bath temperature controls at about 10 DEG C, mixed described in moderate-speed mixer
Close liquid thing and form intermediate reaction thing；
Step 3,75 milliliters of ammonia are poured in 500 milliliters of flasks of band arm and piston, flask is placed in about 60 DEG C
Temperature control hot bath in, be thermally formed ammonia steam, ammonia steam by arm enter moderate-speed mixer intermediate reaction thing in, treat centre
The pH value of reactant reaches to close the piston on flask arm when about 9, stops logical ammonia, and Titanium is about with the mol ratio of ammonia
1:10；
Step 4, continuously stirred reaction 6 hours, period can repeatedly open the piston on flask arm, and logical ammonia is to keep
PH value, about 9, obtains transparent yellow complex TiO [(H2O2)]2+Aqueous solution；
Step 5, by yellow complex TiO [(H2O2)]2+Aqueous solution is transferred in the flask of band arm, puts into 60 DEG C of left sides
In right hot bath, evaporation removes hydrogen peroxide and the ammonia of excess, obtains yellow complex colloid, and the ammonia evaporated is passed through pure water
In, recyclable use again；
Step 6, again yellow complex colloid is poured in autoclave, 150 DEG C of hydro-thermal reactions 8 hours, obtain pure white
The Ti (OH) of color4Water-based emulsion；
Step 7, by lily Ti (OH)4Water-based emulsion is refunded in glass beaker, drips 40% under room temperature while stirring
Dust technology, regulation emulsion pH value obtains within the scope of 2 ~ 2.5 be acidified after water-based emulsion；
Step 8, being put into by glass beaker in heated for controlling temperature water bath device, bath temperature controls at about 60 DEG C, during stirring
Between be 5 hours, after making acidifying under continuous stirring, water-based emulsion gel gradually becomes nanometer titanium dioxide water colloid, weighs about 80 grams
Left and right, in colloid, the content of titanium dioxide is about 10% wt.
In above-mentioned aqueous hydrogen peroxide solution, content of hydrogen peroxide is 30%, proportion 1.1g/ml, and above-mentioned moderate-speed mixer speed is
400 revs/min；
Above-mentioned ammonia content 26%, proportion 0.9g/ml；The ammonia evaporated in above-mentioned steps five is passed through in pure water, recyclable again
With.
Fig. 1 is the nanometer titanium dioxide water colloid transmission electron microscope of the preparation method acquisition of the present embodiment high efficiency photocatalyst
Photo, can show that from photo granule presents near-spherical, and particle diameter is less than 10nm(and the scale pair of lower right corner 100nm in figure
Than), the bright colloidal solid of right chart belongs to anatase phase.
Fig. 2 is the nanometer titanium dioxide water colloidal solid particle diameter of the preparation method acquisition of the present embodiment high efficiency photocatalyst
Scattergram, average particulate diameter is less than 10nm.
Fig. 3 is that the nanometer titanium dioxide water colloid of the preparation method acquisition of the present embodiment high efficiency photocatalyst is made pottery in porous
Spray on porcelain base material, sinter and make high efficiency photocatalysis agent film, the Formaldehyde decomposition curve recorded under ultraviolet light irradiation, test machine
Structure is Chinese environmental and energy nano material development center, and through the light-catalyzed reaction of 60 minutes, concentration of formaldehyde was from initial
1.05ppm drops to 0.05ppm, and clearance is high and the time of removal is short.
Fig. 4 is that the nanometer titanium dioxide water colloid of the preparation method acquisition of the present embodiment high efficiency photocatalyst is made pottery in porous
Spray on porcelain base material, sinter and make high efficiency photocatalysis agent film, the bactericidal effect curve recorded under ultraviolet light irradiation, Shanghai City
The detection of environmental protection product quality supervision and test master station, test condition: temperature 23 ~ 27 DEG C, relative humidity 40 ~ 60%, the test space
30 cubic metres of experimental cabins；Total bacterium clearance is drawn: 30 minutes, more than 70% from accompanying drawing 4；60 minutes, more than 99%.
Embodiment 2: the preparation method of a kind of high efficiency photocatalyst-nanometer titanium dioxide water colloid, comprises the following steps:
Step one, 5 grams of Titaniums are put in glass beaker, add 107mL aqueous hydrogen peroxide solution and form mixed liquor, gold
The mol ratio belonging to titanium and hydrogen peroxide is 1:10, and described Titanium is participated sponge titanium；
Step 2, being placed in ice-water bath by glass beaker, ice-water bath temperature controls between 12 DEG C, mixed described in moderate-speed mixer
Close liquid thing and form intermediate reaction thing；
Step 3, the ammonia of 91mL is poured in the flask of band arm and piston, flask is placed in hot bath, water-bath temperature
Degree controls at about 60 DEG C, and heating makes ammonia volatilization form ammonia steam, and this ammonia steam enters in intermediate reaction thing by arm, regulation
The pH value of intermediate reaction thing is to obtaining intermediate reaction thing after regulation in the range of 9.5, and now Titanium is 1:12 with the mol ratio of ammonia；
Intermediate reaction thing 5 hours after step 4, continuously stirred regulation, until obtaining transparent yellow complex TiO
[(H2O2)]2+Aqueous solution；
Step 5, yellow complex aqueous solution is transferred in the flask of band arm, puts in the hot bath of about 60 DEG C,
Evaporation removes hydrogen peroxide and the ammonia of excess, obtains yellow complex colloid；
Step 6, yellow complex colloid is poured in autoclave, 175 DEG C of hydro-thermal reactions 7 hours, it is thus achieved that pure white
Ti(OH)4Water-based emulsion；
Step 7, by pure white Ti (OH)4Water-based emulsion is refunded in glass beaker, adds inorganic under room temperature while stirring
Acid, the pH value of regulation emulsion to 3.0 ~ 3.5 obtains water-based emulsion after acidifying；
Step 8, glass beaker is put in 70 DEG C of water bath devices, water-based emulsion after making acidifying at continuously stirred 4.5 hours
Gradually gel becomes nanometer titanium dioxide water colloid, weighs about about 110 grams, and in colloid, the content of titanium dioxide is about 7.6%
wt。
As preferably, the Titanium of employing is participated sponge titanium, greatly reduces the probability of the introducing of raw material impurity, thus
Improve product and purity and the stability of performance.
As preferably, using in step 3 and be placed in hot bath by flask, bath temperature controls at about 60 DEG C, and heating makes
Ammonia volatilization forms ammonia steam, and this ammonia steam is entered in intermediate reaction thing by arm.Use logical ammonia rather than drip ammonia
It is the concentration in order to keep hydrogen peroxide in reactant that way regulates the reason of pH value, it is to avoid dropping ammonia can diluting reaction
Liquid, thus response speed can be made to reduce, the response time increases.
Above-described embodiment, only for technology design and the feature of the explanation present invention, its object is to allow person skilled in the art
Scholar will appreciate that present disclosure and implements according to this, can not limit the scope of the invention with this.All according to the present invention
The equivalence that spirit is made changes or modifies, and all should contain within protection scope of the present invention.
Claims (4)
1. the preparation method of high efficiency photocatalyst-nanometer titanium dioxide water colloid, it is characterised in that: include following step
Rapid:
Step one, Titanium is put in glass beaker, add aqueous hydrogen peroxide solution and form mixed liquor, Titanium and peroxidating
The mol ratio of hydrogen is 1:8 ~ 12, and described Titanium is participated sponge titanium；
Step 2, being placed in ice-water bath by glass beaker, ice-water bath temperature controls between 5～15 DEG C, mixed described in moderate-speed mixer
Close liquid thing and form intermediate reaction thing；
Step 3, a certain amount of ammonia is poured in the flask of band arm and piston, flask is placed in hot bath, bath temperature
Controlling at about 60 DEG C, heating makes ammonia volatilization form ammonia steam, and this ammonia steam enters in intermediate reaction thing by arm, in regulation
Between the pH value of reactant in the range of 8 ~ 11, it is thus achieved that intermediate reaction thing after regulation, now the mol ratio of Titanium and ammonia be 1:9 ~
15；
Intermediate reaction thing 3 ~ 8 hours after step 4, continuously stirred regulation, until obtaining transparent yellow complex aqueous solution；
Step 5, yellow complex aqueous solution is transferred in the flask of band arm, puts in the hot bath of about 60 DEG C, evaporation
Remove the hydrogen peroxide of excess, obtain yellow complex colloid；
Step 6, yellow complex colloid is poured in autoclave, 150 DEG C ~ 200 DEG C hydro-thermal reactions 4 ~ 8 hours, it is thus achieved that pure
White water-borne emulsion；
Step 7, pure white water-based emulsion is refunded in glass beaker, under room temperature, add mineral acid while stirring, regulation emulsion
PH value obtains water-based emulsion after being acidified to 2～4；
Step 8, glass beaker is put in 60～80 DEG C of water bath devices, within continuously stirred 3～6 hours, make water-based emulsion after acidifying
Gradually gel becomes nanometer titanium dioxide water colloid.
The preparation method of high efficiency photocatalyst the most according to claim 1-nanometer titanium dioxide water colloid, its feature exists
In: in described aqueous hydrogen peroxide solution, content of hydrogen peroxide is 30%, proportion 1.1g/ml.
The preparation method of high efficiency photocatalyst the most according to claim 1-nanometer titanium dioxide water colloid, its feature exists
In: described moderate-speed mixer speed is 300 ~ 600 revs/min.
The preparation method of high efficiency photocatalyst the most according to claim 1-nanometer titanium dioxide water colloid, its feature exists
In: described ammonia content 26%, proportion 0.9g/ml.
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| CN106629835B (en) * | 2016-11-18 | 2018-03-23 | 浙江理工大学 | A kind of controllable method for preparing of titania nanoparticles |
| CN107473770B (en) * | 2017-06-27 | 2020-06-30 | 唐山佐仑环保科技有限公司 | Manufacturing process of photocatalyst film composite ceramic |
| WO2022007764A1 (en) * | 2020-07-06 | 2022-01-13 | 宁波极微纳新材料科技有限公司 | Method for preparing titanium dioxide and method for improving titanium dioxide dispersibility |
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Denomination of invention: Preparation method for high-efficient photocatalyst-nanometer titanium dioxide water-based colloid Effective date of registration: 20180206 Granted publication date: 20170111 Pledgee: Suzhou Xinsheng Financing Leasing Co., Ltd. Pledgor: Jiangsu Hengzhi Nano Technology Co., Ltd. Registration number: 2018320010006 |
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Date of cancellation: 20210111 Granted publication date: 20170111 Pledgee: Suzhou Xinsheng Financing Leasing Co.,Ltd. Pledgor: JIANGSU EVER SMART NANOTECHNOLOGY Co.,Ltd. Registration number: 2018320010006 |