CN1330414C - Method for preparing anatase type nano titanium dioxide photocatalyst - Google Patents
Method for preparing anatase type nano titanium dioxide photocatalyst Download PDFInfo
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- CN1330414C CN1330414C CNB2005100472304A CN200510047230A CN1330414C CN 1330414 C CN1330414 C CN 1330414C CN B2005100472304 A CNB2005100472304 A CN B2005100472304A CN 200510047230 A CN200510047230 A CN 200510047230A CN 1330414 C CN1330414 C CN 1330414C
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- hydrolysis
- anatase type
- aqueous solution
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Abstract
The present invention provides a preparation method for an anatase type nanometer titanium dioxide photocatalyst. The present invention is characterized in that a titanium sulfate water solution is heated to boil to make the titanium sulfate hydrolyzed to generate sodium titanium dioxide crystal nucleus; ammonium hydroxide is used for gradually and upwards adjusting the pH value of the solution; the hydrolysis of the titanium sulfate is accelerated to make the sodium titanium dioxide uniformly grow and completely deposited; the deposition is separated, washed, dried and calcined at 300 to 600 DEG C to obtain the anatase type nanometer titanium dioxide photocatalyst. The technique has the advantages of low cost, short flow, no pollution, high yield and easy realization of industrialization. Obtained products are characterized in that the average value of primary particle diameters is from 5 to 25 nm, and the products exist in a coacervate form. The anatase type nanometer titanium dioxide photocatalyst can effectively degrade organic pollutants in water under the action of ultraviolet light or sunlight and has bactericidal action; the photocatalyst has the advantages of repeatable use and hard leakage.
Description
Technical field
The invention belongs to field of fine chemical, particularly a kind of preparation method of anatase type nano titanium dioxide photocatalyst.
Background technology
At present, development of new organic pollutant wastewater treatment technology is needed in the whole world badly, and with the environment sustainable development that guarantees that the mankind depend on for existence, people drop into photocatalytic titanium oxide degradation technique that big energy studies very much and are expected to become and handle the organic pollutant wastewater new technique.
It is Detitanium-ore-type, rutile-type and brookite type that titanium dioxide has three kinds of crystal formations, and wherein the Detitanium-ore-type photocatalytic activity is the strongest, and this activity reduces and significantly increases with particle diameter.
Sulfuric acid process be industrial preparation anatase titanium dioxide common method [Tang Zhenning. the production of titanium dioxide and environmental improvement (M). Beijing: Chemical Industry Press, 2001.108-139], the core of this method is titanium sulfate (Ti (SO
4)
2) pyrohydrolysis, the pyrohydrolysis of titanium sulfate divides automatic growing crystal species dilution water solution and plus seed Hydrolyze method again, the former is added to a part of titanium liquid in the hot water earlier, makes and himself generates crystal seed, then all the other titanium liquid is added again and carries out heating hydrolysis; The latter earlier makes a part of titanium liquid to be added to behind the crystal seed with the alkali neutralization again and carries out heating hydrolysis in the titanium liquid.Hydrolysate obtains the micron order anatase titanium dioxide after washing, calcining.This method long flow path, productive rate are low, and the acid waste water that hydrolysis produces can produce environmental pollution.
The titanium dioxide group of Japan chemical company of kingdom, Ishihara Sangyo Kaisha, Ltd., Finland Kai Mila company, Britain uses titanyl sulfate (TiOSO
4) the solution neutralisation prepares superfine titanic oxide, this method is preparation metatitanic acid earlier, wash qualified back and generates titanyl sulfate solution with sulfuric acid reaction, adds alkali neutralizing hydrolysis generation TiO (OH) again
2, be sintered into product then.This product serves many purposes, but with regard to as the photochemical catalyst that is used to handle waste water, easily runs off during this product use, and it is loaded down with trivial details that preparation technology also shows slightly.Direct precipitation method in the liquid-phase precipitation method that patent CN1312223A proposes and patent CN1373089 are similarly.
Patent CN1579946A is with metatitanic acid (H
2TiO
3) be raw material, adopt the Preparation by Uniform Precipitation anatase-type nanometer titanium dioxide.At first make metatitanic acid and sulfuric acid reaction, generate titanyl sulfate solution; In above-mentioned solution, add hydrogen peroxide, urea is made flocculant, adds ammoniacal liquor, NaOH is made precipitating reagent, adds absolute ethyl alcohol or triethanolamine and makes dispersant, the use of these materials has increased the cost of this method.
Patent CN1312335 contains Fe in 50-100 ℃ through hydrolysis in 3-8 hour under normal pressure
2+Titanic liquid generate metatitanic acid, the filter cake of washing after qualified pulled an oar with deionized water, adjusting pH with NaOH is 6-9, the water making beating once more of the filter cake after the washing, heats up, adds MEA again and disperse, after roasting, pulverizing make nano-anatase mine-titanium oxide.This method exist long flow path and loaded down with trivial details, productive rate is low, the shortcoming of contaminated environment.
Patent CN1415550A is a raw material with industrial sulphuric acid titanium liquid, handles by the 80-150 ℃ of pre-crystallization of hydro-thermal, and precipitation separation again through 350-800 ℃ of high temperature sintering, is prepared single dispersing nanometer grade anatase type TiO then
2This method productive rate is low, and hydrolysis produces acid waste water.
Patent CN1287099A is after evenly heating makes the titanium solution complete hydrolysis by microwave, and with the alkali neutralization, isolated sediment makes the nano titanium oxide of the arbitrary size distribution of particle diameter between 10-100nm through washing, dry, calcining.This method has increased equipment investment because of using heating using microwave, and embodiment uses NaOH to make precipitating reagent, is unfavorable for obtaining the nano titanium oxide of highlight catalytic active.
Patent CN1491897 has proposed to prepare at low temperature the method for the anatase type nano crystal titanium dioxide of highlight catalytic active, this method comprises with the hydrated titanium dioxide being primary raw material, through alkaline hydrolysis, cool off, add processes such as nucleus promoter, washing, acid are molten, cooling, filter wash, drying, pulverizing and make the product of average particle size range at 10-80nm, but this method is too loaded down with trivial details.
Summary of the invention
The purpose of this invention is to provide simple and easy, cost is low, flow process is short, pollution-free, productive rate is high, preparation has a preparation method of highly active anatase type nano titanium dioxide photocatalyst.
The objective of the invention is to implement by following step:
(1) compound concentration is the titanium sulfate aqueous solution of 0.1-1.0mol/L, and compound concentration is the ammonia spirit of 1.0-7.0mol/L,
(2) under agitation, the titanium sulfate aqueous solution for preparing is heated to boiling, and keeps refluxing, make the quick hydrolysis of titanium sulfate, evenly produce the hydrated titanium dioxide nucleus,
(3) behind the above-mentioned titanium sulfate aqueous solution boiling reflux 20-100min that has begun hydrolysis, stop heating, lower the temperature naturally,
(4) treat that above-mentioned aqueous temperature reduces to below 85 ℃, under agitation, drip the ammonia spirit for preparing, heighten pH value of solution gradually, make the titanium sulfate hydrolysis complete, form the hydrated titanium dioxide precipitation to 6-8.5,
(5) isolate the hydrated titanium dioxide precipitation, be washed to no SO
4 2-,
(6) hydrated titanium dioxide is deposited in 80-120 ℃ of following oven dry 1-3h and obtains the hydrated titanium dioxide powder,
(7) with the hydrated titanium dioxide powder in 300-600 ℃ of following roasting 1-3h, obtain existing with the aggregate form,
Primary particle size mean value is the anatase type nano titanium dioxide photocatalyst of 5-25nm.
Principle of the present invention is as follows:
Utilize Ti (SO
4)
2Aqueous solution hydrolysis outburst under fluidized state forms hydrated titanium dioxide (TiO
2H
2O) the nucleus principle is carried out evenly nucleation (promptly breaking out the nucleation principle) fast; Afterwards, add ammoniacal liquor and reconcile the pH value, the TiO in the control aqueous solution
2H
2O concentration is: C
s＜C
TiO2H2o＜C
Min, C
sBe solution saturated concentration, C
MinFor critical nucleation concentration, make TiO
2H
2O evenly grows up; By the TiO that produces in the hydrolysis
2Core when beginning as roasting evenly makes the transition, and curve a confirms this TiO among Fig. 1
2The existence of nucleus, transition, temperature should be lower than 700 ℃, otherwise, rutile titanium dioxide (seeing curve g and h among Fig. 1) appears in the product, obtain the uniform target product of particle diameter thus.
Characteristics of the present invention are as follows:
1, makes Ti (SO earlier
4)
2The aqueous solution is hydrolysis fast under the atmospheric boiling state, evenly produces TiO
2H
2The O nucleus.The speed of hydrolysis rate can be investigated with the time that cloud point appears in solution, and time of cloud point occurring, short then hydrolysis rate is fast, otherwise then slow.Experimental results show that: under normal pressure, the time that occurs cloud point during boiling is the shortest, so, under normal pressure, Ti (SO during boiling
4)
2Hydrolysis is the fastest.
2, add ammoniacal liquor after hydrolysis a period of time, in the ammoniacal liquor energy of adding and Ti (SO
4)
2A large amount of acid that hydrolysis produces, this makes on the one hand reconciles TiO in the aqueous solution
2H
2The degree of supersaturation of O becomes possibility, thereby makes TiO
2H
2O evenly grows up, and can shorten the complete time of hydrolysis on the other hand, improves productive rate, and this process yield is higher than 90%.The ammoniacal liquor that adds can make the photocatalytic activity of product be higher than with other common alkali (as NaOH, Na
2CO
3) as the photocatalytic activity of product that precipitating reagent obtains.Volatile because of ammoniacal liquor, be necessary in the process of cooling, to add.
3, the condition that is prepared as follows that the present invention is given, that is: titanium sulfate aqueous solution concentration is 0.1-1.0mol/L; The titanium sulfate aqueous solution boiling reflux 20-100min that maintenance has begun hydrolysis; With concentration is the ammonia spirit adjust pH of 2.0-7.0mol/L; 300-600 ℃ of following roasting is the optimum condition that obtains to have high light catalytic activity target product.
4, the condition that is prepared as follows that the present invention is given, that is: titanium sulfate aqueous solution concentration is 0.3-1.0mol/L; The titanium sulfate aqueous solution boiling reflux 25-70min that maintenance has begun hydrolysis; With concentration is the ammonia spirit adjust pH of 2.0-5.0mol/L; 300-600 ℃ of following roasting is to obtain to have the more optimum condition of highlight catalytic active target product.
5, under the given condition that is prepared as follows of the present invention, that is: titanium sulfate aqueous solution concentration is 0.5mol/L; The titanium sulfate aqueous solution boiling reflux 40min that maintenance has begun hydrolysis; With concentration is the ammonia spirit adjust pH of 2.0mol/L; 400 ℃ of following roastings, can with high efficiency more and more low energy consumption production have the more target product of highlight catalytic active.
4, the feature of this product is that primary particle size mean value is 5-25nm, exists with the aggregate form.
5, the feature of this product is under the effect of ultraviolet light or sunshine, but organic pollution in the efficient degradation water, and have bactericidal action, this catalyst is reusable, is difficult for running off.
6, this is simple for process, and is efficient, cost is low, pollution-free, easily realize industrialization.
Description of drawings
Fig. 1: the hydrated titanium dioxide powder is through the X-ray diffractogram of heat treatments at different 2h.
A.100 ℃ b.200 ℃ c.300 ℃ (product) d.400 ℃ (product) e.500 ℃ (product) f.600 ℃ (product) g.700 ℃ h.800 ℃
The transmission electron microscope photo of the product of Fig. 2: embodiment 1 preparation.
The specific embodiment
Below by embodiment in detail the specific embodiment of the present invention is described in detail, but not only is confined to following examples.
Embodiment 1
Prepare anatase type nano titanium dioxide photocatalyst by following step:
(1) compound concentration is the titanium sulfate aqueous solution of 0.5mol/L, and compound concentration is the ammonia spirit of 2.0mol/L,
(2) under agitation, the titanium sulfate aqueous solution for preparing is heated to boiling, and keeps refluxing, make the quick hydrolysis of titanium sulfate, evenly produce the hydrated titanium dioxide nucleus,
(3) behind the above-mentioned titanium sulfate aqueous solution boiling reflux 40min that has begun hydrolysis, stop heating, lower the temperature naturally,
When (4) treating that above-mentioned aqueous temperature is reduced to 80 ℃, under agitation, drip the ammonia spirit for preparing, heighten pH value of solution value to 8.5 gradually, make the titanium sulfate hydrolysis complete, form the hydrated titanium dioxide precipitation,
(5) isolate the hydrated titanium dioxide precipitation, be washed to no SO
4 2-,
(6) hydrated titanium dioxide is deposited in 100 ℃ of oven dry 2h down, obtains the hydrated titanium dioxide powder,
(7) with the hydrated titanium dioxide powder in 400 ℃ of following roasting 2h, obtain existing with the aggregate form, primary particle size mean value is Detitanium-ore-type (seeing curve d among Fig. 1) nano titanium dioxide photocatalyst of 10nm (see figure 2).
The photochemical catalyst degrade methyl orange that makes with embodiment 1.Methyl orange is a kind of common and dye molecule of being difficult to degrade, often is used to carry out the active testing test of light degradation organic molecule.0.1g photochemical catalyst (28 ℃ of temperature) under sunshine with embodiment 1 makes can be degraded 25ml 16ppm methyl orange 1h fully; Under the radiation of 10W-254nm uviol lamp, 25ml 20ppm methyl orange 20min can be decoloured fully, promptly percent of decolourization 100%.This shows that the prepared catalyst of the present invention has very high photocatalytic activity, the ability of degraded methyl orange is higher than the photocatalytic activity of like product far away.
Making 0.4g photochemical catalyst degradable 100ml CODcr with embodiment 1 is 1400 De perylene based dye actual waste water, (28 ℃ of temperature) the degraded 4h or the 1h that under the ultraviolet light of 254nm, degrades under sunshine, CODcr can be reduced to below 115, catalyst is reusable.
With the experiment of sterilizing of embodiment 1 gained 0.1g photochemical catalyst, with the radiation 1h of 10W-254nm uviol lamp, for bacterium in the actual lake water, sterilization rate is 93.9%; For Escherichia coli in the water (artificial preparation), sterilization rate is 71.5%; For assorted bacterium in the water (artificial preparation), sterilization rate is 93.1%.Sterilization rate increases along with the increase of time.
Embodiment 2～embodiment 9
The preparation method of embodiment 2～embodiment 9 is except that certain preparation condition changes, and other is all with embodiment 1.
The sign of the preparation condition of embodiment 2～embodiment 9 and the corresponding product that obtains is listed in the table 1.
Use the product photocatalyst of embodiment 2～embodiment 9 gained respectively, make the degraded target compound with methyl orange.The product consumption of embodiment 2～embodiment 9 gained is 0.1g, handles 25ml 20ppm methyl orange solution, and with the radiation 20min of 10W-254nm uviol lamp, experimental result is also listed in the table 1.
Table 1 preparation condition, product characterize and methyl orange decolouring situation
| Sequence number | Preparation condition | Product characterizes | Methyl orange percent of decolourization (%) | ||||
| Titanium sulfate aqueous solution concentration (mol/L) | Ammonia concn (mol/L) | The boiling reflux time (min) | Sintering temperature (℃) | Crystal formation | Primary particle size mean value (nm) | ||
| Embodiment 2 | 0.5 | 2 | 40 | 300 | Anatase | 5.2 | 88.1 |
| Embodiment 3 | 0.5 | 2 | 40 | 500 | Anatase | 14.4 | 97.0 |
| Embodiment 4 | 0.5 | 2 | 40 | 600 | Anatase | 16.7 | 100.0 |
| Embodiment 5 | 0.5 | 7 | 40 | 600 | Anatase | 18.5 | 86.1 |
| Embodiment 6 | 0.5 | 2 | 25 | 600 | Anatase | 11.3 | 97.0 |
| Embodiment 7 | 0.5 | 2 | 70 | 600 | Anatase | 19.1 | 100.0 |
| Embodiment 8 | 0.1 | 2 | 40 | 600 | Anatase | 11.0 | 84.2 |
| Embodiment 9 | 1.0 | 2 | 40 | 600 | Anatase | 16.7 | 95.8 |
Claims (5)
1, a kind of preparation method of anatase type nano titanium dioxide photocatalyst is characterized in that comprising the steps:
(1) compound concentration is the titanium sulfate aqueous solution of 0.1-1.0mol/L, and compound concentration is the ammonia spirit of 2.0-7.0mol/L,
(2) under agitation, the titanium sulfate aqueous solution for preparing is heated to boiling, and keeps refluxing, make the quick hydrolysis of titanium sulfate, evenly produce the hydrated titanium dioxide nucleus,
(3) behind the above-mentioned titanium sulfate aqueous solution boiling reflux 20-100min that has begun hydrolysis, stop heating, lower the temperature naturally,
When (4) treating that above-mentioned aqueous temperature is reduced to below 85 ℃, under agitation, drip the ammonia spirit for preparing, heighten the pH value of solution value gradually, make the titanium sulfate hydrolysis complete, form the hydrated titanium dioxide precipitation to 6-8.5,
(5) isolate the hydrated titanium dioxide precipitation, be washed to no SO
4 2-,
(6) hydrated titanium dioxide is deposited in 80-120 ℃ of oven dry 1-3h down, obtains the hydrated titanium dioxide powder,
(7) with the hydrated titanium dioxide powder in 300-600 ℃ of following roasting 1-3h, obtain existing with the aggregate form, primary particle size mean value is the anatase type nano titanium dioxide photocatalyst of 5-25nm.
2, by the preparation method of the described anatase type nano titanium dioxide photocatalyst of claim 1, it is characterized in that described titanium sulfate aqueous solution compound concentration is 0.3-1.0mol/L.
3, by the preparation method of the described anatase type nano titanium dioxide photocatalyst of claim 1, it is characterized in that described ammonia spirit compound concentration is 2.0-5.0mol/L.
4, by the preparation method of the described anatase type nano titanium dioxide photocatalyst of claim 1, it is characterized in that the described titanium sulfate aqueous solution boiling reflux 25-70min that has begun hydrolysis.
5, by the preparation method of the described anatase type nano titanium dioxide photocatalyst of claim 1, it is characterized in that comprising the steps:
(1) compound concentration is the titanium sulfate aqueous solution of 0.5mol/L, and compound concentration is the ammonia spirit of 2.0mol/L,
(2) under agitation, the titanium sulfate aqueous solution for preparing is heated to boiling, and keeps refluxing, make the quick hydrolysis of titanium sulfate, evenly produce the hydrated titanium dioxide nucleus,
(3) behind the above-mentioned titanium sulfate aqueous solution boiling reflux 40min that has begun hydrolysis, cooling naturally,
When (4) treating that above-mentioned aqueous temperature is reduced to 80 ℃, under agitation, drip the ammonia spirit for preparing, heighten pH value of solution value to 8.5 gradually, make the titanium sulfate hydrolysis complete, form the hydrated titanium dioxide precipitation,
(5) isolate the hydrated titanium dioxide precipitation, be washed to no SO
4 2-,
(6) hydrated titanium dioxide is deposited in 100 ℃ of oven dry 2h down, obtains the hydrated titanium dioxide powder,
(7) with the hydrated titanium dioxide powder in 400 ℃ of following roasting 2h, obtain existing with the aggregate form, primary particle size mean value is the anatase-type nanometer titanium dioxide of 10nm.
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| CN101757906B (en) * | 2008-12-23 | 2012-01-18 | 南京大学 | Preparation method for V-Ti-Al-O composite catalyst for methylal synthesis through methanol oxidation |
| WO2015016779A1 (en) * | 2013-07-29 | 2015-02-05 | National University Of Singapore | Titanium dioxide photocatalysts for reverse osmosis concentrate recovery |
| CN114425330B (en) * | 2022-01-14 | 2023-07-28 | 山东大学 | Double noble metal loaded nano titanium dioxide and preparation method and application thereof |
Citations (4)
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|---|---|---|---|---|
| EP0722905A1 (en) * | 1995-01-20 | 1996-07-24 | Tioxide Group Services Limited | Preparation of anatase titanium dioxide |
| CN1373089A (en) * | 2002-02-01 | 2002-10-09 | 武汉大学 | Process for preparing anatase-phase nano TiO2 |
| CN1415550A (en) * | 2002-12-12 | 2003-05-07 | 中山大学 | Method for preparing nano titanium dioxide in anatase type from fluid of hydrothermal crystallized titanium sulfate |
| CN1478725A (en) * | 2003-01-13 | 2004-03-03 | 复旦大学 | Preparation method of crystal phase controllable titanium dioxide nanometer crystal |
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2005
- 2005-09-20 CN CNB2005100472304A patent/CN1330414C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| EP0722905A1 (en) * | 1995-01-20 | 1996-07-24 | Tioxide Group Services Limited | Preparation of anatase titanium dioxide |
| CN1373089A (en) * | 2002-02-01 | 2002-10-09 | 武汉大学 | Process for preparing anatase-phase nano TiO2 |
| CN1415550A (en) * | 2002-12-12 | 2003-05-07 | 中山大学 | Method for preparing nano titanium dioxide in anatase type from fluid of hydrothermal crystallized titanium sulfate |
| CN1478725A (en) * | 2003-01-13 | 2004-03-03 | 复旦大学 | Preparation method of crystal phase controllable titanium dioxide nanometer crystal |
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| Title |
|---|
| 晶种对硫酸钛液水解过程影响的研究 法浩然，朱贤荣，谢登岗，现代涂料与涂装，第6期 2003 * |
| 晶种对硫酸钛液水解过程影响的研究 法浩然，朱贤荣，谢登岗，现代涂料与涂装，第6期 2003;纳米二氧化钛制备工艺研究进展 吴迪，王鼎聪，赵德智，钛工业进展，第22卷第3期 2005;锐钛矿型纳米二氧化钛的制备方法及其在抗菌材料中的应用 包春磊，符新，王江，廖小雪，赵同建，热带农业科学，第23卷第6期 2003;水热晶化法制备纳米TiO_2的动力学研究 吕德义，王晖，郇昌永，周春晖，葛忠华，浙江工业大学学报，第32卷第1期 2004 * |
| 水热晶化法制备纳米TiO_2的动力学研究 吕德义，王晖，郇昌永，周春晖，葛忠华，浙江工业大学学报，第32卷第1期 2004 * |
| 纳米二氧化钛制备工艺研究进展 吴迪，王鼎聪，赵德智，钛工业进展，第22卷第3期 2005 * |
| 锐钛矿型纳米二氧化钛的制备方法及其在抗菌材料中的应用 包春磊，符新，王江，廖小雪，赵同建，热带农业科学，第23卷第6期 2003 * |
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