CN101513609A - Photocatalyst for water treatment and preparation and application thereof - Google Patents
Photocatalyst for water treatment and preparation and application thereof Download PDFInfo
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- CN101513609A CN101513609A CNA2009100296048A CN200910029604A CN101513609A CN 101513609 A CN101513609 A CN 101513609A CN A2009100296048 A CNA2009100296048 A CN A2009100296048A CN 200910029604 A CN200910029604 A CN 200910029604A CN 101513609 A CN101513609 A CN 101513609A
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Abstract
The invention discloses a photocatalyst for water treatment. The photocatalyst is prepared in a manner that nanometer titania modifies silica power, silicon is selected from either monocrystal line silicon or polysilicon, and nanometer titania is composed of 60%-80% of anatase phase and 20%-40% of rutile phase titanium dioxide. Titanium dioxide is loaded on the surface of silica power, thus benefiting the separation of photocarriers and electrons and promoting catalysts to absorb and utilize visible light. In the preparation of catalyst, by changing roasting temperature to control the proportion of anatase phase and rutile phase in titanium dioxide, the catalytic performance of catalyst is improved. The catalyst has good photo-catalytic oxidation performance on benzene series such as toluene in water, wherein, the removal rate of toluene is over 90%. Reusing the catalyst for 9 times, the removal rate of toluene is still greater than 80%, the recovery utilization rate of the catalyst is over 90%, thus the catalyst has the characteristics of high catalytic efficiency and fast speed, moderate reaction, convenient operation and the like.
Description
Technical field
The invention belongs to the photochemical catalyst in water, waste water or the sewage treatment area, be specifically related to a kind of silicon/TiO2 photochemical catalyst and preparation method thereof.
Background technology
In recent years, the photochemical catalytic oxidation water technology of based semiconductor material has received various countries scholars' concern, in photochemical catalytic oxidation dynamics, the preparation of nano material, finishing, fixing phase catalyst, aspects such as mechanism of degradation and treatment of Organic Wastewater have obtained a large amount of achievements.The design of high efficiency photocatalyst and preparation are the core topic of photochemical catalytic oxidation research.Problems such as existing photochemical catalytic oxidation catalyst ubiquity efficient is not high, and especially reusable number of times is few, efficient is low.TiO
2Crystal formation catalytic oxidation efficient is also had tangible influence, but research in this regard is not deeply.
The catalyst of photochemical catalytic oxidation at present is with TiO
2Be main, its carrier has zeolite, activated carbon (fiber), CuMn, beta-schardinger dextrin-/Ce, SiO
2, Al
2O
3, glass fiber mesh (cloth), hollow ceramic ball, extra large sand, lamellar graphite, hollow glass bead, quartz glass tube (sheet), common (conduction) sheet glass, lucite, optical fiber, natural clay, foamed plastics, resin, wood chip, expanded perlite etc.When carrier is selected, must take all factors into consideration works such as the fastness of efficient, catalytic activity, catalyst cupport, service life, prices.
Seek to have the TiO of good photochemical catalytic oxidation activity
2Carrier, and seek and can effectively control the component of catalyst and crystalline phase and form by the control preparation condition to obtain high performance catalysis material, is those skilled in the art's continuous directions of effort.
Silicon has excellent photoelectric effect, if with nano-TiO
2Particle and silicon are compound, may strengthen absorption and the utilization of catalyst to visible light, but both at home and abroad to silicon load TiO
2Photochemical catalyst but rarely has report.
Summary of the invention
The object of the invention provides a kind of silicon load TiO
2Photochemical catalyst and preparation method thereof is controlled the crystal formation of catalyst more easily, improves the photocatalytic oxidation properties of catalyst.
For achieving the above object, the concrete technical scheme of the present invention is that a kind of preparation method of photochemical catalyst may further comprise the steps:
(1) in the whole process of preparation, being mete-wand with the amount of substance, is 1 part with the amount of substance of butyl titanate; Under 10～30 ℃, 1 part of butyl titanate slowly is added dropwise in 8.5～9 parts of absolute ethyl alcohols dissolves, obtain solution A;
(2) get 8.5～9 parts of absolute ethyl alcohols, add 2～2.5 parts deionized water, regulate pH with hydrochloric acid and be about 3.0, obtain solution B;
(3) solution B is slowly joined in the solution A, stir and formed colloidal sol in 0.4～0.6 hour;
In the optimized technical scheme, described hydrochloric acid is the hydrochloric acid of mass fraction 36～38%; The amount of hydrochloric acid is 0.2～0.3 part;
(4) in above-mentioned colloidal sol, add silica flour and continue to stir 2～3 hours, form gel;
The quality of described silica flour is 2～13 times of butyl titanate quality, and the particle diameter of silica flour is 70～120 μ m, and the silica flour average grain diameter is 90～100 μ m; Described silica flour is selected from a kind of in monocrystalline silicon or the polysilicon;
(5) step (4) gained gel was placed ageing 24～28 hours, heated 5～7 hours down in 105～110 ℃ then,, obtain the predecessor of catalyst with thorough volatilization organic solvent and water;
Described ageing process preferably should be in darkness, carries out in the dark environment of light; Described heating process can but be not limited in baking oven, carry out;
(6) predecessor with the catalyst of step (5) gained carries out roasting after grinding, and 200～550 ℃ of following roastings 1～3 hour, obtains containing the photochemical catalyst of 60%～80% anatase and 20%～40% red schorl phase titanium dioxide;
Described roasting process can but be not limited in Muffle furnace, carry out;
In the optimized technical scheme, the process of roasting is in the step (6): at first 250 ℃ of following roastings 1～1.5 hour, be warming up to 450～550 ℃ of roastings 0.5～1.0 hour again; In the preferred technical scheme, the process of roasting is in the step (6): at first 250 ℃ of following roastings 1～1.5 hour, be warming up to 530～550 ℃ of roastings 1.5～2.5 hours again.
Phase I roasting in the roasting is the pre-burning stage stage by stage, can go out volatilizable compound, organic compound, for example ethanol, water and ester class; The second stage sintering temperature is higher, and purpose is the crystal formation of control catalyst.
The present invention also comprises by above-mentioned two kinds and prepares the photochemical catalyst that photocatalytic method obtains being used for water treatment, described photochemical catalyst is to be modified silicon and got by nano titanium oxide, described silicon is selected from a kind of in monocrystalline silicon or the polysilicon, described nano titanium oxide by 60%～80% anatase and 20%～40% rutile mutually two titaniums form.
The present invention also comprises the processing of technique scheme gained catalyst to sewage, and described sewage is the sewage that contains the benzene series thing, and described benzene series thing is often referred to toluene, ethylbenzene, phenol or nitrobenzene or the like for well known to a person skilled in the art notion; Photochemical catalyst of the present invention has good photocatalytic oxidation properties to benzene series things such as toluene in the water, can reach more than 90% the clearance of toluene.Catalyst is reused 9 times, and benzene series thing clearance is still greater than 80%, and the catalyst recovery utilization rate reaches more than 90%, with respect to activated carbon fiber/TiO
2Catalyst among purification efficiency (63.27%) the present invention of low concentration toluene in the room air (referring to Sun Rubao, is attacked the work leather, Chao Fuhuan to the clearance of toluene is higher, Zhang Huashan, open big. toluene in the activated carbon fiber loaded titanium dioxide clean room. Chinese sanitary engineering, 2005,4 (6)); With respect to CuMn/TiO
2Condition (room temperature) milder to catalytic oxidation toluene among catalytic oxidation (bed temperature is 215 ℃) the present invention of toluene, easy operating (referring to: Li Peng, Tong Zhiquan, Huang Yan, Zhang Junfeng. the development and the activity experiment of novel C uMn/TiO2 benzene class catalyst for catalytic combustion, ACTA Scientiae Circumstantiae, 2008, (3)); (time of catalytic oxidation toluene is lacked (2 hours) (referring to Sun Mengjun among reaction time 4～5h) the present invention with respect to beta-schardinger dextrin-/Ce/TiO2 photochemical catalytic oxidation vapor phase toluene, Liu Lifen, Yang Fenglin. beta-schardinger dextrin-/Ce/TiO2 photochemical catalytic oxidation vapor phase toluene. China Environmental Science, 2008,28 (7)).
Basic principle of the present invention is: with nano-TiO
2Particle and Polysilicon Composite Structures can form heterojunction structure between two kinds of semi-conducting materials, help separating of photo-generated carrier and electronics, can strengthen absorption and the utilization of catalyst to visible light.
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
1, since with titanium dichloride load in silicon powder surface, help separating of photo-generated carrier and electronics, promoted absorption and the utilization of catalyst to visible light.
2, in Preparation of catalysts, owing to can therefore can effectively improve the catalytic performance of catalyst by changing anatase and rutile ratio mutually in the sintering temperature control titanium dioxide.
Description of drawings
Catalyst preparation process flow chart in Fig. 1 embodiment of the invention one;
Catalyst preparation process flow chart in Fig. 2 embodiment of the invention two;
Photocatalysis oxidation reaction apparatus in Fig. 3 embodiment of the invention four;
The reaction time is to the influence of benzene series thing clearance in Fig. 4 embodiment of the invention four.
The specific embodiment
Below in conjunction with drawings and Examples the present invention is further described:
Embodiment one: shown in accompanying drawing 1:
The first step at room temperature slowly splashes into 10ml (0.03mol) butyl titanate in 35mL (0.74mol) absolute ethyl alcohol, with the powerful 10min that stirs of magnetic stirring apparatus, mixes, and forms yellow settled solution A;
4mL (0.07mol) glacial acetic acid and 10mL distilled water (0.56mol) are added in other 35mL (0.74mol) absolute ethyl alcohol, and vigorous stirring obtains solution B, splashes into 1～2 hydrochloric acid (mass fraction is 36%), regulates the pH value and makes pH≤3;
In second step, under the room temperature, the solution B that will move under vigorous stirring in the constant pressure funnel slowly splashes in the A solution, drips approximately 3mL/min of speed, gets light yellow colloidal sol after dropwising;
In the 3rd step, (average grain diameter is 90～100um), 40 ℃ of water-bath heating, continues to stir 2 hours, forms gel to add 0.86mol (24g) silica flour in above-mentioned colloidal sol;
The 4th step placed the shady place ageing to heat 5 hours down at 105 ℃ in baking oven after 24 hours above-mentioned gel, with thorough volatilization organic solvent and water, obtained brown powder;
The 5th step placed the Muffle furnace roasting with brown powder, at first 250 ℃ of following roastings 1 hour, was warming up to 550 ℃ of roastings 1 hour again, obtained containing the photochemical catalyst of 78% anatase and 22% red schorl phase titanium dioxide.
Embodiment two: referring to accompanying drawing 2:
The first step at room temperature slowly splashes into 0.06mol (20mL) butyl titanate in 70mL (1.52mol) absolute ethyl alcohol, with the powerful 12min that stirs of magnetic stirring apparatus, mixes, and forms yellow settled solution A.
8mL (0.14mol) glacial acetic acid and 20mL distilled water (1.11mol) are added in other 70mL (1.12mol) absolute ethyl alcohol, and vigorous stirring obtains solution B, splashes into 3～4 hydrochloric acid (mass fraction is 36%), regulates the pH value and makes pH≤3;
In second step, under the room temperature, the solution B that will move under vigorous stirring in the constant pressure funnel slowly splashes in the A solution, drips approximately 6mL/min of speed, gets light yellow colloidal sol after dropwising;
The 3rd step added 52g (1.72mol) silica flour in above-mentioned colloidal sol, after continuing to stir half an hour, 40 ℃ of water-bath heating obtain gel behind the 2h;
The 4th step placed the shady place ageing to heat 5 hours down at 105 ℃ in baking oven after 24 hours above-mentioned gel, with thorough volatilization organic solvent and water, obtained brown powder;
The 5th step replaced silica flour with the brown powder that obtains, and repeated the 3rd and went on foot FOUR EASY STEPS, obtained the complex catalyst precursor thing of the two-layer butyl titanate gel of surface-coated;
In the 6th step, the 5th brown powder that obtain of step places the Muffle furnace roasting, at first 250 ℃ of following roastings 1 hour, is warming up to 550 ℃ of roastings 1 hour again, obtains containing the photochemical catalyst of 69% anatase and 31% red schorl phase titanium dioxide.
Embodiment three
The first step at room temperature slowly splashes into 10ml (0.03mol) butyl titanate in the 35mL absolute ethyl alcohol, with the powerful 10min that stirs of magnetic stirring apparatus, mixes, and forms yellow settled solution A;
4mL (0.07mol) glacial acetic acid and 10mL (0.56mol) distilled water are added in other the 35mL absolute ethyl alcohol (0.74mol), and vigorous stirring obtains solution B, splashes into 1～2 hydrochloric acid (mass fraction is 38%), regulates the pH value and makes pH≤3;
In second step, under the room temperature, the solution B that will move under vigorous stirring in the constant pressure funnel slowly splashes in the A solution, drips approximately 3mL/min of speed, gets light yellow colloidal sol after dropwising;
In the 3rd step, (average grain diameter is 90～100um), 40 ℃ of water-bath heating, continues to stir 2 hours, forms gel to add 24g (0.86mol) silica flour in above-mentioned colloidal sol;
The 4th step placed the shady place ageing to heat 5 hours down at 105 ℃ in baking oven after 24 hours above-mentioned gel, with thorough volatilization organic solvent and water, obtained brown powder;
The 5th step placed the Muffle furnace roasting with brown powder, 450 ℃ of following roastings 2.5 hours, obtained containing the photochemical catalyst of 63% anatase and 37% red schorl phase titanium dioxide.
Embodiment four
Adopt photocatalysis oxidation reaction apparatus (as Fig. 3) to handle benzene series thing in the water.The initial concentration of toluene is 4～40mg/L, and catalyst consumption is 0.5～5g/L.The high 400mm of cylinder type glass container made, internal diameter is 150mm, light source is the 30W low pressure mercury lamp that is fixed on the reactor axis.Reactor is placed on the magnetic stirring apparatus, with the uniform rotating speed of 200～400r/min reactant liquor is mixed fully with catalyst, behind the photochemical catalytic oxidation toluene 120min, and sampling gas chromatographic detection toluene concentration, calculating toluene clearance.
Toluene clearance=(initial toluene concentration-processing back toluene concentration)/initial toluene concentration * 100%
Chromatographic condition: chromatographic column is the PEG-20M capillary column, and column temperature adopts temperature programming, and concrete operations are 40 ℃ of initial temperature, constant temperature 1min, and the speed with 10 ℃/min rises to 100 ℃ then, keeps constant temperature 1min; The vaporizer temperature is 220 ℃, and detector temperature is 230 ℃, and detector is FID, and carrier gas is a high pure nitrogen, presses before the post to be 49kPa, and split ratio is 1: 50; Sample size is controlled at 2 μ L.
Quantitative analysis method: carry out with reference to " water and waste water check and analysis method " ([) (the 4th edition) extraction with carbon disulfide gas chromatography, carbon disulfide is purified to be occurred through the assorted peak of gas-chromatography check nothing later.With carbon disulfide is that extractant carries out chromatographic quantitative analysis to each component of the benzene series thing after degrading, measures each component concentrations, and calculates its corresponding degradation rate.
(1) light application time the results are shown in Figure 4 to the influence of benzene series thing degradation efficiency.
(2) catalyst amounts the results are shown in Table 1 to the influence of photocatalytic degradation benzene series thing efficient:
The dosage of table 1 catalyst is to the influence of toluene clearance
| The dosage of catalyst/g toluene clearance/% catalyst treatment amount/mgg -1 0.5 66.43 10.91 1.0 91.18 9.13 2.0 84.27 5.28 3.0 81.66 2.32 4.0 66.98 1.41 5.0 62.72 0.98 |
(3) initial concentration of benzene series thing the results are shown in Table 2 to the influence of its photocatalytic degradation experiment:
Table 2 toluene initial concentration is to the influence of its clearance and catalyst treatment amount
The initial concentration of toluene/mg/L toluene clearance/% catalyst treatment amount/mgg
-1
5.0 83.48 6.25
10.0 91.18 9.13
20.0 73.36 15.85
30.0 69.53 20.53
40.0 63.41 25.41
Claims (6)
1. the preparation method of a photochemical catalyst is characterized in that: may further comprise the steps:
(1) in the whole process of preparation, being mete-wand with the amount of substance, is 1 part with the amount of substance of butyl titanate; Under 10～30 ℃, 1 part of butyl titanate slowly is added dropwise in 8.5～9 parts of absolute ethyl alcohols dissolves, obtain solution A;
(2) get 8.5～9 parts of absolute ethyl alcohols, add 2～2.5 parts deionized water, regulate pH with hydrochloric acid and be about 3.0, obtain solution B;
(3) solution B is slowly joined in the solution A, stir and formed colloidal sol in 0.4～0.6 hour;
(4) in above-mentioned colloidal sol, add silica flour and continue to stir 2～3 hours, form gel;
(5) step (4) gained gel is placed ageing 24～28 hours, heated 5～7 hours down in 105～110 ℃ then, obtain the predecessor of catalyst;
(6) predecessor with the catalyst of step (5) gained carries out roasting after grinding, and 200～550 ℃ of following roastings 1～3 hour, obtains containing the photochemical catalyst of 60%～80% anatase and 20%～40% red schorl phase titanium dioxide.
2. the method for preparing photochemical catalyst according to claim 1 is characterized in that: the quality of silica flour described in the step (4) is 2～13 times of butyl titanate quality, and the particle diameter of silica flour is 70～120 μ m, and the silica flour average grain diameter is 90～100 μ m; Described silica flour is selected from a kind of in monocrystalline silicon or the polysilicon.
3. the method for preparing photochemical catalyst according to claim 1 is characterized in that: the process of roasting is in the step (6): at first 250 ℃ of following roastings 1～1.5 hour, be warming up to 450～550 ℃ of roastings 0.5～1.0 hour again.
4. the method for preparing photochemical catalyst according to claim 1 is characterized in that: the process of roasting is in the step (6): at first 250 ℃ of following roastings 1～1.5 hour, be warming up to 530～550 ℃ of roastings 1.5～2.5 hours again.
5. the photochemical catalyst for preparing by the described method for preparing photochemical catalyst of claim 1～4.
6. the application of the described photochemical catalyst of claim 5 in disposing of sewage, described sewage is the sewage that contains benzene series thing pollutant.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102433978A (en) * | 2011-09-07 | 2012-05-02 | 南昌大学 | Novel nanometer titanium dioxide self-cleaning fluorine-carbon aluminum single sheet as well as low-temperature preparation method and application thereof |
| CN102728350A (en) * | 2012-07-10 | 2012-10-17 | 北京纬纶华业环保科技股份有限公司 | Catalyst for treating industrial waste water by catalytic wet air oxidation (CWAO) |
| CN105214633A (en) * | 2015-09-08 | 2016-01-06 | 北京化工大学 | A kind of preparation method of photocatalytic degradation titanium dioxide integral post |
| CN106757128A (en) * | 2016-11-30 | 2017-05-31 | 彭州市运达知识产权服务有限公司 | A kind of indoor oxygenation device |
| CN108889289A (en) * | 2018-07-24 | 2018-11-27 | 华东师范大学 | A kind of titanium dioxide optical catalyst preparation and its application for receiving micron silicon Particles dispersed |
| WO2019051734A1 (en) * | 2017-09-14 | 2019-03-21 | 季春柳 | Method for preparing tio2 capillary monolithic column |
| CN110548500A (en) * | 2019-09-05 | 2019-12-10 | 刘美端 | Photocatalyst, preparation method thereof and air purifying agent |
| CN111715303A (en) * | 2020-05-19 | 2020-09-29 | 中国石油天然气股份有限公司 | Pretreatment method for decomposing cyclohexane photocatalyst in oil field station |
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2009
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102433978A (en) * | 2011-09-07 | 2012-05-02 | 南昌大学 | Novel nanometer titanium dioxide self-cleaning fluorine-carbon aluminum single sheet as well as low-temperature preparation method and application thereof |
| CN102433978B (en) * | 2011-09-07 | 2015-05-20 | 南昌大学 | Novel nanometer titanium dioxide self-cleaning fluorine-carbon aluminum single sheet as well as low-temperature preparation method and application thereof |
| CN102728350A (en) * | 2012-07-10 | 2012-10-17 | 北京纬纶华业环保科技股份有限公司 | Catalyst for treating industrial waste water by catalytic wet air oxidation (CWAO) |
| CN105214633A (en) * | 2015-09-08 | 2016-01-06 | 北京化工大学 | A kind of preparation method of photocatalytic degradation titanium dioxide integral post |
| CN105214633B (en) * | 2015-09-08 | 2018-05-25 | 北京化工大学 | A kind of preparation method of photocatalytic degradation titanium dioxide integral post |
| CN106757128A (en) * | 2016-11-30 | 2017-05-31 | 彭州市运达知识产权服务有限公司 | A kind of indoor oxygenation device |
| WO2019051734A1 (en) * | 2017-09-14 | 2019-03-21 | 季春柳 | Method for preparing tio2 capillary monolithic column |
| CN108889289A (en) * | 2018-07-24 | 2018-11-27 | 华东师范大学 | A kind of titanium dioxide optical catalyst preparation and its application for receiving micron silicon Particles dispersed |
| CN110548500A (en) * | 2019-09-05 | 2019-12-10 | 刘美端 | Photocatalyst, preparation method thereof and air purifying agent |
| CN111715303A (en) * | 2020-05-19 | 2020-09-29 | 中国石油天然气股份有限公司 | Pretreatment method for decomposing cyclohexane photocatalyst in oil field station |
| CN111715303B (en) * | 2020-05-19 | 2023-07-25 | 中国石油天然气股份有限公司 | Pretreatment method of cyclohexane decomposition photocatalyst for oilfield field station |
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