CN101773841A - Photocatalyst for water treatment - Google Patents

Photocatalyst for water treatment Download PDF

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Publication number
CN101773841A
CN101773841A CN201010105247A CN201010105247A CN101773841A CN 101773841 A CN101773841 A CN 101773841A CN 201010105247 A CN201010105247 A CN 201010105247A CN 201010105247 A CN201010105247 A CN 201010105247A CN 101773841 A CN101773841 A CN 101773841A
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titanium dioxide
catalyst
solution
photochemical catalyst
preparation
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董延茂
鲍治宇
赵丹
杨敏
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Suzhou University of Science and Technology
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Suzhou University of Science and Technology
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Abstract

The invention discloses a photocatalyst for water treatment, which is prepared by compounding nano-titanium dioxide and CuO/Cu2O (SeO3). The photocatalyst comprises the following components in mass percent: 20%-60% of titanium dioxide and 40%-80% of Cu2O (SeO3) or CuO, wherein the titanium dioxide is selected from one or two of anatase titanium dioxide and rutile titanium dioxide. Because the titanium dioxide is compounded with the CuO/Cu2O (SeO3), the invention is favorable for separating photon-generated carriers from electrons and promotes the light absorption and utilization of the catalyst. In the preparation of the catalyst, by changing the roasting temperature to control the ratio of the anatase to the rutile in the titanium dioxide, the catalytic performance of the catalyst is effectively improved. The catalyst has good photocatalytic oxidation performance to humic acid in water, and the removing ratio to the humic acid can reach more than 80%.

Description

A kind of photochemical catalyst that is used for water treatment
Technical field
The present invention relates to a kind of photochemical catalyst that is used for water treatment, be specifically related to a kind of compound TiO 2Photochemical catalyst and preparation method thereof.
Background technology
In recent years, TiO 2With its high activity, cheapness, safety, advantage such as pollution-free and be used to the Treatment by Photocatalysis Oxidation organic pollution.
TiO 2Energy gap (Eg) be 3.2eV, wavelength is just had stronger absorption less than the ultraviolet light of 387.5nm, promptly can only absorb the ultraviolet light part in the solar spectrum, and ultraviolet light only accounts for about 5% of sunshine gross energy.In addition, TiO 2The carrier recombination rate higher, quantum efficiency is lower, so how to improve TiO 2To the photoresponse of ultraviolet light (visible light), improve TiO 2Photocatalysis efficiency be the present research focus in this field.
Mainly concentrate on TiO 2Carry out modification aspects such as metal ion mixing, nonmetal doping, surperficial noble metal loading, semiconductor are compound, dye photoactivation, satisfy greatly in 1.9～3.1eV (electron-volt) scope to adjust its band gap.Studies show that mix up nonmetalloid such as the N littler than oxygen electronegativity, S etc. can improve the valence band current potential, dwindle energy gap; Mix up metal and can reduce the conduction band current potential; TiO 2Be compounded to form solid solution with the little semiconductor of band gap and can dwindle energy gap.The energy gap of selenium is 1.79eV in semi-conducting material, Cu 2The energy gap of Se is 1.1～1.4eV.The energy gap of selenium and selenides is less, the photoelectric transformation efficiency height, thereby be widely used in fields such as solar cell, glass material, optical filter, superionic conductors, thermoelectric converter.With TiO 2Compound with selenides is to improve TiO 2The effective way of photocatalysis efficiency.
For example, the patent No. is 200610098289.0 Chinese disclosure of the Invention a kind of mesoporous titania meterial that contains selenium and preparation method thereof, this method is to be the presoma of selenium with the sodium selenite, butyl titanate is the presoma of titanium, non-ionic surface active agent macromolecule block polymer P123 is the template agent, the body phase of original position selenium implantation meso-porous titanium oxide under the one-step method low temperature in collosol-gelatum system, then with the product ageing, dry, obtain containing selenium meso-porous titanium oxide novel photocatalysis material, it includes inorganic oxide skeleton Ti-O-Ti and Ti-O-Se, 0＜Se/Ti mol ratio＜0.1 wherein, and molecular formula is (TiO 2) 1-x(SeO 2) x, in the formula, 0＜X＜0.1.Synthetic meso-porous titanium oxide selenium amount is controlled, and specific area is big, has regular one-dimensional tunnel structure.
Summary of the invention
The object of the invention provides a kind of photochemical catalyst that is used for water treatment.
For achieving the above object, the concrete technical scheme of the present invention is that a kind of photochemical catalyst that is used for water treatment, described photochemical catalyst comprise that mass percent is 20%～60% titanium dioxide, comprise that also mass percent is 40～80% selenous acid copper Cu 2O (SeO 3) or cupric oxide CuO; Wherein titanium dioxide is selected from: one or both in anatase phase titanium dioxide or the red schorl phase titanium dioxide.
In the optimized technical scheme, described photochemical catalyst comprises that mass percent is 20%～30% titanium dioxide, comprises that also mass percent is 60%～70% selenous acid copper Cu 2O (SeO 3) and cupric oxide CuO; Wherein titanium dioxide is anatase phase titanium dioxide.
A kind of preparation method who is used for the photochemical catalyst of water treatment may further comprise the steps:
(1) in the whole process of preparation, being mete-wand with the volume, is 1 part with the volume of butyl titanate; Under 10～30 ℃, 1 part of butyl titanate slowly is added dropwise in 2～4 parts of absolute ethyl alcohols dissolves, add 0.05～0.15 part of glacial acetic acid again, stirring obtains solution A;
(2) get 1～2 part of absolute ethyl alcohol, add 0.1～0.2 part 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 tetraethyl titanate colloidal sol in 0.4～0.6 hour;
(4) in above-mentioned colloidal sol, add the Berzeline powder and continue to stir 2～3 hours formation gels;
(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;
(6) predecessor with the catalyst of step (5) gained carries out roasting after grinding, 200～550 ℃ of following roastings at least 1 hour, described photochemical catalyst;
In the technique scheme, the quality of Berzeline powder described in the step (4) is 2～13 times of quality of 1 parts by volume butyl titanate, and the particle diameter of powder is 70～120 μ m.
In the optimized technical scheme, hydrochloric acid is the hydrochloric acid of mass fraction 36～38% described in the step (2); The amount of hydrochloric acid is 0.2～0.3 part.
In the optimized technical scheme, what ageing process described in the step (5) should be in darkness, carry out in the dark environment of light; Heating process described in the step (5) can but be not limited in baking oven, carry out.
In the technique scheme, in the step (6), 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.Through the catalyst of this condition preparation to water in humic acid have good photocatalytic oxidation properties, can reach 80% to the clearance of humic acid.。
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; In roasting process, the amount of titanium elements and copper can not reduce, and the amount of selenium element can reduce.
In the technique scheme, the analytical method of each component is in the described photochemical catalyst:
According to XRD analysis data (Fig. 5), utilize thing phase quantitative analysis-adiabatic method to calculate each constituent content:
W x = I x K A X Σ i = 1 N I i K A i - - - ( 1 )
In the formula
K A X = K X K A - - - ( 2 )
Wherein A is the thing phase of interior mark phase; X is any phase, X=1,2 ... N; K X, K ABe respectively the RIR value of thing phase X and A.
According to the aforementioned calculation result, contrast JCPDS (PDF2004) standard spectrogram, in conjunction with results of elemental analyses, catalytic component and crystal formation are as shown in table 1.
Utilize software Jade 5 to check rutile phase TiO 2With anatase TiO mutually 2RIR value and diffracted intensity, calculate anatase TiO with thing phase quantitative analysis-adiabatic method again 2Mass fraction:
W A = I A I A + I R K A R - - - ( 3 )
In the formula
K A R = K R K A - - - ( 4 )
W wherein AExpression anatase phase TiO 2Proportion; K R, K ARIR value (the K that represents rutile R110 and anatase A101 respectively R=3.4; K A=3.3); I R, I AThe diffracted intensity of representing rutile R110 and anatase A101 respectively.
Above-mentioned photochemical catalyst can be used for disposing of sewage, and is particularly useful for handling the sewage that contains humic acid.
Basic principle of the present invention is: with nano-TiO 2Particle and CuO/Cu 2O (SeO 3) compound, can between two kinds of semi-conducting materials, form heterojunction structure, 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 the present invention with titanium dioxide and CuO/Cu 2O (SeO 3) compound, help separating of photo-generated carrier and electronics, promoted absorption and the utilization of catalyst to light, the gained catalyst can reach 80% to the humic acid clearance under the ultraviolet light synergistic effect, be higher than TiO 2/ UV system (the humic acid degradation rate is up to 65.61%) (Zhang Hongmei. the Study on influencing factors [J] of suspended state photocatalytic degradation humic acid. use chemical industry, 2009,38 (7): 970-976);
2, in Preparation of catalysts,, therefore can effectively improve the catalytic performance of catalyst owing to can form by the crystal formation and the element that change titanium dioxide in the sintering temperature control catalyst.
Description of drawings
Catalyst preparation process flow chart in Fig. 1, the embodiment of the invention one;
Catalyst preparation process flow chart in Fig. 2, the embodiment of the invention two;
Catalyst preparation process flow chart in Fig. 3, the embodiment of the invention three;
The processing of Fig. 4, embodiment four contains the device schematic diagram of the sewage of humic acid;
The XRD figure of catalyst ((a) 350 ℃ under Fig. 5, the different sintering temperature; (b) 400 ℃; (c) 450 ℃; (d) 500 ℃; (e) 550 ℃, wherein, A: Detitanium-ore-type; R: rutile-type; B:Cu 2-xSe; C:Cu 2O (SeO 3); D:CuO; Along with temperature is brought up to 450 ℃, Detitanium-ore-type TiO from 350 ℃ 2Characteristic peak intensity improve gradually; Continue to improve sintering temperature, Detitanium-ore-type TiO 2Mass percent descend rutile TiO 2Mass percent improve gradually; Because Detitanium-ore-type TiO 2Photocatalysis efficiency be higher than rutile TiO 2, so sintering temperature is with 450 ℃ of the bests);
The EDAX of catalyst figure under 450 ℃ of heat treatment 1h among Fig. 6, the embodiment one;
The reaction time is to the influence of HA clearance among Fig. 7, the embodiment four;
Fig. 8, embodiment four sintering temperatures are to the influence of humic acid clearance;
Fig. 9, embodiment four pH value of solution values are to the influence of humic acid clearance;
Figure 10, embodiment four catalyst amountses are to the influence of humic acid clearance;
350 ℃ of catalyst elements analysis charts that roasting obtains among Figure 11, the embodiment four;
400 ℃ of catalyst elements analysis charts that roasting obtains among Figure 12, the embodiment two;
450 ℃ of catalyst elements analysis charts that roasting obtains among Figure 13, the embodiment one;
550 ℃ of catalyst elements analysis charts that roasting obtains among Figure 14, the embodiment five.
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 (0.57mol) absolute ethyl alcohol, adds the 1ml glacial acetic acid, with the powerful 30min that stirs of magnetic stirring apparatus, mixes, and forms yellow settled solution A;
1.3mL distilled water (0.07mol) is added in other 13mL (0.27mol) absolute ethyl alcohol, and vigorous stirring adds 1～2 hydrochloric acid (mass fraction is 36%), regulates the pH value and makes pH be about 3～4, gets solution B;
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, in above-mentioned colloidal sol, add 0.2mol (41.2g) Cu 2(average grain diameter is 90～100um), 40 ℃ of water-bath heating to the Se powder, continues to stir 2 hours, forms gel;
The 4th step placed the shady place ageing to heat 5 hours down at 100 ℃ 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 450 ℃ of roastings 1 hour again, obtained containing 24.3% anatase phase titanium dioxide, 16.7%CuO and 59%Cu 2O (SeO 3) photochemical catalyst (data of correspondence table 1-C-3 and Fig. 5-(c) are with reference to Figure 13).
Embodiment two: referring to accompanying drawing 2:
The first step at room temperature slowly splashes into 10ml (0.03mol) butyl titanate in 35mL (0.57mol) absolute ethyl alcohol, adds the 1ml glacial acetic acid, with the powerful 30min that stirs of magnetic stirring apparatus, mixes, and forms yellow settled solution A;
1.3mL distilled water (0.07mol) is added in other 13mL (0.27mol) absolute ethyl alcohol, and vigorous stirring adds 1～2 hydrochloric acid (mass fraction is 36%), regulates the pH value and makes pH be about 3～4, gets solution B;
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, in above-mentioned colloidal sol, add 0.2mol (41.2g) Cu 2(average grain diameter is 90～100um), 40 ℃ of water-bath heating to the Se powder, continues to stir 2 hours, forms gel;
The 4th step placed the shady place ageing to heat 5 hours down at 100 ℃ 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 400 ℃ of roastings 1 hour again, obtained containing 32.4% anatase phase titanium dioxide and 67.6%Cu 2O (SeO 3) photochemical catalyst (data of correspondence table 1-C-2 and Fig. 5-(b) are with reference to Figure 12).
Embodiment three
The first step at room temperature slowly splashes into 10ml (0.03mol) butyl titanate in 35mL (0.57mol) absolute ethyl alcohol, adds the 1ml glacial acetic acid, with the powerful 30min that stirs of magnetic stirring apparatus, mixes, and forms yellow settled solution A;
1.3mL distilled water (0.07mol) is added in other 13mL (0.27mol) absolute ethyl alcohol, and vigorous stirring adds 1～2 hydrochloric acid (mass fraction is 36%), regulates the pH value and makes pH be about 3～4, gets solution B;
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, in above-mentioned colloidal sol, add 0.2mol (41.2g) Cu 2(average grain diameter is 90～100um), 40 ℃ of water-bath heating to the Se powder, continues to stir 2 hours, forms gel;
The 4th step placed the shady place ageing to heat 5 hours down at 100 ℃ in baking oven after 24 hours above-mentioned gel, with thorough volatilization organic solvent and water, obtained brown powder;
The 5th step, brown powder is placed the Muffle furnace roasting, at first 250 ℃ of following roastings 1 hour, be warming up to 500 ℃ of roastings 1 hour again, obtain containing 38.9% anatase phase titanium dioxide, the photochemical catalyst of 16.3% rutile ore phase titanic oxide and 44.8%CuO (correspondence table 1-C-4 and Fig. 5-(d) data).
Embodiment four
The first step at room temperature slowly splashes into 10ml (0.03mol) butyl titanate in 35mL (0.57mol) absolute ethyl alcohol, adds the 1ml glacial acetic acid, with the powerful 30min that stirs of magnetic stirring apparatus, mixes, and forms yellow settled solution A;
1.3mL distilled water (0.07mol) is added in other 13mL (0.27mol) absolute ethyl alcohol, and vigorous stirring adds 1～2 hydrochloric acid (mass fraction is 36%), regulates the pH value and makes pH be about 3～4, gets solution B;
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, in above-mentioned colloidal sol, add 0.2mol (41.2g) Cu 2(average grain diameter is 90～100um), 40 ℃ of water-bath heating to the Se powder, continues to stir 2 hours, forms gel;
The 4th step placed the shady place ageing to heat 5 hours down at 100 ℃ 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 350 ℃ of roastings 1 hour again, obtained containing 33.5% anatase phase titanium dioxide, 44.5%Cu 2O (SeO 3) and 22%Cu 2The photochemical catalyst of Se.(data of correspondence table 1-C-1 and Fig. 5-(a) are with reference to Figure 11)
Embodiment five
The first step at room temperature slowly splashes into 10ml (0.03mol) butyl titanate in 35mL (0.57mol) absolute ethyl alcohol, adds the 1ml glacial acetic acid, with the powerful 30min that stirs of magnetic stirring apparatus, mixes, and forms yellow settled solution A;
1.3mL distilled water (0.07mol) is added in other 13mL (0.27mol) absolute ethyl alcohol, and vigorous stirring adds 1～2 hydrochloric acid (mass fraction is 36%), regulates the pH value and makes pH be about 3～4, gets solution B;
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, in above-mentioned colloidal sol, add 0.2mol (41.2g) Cu 2(average grain diameter is 90～100um), 40 ℃ of water-bath heating to the Se powder, continues to stir 2 hours, forms gel;
The 4th step placed the shady place ageing to heat 5 hours down at 100 ℃ 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 13.7% anatase phase titanium dioxide, the photochemical catalyst of 35.3% rutile ore phase titanic oxide and 51%CuO.(data of correspondence table 1-C-5 and Fig. 5-(e) are with reference to Figure 14)
Table 1 sintering temperature is to the influence of catalytic component and crystal formation
Numbering Sintering temperature (℃) Catalytic component The RIR value Each constituent mass mark (%) Standard card JCPDS
??C-1 ??350 ??Cu 2Se??TiO 2(A)??Cu 2O(SeO 3) ??5.79??3.30??2.33 ??22.0??33.5??44.5 ??[06-0680]??[21-1272]??[46-0793]
??C-2 ??400 ??TiO 2(A)??Cu 2O(SeO 3) ??3.30??2.33 ??32.4??67.6 ??[21-1272]??[46-0793]
??C-3 ??450 ??TiO 2(A)??Cu 2O(SeO 3)??CuO ??3.30??2.33??3.91 ??24.3??59.0??16.7 ??[21-1272]??[46-0793]??[80-1917]
??C-4 ??500 ??TiO 2(A)??TiO 2(R)??CuO ??3.30??3.40??3.91 ??38.9??16.3??44.8 ??[21-1272]??[21-1276]??[80-1917]
??C-5 ??550 ??TiO 2(A)??TiO 2(R)??CuO ??3.30??3.40??3.91 ??13.7??35.3??51.0 ??[21-1272??[21-1276]??[80-1917]
(annotate: A is the anatase phase, and R is the rutile phase)
Embodiment six
Take by weighing a certain amount of humic acid, add a certain amount of 0.1mol/L NaOH solution (50～60 ℃), stirring makes it abundant dissolving, with 5～18% hydrochloric acid pH value of solution is transferred to 6.5～8.0 then, use miillpore filter (aperture is 0.45 μ m) filtering solution again, be transferred in the volumetric flask of 1000mL, add deionized water and carry out constant volume, stand-by as storing solution.Residue after the filtration is put into baking oven 80～100 ℃ of oven dry after with the appropriate hydrochloric acid pickling, adopts mass method to calculate the concentration of storing solution, and again storing solution being diluted to concentration with deionized water is that the solution of 10mg/L is as pending sample solution.
Adopt photocatalysis oxidation reaction apparatus (as Fig. 4) to handle humic acid in the water.The initial concentration of humic acid is 10mg/L, and catalyst consumption is 0.5～2g/L.The high 400mm of cylinder type glass container made, internal diameter is 150mm, light source is the 20W ultraviolet germicidal that is fixed on the reactor axis.Reactor is placed on the magnetic stirring apparatus, uniform rotating speed with 200～400r/min makes reactant liquor mix fully with catalyst, every 20min sampling once detects humic acid concentration with ultraviolet-visible spectrophotometer behind the photochemical catalytic oxidation humic acid, calculates the humic acid clearance.
Humic acid clearance=(initial humic acid concentration-processing back humic acid concentration)/initial humic acid concentration * 100%
Quantitative analysis method: reference literature (Yan Xiaoju, in water conservancy, Fu Shengtao, the sudden and violent auspicious tinkling of pieces of jade, Li Lizheng. the experimental study of optically catalytic TiO 2 degraded humic acid. Chinese water supply and drainage, 2009,25 (7): 94-101) use UV 254Light source detects humic acid concentration in the solution with ultraviolet-visible spectrophotometer, calculates the humic acid clearance.
Observing differential responses time, difference bakes the influence to the clearance of degraded humic acid of temperature gained photochemical catalyst, different pH, different catalysts consumption, sees Fig. 7,8,9,10 respectively.
As shown in Figure 7, the reaction time should be at least greater than 3 hours; As shown in Figure 8, the effect of gained photochemical catalyst C-3 best (representing embodiment one); As shown in Figure 9, the pH of suitable processing environment is 5.5～7.5, is preferably 6.5; As shown in Figure 10, suitable catalyst amount is 1.0～2.0g/L, is preferably 1.50g/L.
Embodiment seven
Get a few gained photochemical catalysts of embodiment according to the method for embodiment four humic acid of degrading, when dosage is 1.5g/L, the humic acid initial concentration solution is 10mg/L, and the pH value is 6.5 o'clock, and through the 3h degraded, the degradation rate of humic acid can reach 78.8%.Continuing increases reaction time to 5～6h, and the humic acid clearance can reach 85%; And under the same condition, only use in the titanium dioxide 3h humic acid degradation rate be up to 65.61% (Zhang Hongmei. the Study on influencing factors [J] of suspended state photocatalytic degradation humic acid. use chemical industry, 2009,38 (7): 970-976), compare and have the advantage high to the humic acid degradation rate.
With TiO 2/ UV/ aeration system (is worked as pH=3.5, dosage is 1.0g/L, when aeration rate was 0.12m3/h, the humic acid degradation rate was 96.83%) (Liu Xudong, Hu Guiling, Liu Xiaoxin, Wang Ye. the research of humic acid [J] in the photocatalytic degradation micro-polluted water. meteorological and environment journal, 2008,24 (2): 38-41) compare and have the reaction condition gentleness (pH is near neutral, meet the drinking original water physical condition), the low advantages such as (not needing aeration) of energy consumption.

Claims (6)

1. a photochemical catalyst that is used for water treatment is characterized in that, described photochemical catalyst comprises that mass percent is 20%～60% titanium dioxide, comprises that also mass percent is 40～80% selenous acid copper Cu 2O (SeO 3) or cupric oxide CuO; Wherein titanium dioxide is selected from: one or both in anatase phase titanium dioxide or the red schorl phase titanium dioxide.
2. photochemical catalyst according to claim 1 is characterized in that, described photochemical catalyst comprises that mass percent is 20%～30% titanium dioxide, comprises that also mass percent is 60%～70% selenous acid copper Cu 2O (SeO 3) and cupric oxide CuO; Wherein titanium dioxide is anatase phase titanium dioxide.
3. a preparation method who is used for the photochemical catalyst of water treatment is characterized in that, may further comprise the steps:
(1) in the whole process of preparation, being mete-wand with the volume, is 1 part with the volume of butyl titanate; Under 10～30 ℃, 1 part of butyl titanate slowly is added dropwise in 2～4 parts of absolute ethyl alcohols dissolves, add 0.05～0.15 part of glacial acetic acid again, stirring obtains solution A;
(2) get 1～2 part of absolute ethyl alcohol, add 0.1～0.2 part 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 tetraethyl titanate colloidal sol in 0.4～0.6 hour;
(4) in above-mentioned colloidal sol, add the Berzeline powder and continue to stir 2～3 hours formation gels;
(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;
(6) predecessor with the catalyst of step (5) gained carries out roasting after grinding, 200～550 ℃ of following roastings at least 1 hour, described photochemical catalyst;
In the technique scheme, the quality of Berzeline powder described in the step (4) is 2～13 times of quality of 1 parts by volume butyl titanate, and the particle diameter of powder is 70～120 μ m.
4. preparation method according to claim 3 is characterized in that, hydrochloric acid is the hydrochloric acid of mass fraction 36～38% described in the step (2).
5. preparation method according to claim 3 is characterized in that, what ageing process described in the step (5) should be in darkness, carry out in the dark environment of light.
6. preparation method according to claim 3 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.
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Cited By (15)

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CN102391862A (en) * 2011-09-28 2012-03-28 青岛科技大学 Titanium dioxide powders modified by copper oxide quantum dots surfacely and preparation method for titanium dioxide powders
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RU2469788C1 (en) * 2011-06-03 2012-12-20 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Московский государственный университет тонких химических технологий имени М.В. Ломоносова" (МИТХТ им. М.В.Ломоносова) PHOTOCATALYST BASED ON NANOSIZED η-MODIFICATION OF TITANIUM DIOXIDE
CN102391862B (en) * 2011-09-28 2014-03-05 青岛科技大学 Titanium dioxide powders modified by copper oxide quantum dots surfacely and preparation method for titanium dioxide powders
CN102391862A (en) * 2011-09-28 2012-03-28 青岛科技大学 Titanium dioxide powders modified by copper oxide quantum dots surfacely and preparation method for titanium dioxide powders
CN103429346B (en) * 2011-12-22 2016-11-23 昭和电工株式会社 Containing copper and the compositions of titanium and manufacture method thereof
CN103429346A (en) * 2011-12-22 2013-12-04 昭和电工株式会社 Copper-and-titanium-containing composition and production method therefor
US9210939B2 (en) 2011-12-22 2015-12-15 Showa Denko K.K. Copper-and-titanium-containing composition and production method therefor
RU2479349C1 (en) * 2012-01-19 2013-04-20 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Саратовский государственный технический университет имени Гагарина Ю.А." (СГТУ имени Гагарина Ю.А.) Method of producing catalyst for cleaning water from hydrocarbon contaminants
CN107427815A (en) * 2014-09-12 2017-12-01 日东电工株式会社 Multivalence semiconductor light-catalyst material
CN104399464A (en) * 2014-12-09 2015-03-11 齐鲁工业大学 Photocatalyst for activation of organic chlorine inert pollutant molecules in water treatment process, as well as preparation method and application of photocatalyst
CN104399464B (en) * 2014-12-09 2016-06-08 齐鲁工业大学 A kind of photocatalyst for the activation of organochlorine inertia contaminant molecule in water treatment procedure and its preparation method and application
CN106732506A (en) * 2017-03-02 2017-05-31 河北麦森钛白粉有限公司 A kind of preparation technology of carbon yttrium modified titanium dioxide photocatalyst
CN107552082A (en) * 2017-09-29 2018-01-09 河海大学 A kind of quaternary multifunction magnetic nano composite material and preparation method thereof
CN107715848A (en) * 2017-11-15 2018-02-23 中国环境科学研究院 A kind of modified Nano material and its application in stibium-containing wastewater processing
CN107715848B (en) * 2017-11-15 2018-07-17 中国环境科学研究院 A kind of modified Nano material and its application in stibium-containing wastewater processing
CN109292896A (en) * 2018-09-30 2019-02-01 同济大学 A kind of method of humic acid in control drinking water
CN109453766A (en) * 2018-11-05 2019-03-12 北京工业大学 A kind of Ag load TiO of atom level dispersion2The preparation method of mesoporous nano belt photochemical catalyst
CN109772372A (en) * 2019-03-16 2019-05-21 泉州师范学院 A kind of preparation method and application of the copper selenide nanometer material based on egg shell template
CN110548500A (en) * 2019-09-05 2019-12-10 刘美端 Photocatalyst, preparation method thereof and air purifying agent
CN113493190A (en) * 2021-08-26 2021-10-12 辽宁科技大学 Copper selenate material and preparation method and application thereof
CN114588920A (en) * 2022-03-08 2022-06-07 北京理工大学 Boron carbide doped titanium dioxide photocatalyst, preparation method and application thereof

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