CN105233828A - Recoverable titanium dioxide photocatalyst capable of quickly degrading high-concentration bisphenol A waste water as well as preparation method and application thereof - Google Patents
Recoverable titanium dioxide photocatalyst capable of quickly degrading high-concentration bisphenol A waste water as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a recoverable titanium dioxide photocatalyst capable of quickly degrading high-concentration bisphenol A waste water as well as a preparation method and application thereof. The preparation method comprises the steps of: (1) preparing a magnetic core; (2) preparing a SiO2 intermediate layer; (3) loading a TiO2 layer; and (4) performing CuO doping. The photocatalyst comprises the magnetic core which is wrapped with the intermediate layer SiO2, the outside of the intermediate layer SiO2 is also loaded with the TiO2 layer, and a TiO2 surface layer is doped with CuO. The photocatalyst is applied to processing epoxy resin production waste water. The catalyst prepared by the preparation method disclosed by the invention can quickly and efficiently degrade the high-concentration bisphenol A waste water, and the loaded TiO2 is mainly an anatase type of which the catalytic activity is the highest; repeated efficient recovery of the catalyst can be realized by utilizing an external magnetic field, and higher catalytic degradation capacity is maintained. The catalyst also has a better degradation effect on the epoxy resin production waste water.
Description
Technical field
The invention belongs to catalyst preparing and applied technical field, particularly a kind of recyclable titanium dioxide optical catalyst and its preparation method and application of fast degradation high concentration bisphenol-A waste water.
Background technology
Bisphenol-A (bisphenolA, BPA), 2,2-bis-(4-hydroxy phenyl) propane (C
15h
16o
2), be a kind of industrial chemical of Prof. Du Yucang, there is endocrine disruption ability.Can impact the growth of organism, immunity after entering organism, even carcinogenic, harm organism is healthy.American National Environmental Protection Agency, world's Wildlife Fund are organized and are classified as environment incretion interferent (Endocrinedisruptingchemicals, EDCs).Output and the consumption figure of China BPA are huge, and be the commercial synthesis raw material of epoxy resin and Merlon, in its factory effluent, content of bisphenol A is higher, deals with improperly and causes a significant threat to environment.
At present, the method of conventional removal bisphenol-A has the technology such as activated sludge, charcoal absorption, film process, ozone oxidation, but these methods exist, and removal effect is not good, bisphenol-A of can not degrading make it to lose endocrine or ozone oxidation not exclusively, product species and toxicity fails to understand, makes these technology cannot reach the object of safe and effective removal bisphenol-A.And be that the removal effect of traditional wastewater treatment system to BPA of main process is limited with biological treatment, the half-life reaches a couple of days to several weeks.TiO
2photocatalysis oxidation technique catalytic activity is high, easy and simple to handle, the mineralization of organic material of part difficult for biological degradation in water can be become CO
2and H
2o is a kind of environmentally-friendly technique, has huge application prospect.In view of TiO
2be nanometer materials, suspend distribution in the reactor, is difficult to reclaim, and not only wastes resource, also can cause secondary pollution.For bisphenol-A difficult for biological degradation, suspended state TiO
2the problem such as difficulty recovery, the recyclable magnet carried photocatalyst TiO of fast degradation bisphenol-A is prepared in this research
2/ SiO
2/ γ-Fe
2o
3, detect the structure composition of this catalyst, surface characteristic and the degradation effect to BPA in water thereof, inquire into its degradation rule, investigate the repeatedly organic efficiency after this catalyst degradation bisphenol-A simultaneously.
Summary of the invention
Goal of the invention: the invention provides recyclable titanium dioxide optical catalyst of a kind of fast degradation high concentration bisphenol-A waste water and its preparation method and application, to solve in prior art bisphenol-A difficult degradation and TiO in waste water
2the problem that particle is difficult in the solution be separated and can not reuses.
Technical scheme: to achieve these goals, the present invention by the following technical solutions:
A preparation method for the recyclable titanium dioxide optical catalyst of fast degradation high concentration bisphenol-A waste water, comprises the following steps:
(1) magnetic core is prepared: by Fe
2(SO
4)
3and FeSO
47H
2o is dissolved in the deionized water of same volume respectively; be mixed with after concentration is the aqueous solution of 0.15mol/L and mix; ethanol is added in above-mentioned mixed solution; 80 DEG C of water-baths; and stirred under nitrogen atmosphere, add sodium hydroxide solution and pH value is adjusted to 11 ~ 13, after stirring 1h; ageing 3h at 60 DEG C, obtains magnetic core Fe
3o
4, use magnet separated product, and spend deionized water 3 times;
(2) SiO is prepared
2intermediate layer: the magnetic core Fe obtained by step (1)
3o
4sample is placed in 100mL deionized water, add the dispersant of 30ml0.1mol/L, under 50 DEG C of water-baths, first stir and play peptizaiton, then continue to stir, and add 28ml ethyl orthosilicate and 10mL concentrated ammonia liquor successively, after stirring 3h, wash 3 times with ethanol, at 80 DEG C after finish-drying, at temperature is 400 DEG C, calcine 1h; Again temperature is adjusted to 600 DEG C of calcining 2h, obtains SiO
2/ γ-Fe
2o
3;
(3) load TiO
2layer: by step (2) gained SiO
2/ γ-Fe
2o
3sample is placed in 52ml butyl titanate and 150 ~ 180ml ethanol, after ultrasonic disperse 10min, 40 DEG C of stirred in water bath, drip volumetric concentration and be followed successively by the deionized water of 6% ~ 24%, 1% ~ 4%, 72% ~ 93%, the mixed solution of nitric acid and ethanol, in time being hydrolyzed formation colloidal sol, stop stirring; After ageing 1h, through 80 DEG C of finish-dryings, obtain gel, then at 460 DEG C ~ 500 DEG C, calcining 1 ~ 2h, finally grinds to obtain magnet carried photocatalyst TiO
2/ SiO
2/ γ-Fe
2o
3.
(4) CuO doping: adopt infusion process to carry out copper ion doped, by TiO
2/ SiO
2/ γ-Fe
2o
3photochemical catalyst is placed in 100ml deionized water, in above-mentioned mixed solution, add Cu (NO
3)
2solution, ultrasonic disperse 30min, after 104 DEG C of finish-dryings, through 350 ~ 450 DEG C of high-temperature calcination 4h, grinding obtains the magnetic carrying of titanium dioxide photocatalyst CuO/TiO of Copper-cladding Aluminum Bar modification
2/ SiO
2/ γ-Fe
2o
3.
Further, the amount of the ethyl orthosilicate dripped in step (2) is 1.0 times of Fe element molal quantity, and in step (3), the amount of butyl titanate is 2.0 times of Fe element molal quantity.
Further, in step (4), copper ion doped concentration is remembered with CuO, and the ratio that CuO content accounts for catalyst total amount is 2 ~ 4%.
Further, paddle is used to stir with the speed of 1000rad/min in described step (1).
Further, first stir with the speed of 200rad/min in described step (2) and play peptizaiton, then stir with the speed of 1000rad/min.
Further, in described step (3) in 40 DEG C of water-baths, stir with the speed of 1000rad/min, drip volumetric concentration with the speed of 120/min and be followed successively by the deionized water of 6% ~ 24%, 1% ~ 4%, 72% ~ 93%, the mixed solution of nitric acid and ethanol.
Further, in described step (2), dispersant is sodium dodecyl sulfate solution.
Further, in described step (3), the gel of gained, is warmed up to 460 DEG C ~ 500 DEG C according to 5 DEG C/min.
A recyclable titanium dioxide optical catalyst for fast degradation high concentration bisphenol-A waste water, comprises magnetic core Fe
3o
4, magnetic core Fe
3o
4be wrapped with intermediate layer SiO
2, intermediate layer SiO
2outer also load has TiO
2layer, TiO
2top layer is doped with CuO.
An application for the recyclable titanium dioxide optical catalyst of fast degradation high concentration bisphenol-A waste water, the recyclable magnetic titanium dioxide photocatalyst applications of fast degradation high concentration bisphenol-A waste water is in process epoxy resin production waste-water; Containing bisphenol-A, phenol and NaCl in described epoxy resin production waste-water, the pH value of described epoxy resin production waste-water is 6 ~ 13; During process epoxy resin production waste-water, the consumption of the recyclable magnetic titanium dioxide photochemical catalyst of fast degradation high concentration bisphenol-A waste water is 4.0g/L.
Beneficial effect: catalyst prepared by the present invention can degrading high concentration bisphenol-A waste water fast and efficiently, the TiO of load
2be mainly the Detitanium-ore-type that catalytic activity is the highest; Utilize externally-applied magnetic field can realize repeatedly effectively reclaiming of catalyst, and keep higher catalytic degradation ability.Also good degradation effect is had for epoxy resin production waste-water.
Accompanying drawing explanation
Fig. 1 shows the surface structure of the copper-doped titanium dioxide magnet carried photocatalyst that the embodiment of the present invention provides;
Fig. 2 shows copper-doped titanium dioxide photochemical catalyst that the embodiment of the present invention the provides degradation efficiency for BPA;
Fig. 3 shows copper-doped titanium dioxide photochemical catalyst that the embodiment of the present invention the provides degradation efficiency for actual bifunctional epoxy resin factory effluent;
Fig. 4 shows the organic efficiency of the titanium dioxide magnet carried photocatalyst that the embodiment of the present invention provides.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further described.
Embodiment 1
A preparation method for the recyclable magnetic titanium dioxide photochemical catalyst of fast degradation high concentration bisphenol-A waste water, comprises the following steps:
(1) magnetic core is prepared:
Take 6.0gFe respectively
2(SO
4)
3and 4.2gFeSO
47H
2o is dissolved in the deionized water of same volume respectively; be mixed with each 100ml of the aqueous solution that concentration is 0.15mol/L; then mix, in above-mentioned mixed solution, add 100ml ethanol, 80 DEG C of water-baths; and under nitrogen protection; use paddle to carry out rapid stirring with 1000rad/min, add sodium hydroxide solution and pH value is adjusted to 11, after stirring 1h; ageing 3h at 60 DEG C, with magnet separated product Fe
3o
4, and spend deionized water 3 times.
(2) SiO is prepared
2intermediate layer:
The magnetic core Fe obtained by step (1)
3o
4sample is placed in 100mL deionized water, add the sodium dodecyl sulfate solution of 30ml0.1mol/L, under 50 DEG C of water-baths, first 200rad/min stirring at low speed plays peptizaiton, then with 1000rad/min rapid stirring, and add 28ml ethyl orthosilicate and 10mL concentrated ammonia liquor successively, after stirring 3h, wash 3 times with ethanol, at 80 DEG C after finish-drying, at temperature is 400 DEG C, calcine 1h; Again temperature is adjusted to 600 DEG C of calcining 2h, obtains SiO
2/ γ-Fe
2o
3;
(3) load TiO
2layer:
By step (2) gained SiO
2/ γ-Fe
2o
3sample is placed in 52ml butyl titanate and 150ml ethanol, after ultrasonic disperse 10min, with 1000rad/min rapid stirring in 40 DEG C of water-baths, slowly drip volumetric concentration with 120/min and be followed successively by the deionized water of 24%, 4%, 72%, the mixed solution of nitric acid and ethanol, in time being hydrolyzed formation colloidal sol, stop stirring; After ageing 1h, through 80 DEG C of finish-dryings, obtain gel, at being then warmed up to 460 DEG C according to 5 DEG C/min, calcine 1h, finally grind to obtain magnet carried photocatalyst TiO
2/ SiO
2/ γ-Fe
2o
3.
(4) CuO doping:
Adopt infusion process to carry out copper ion doped, get 1gTiO
2/ SiO
2/ γ-Fe
2o
3photochemical catalyst is placed in 100ml deionized water, adds the Cu (NO of 3.78ml0.01mol/L in above-mentioned mixed solution
3)
2solution, ultrasonic disperse 30min, after 104 DEG C of finish-dryings, through 350 DEG C of high-temperature calcination 4h, grinding obtains the magnetic carrying of titanium dioxide photocatalyst CuO/TiO of Copper-cladding Aluminum Bar modification
2/ SiO
2/ γ-Fe
2o
3.
The amount of the ethyl orthosilicate dripped in described step (2) is 1.0 times of Fe element molal quantity.
In described step (3), the amount of butyl titanate is 2.0 times of Fe element molal quantity.
In described step (4), the doping content of CuO is 3%.
Embodiment 2
A preparation method for the recyclable magnetic titanium dioxide photochemical catalyst of fast degradation high concentration bisphenol-A waste water, comprises the following steps:
(1) magnetic core is prepared:
Take 6.0gFe respectively
2(SO
4) 3and 4.2gFeSO
47H
2o is dissolved in the deionized water of same volume respectively; be mixed with each 100ml of the aqueous solution that concentration is 0.15mol/L; then mix, in above-mentioned mixed solution, add 100ml ethanol, 80 DEG C of water-baths; and under nitrogen protection; use paddle to carry out rapid stirring with 1000rad/min, add sodium hydroxide solution and pH value is adjusted to 12, after stirring 1h; ageing 3h at 60 DEG C, with magnet separated product Fe
3o
4, and spend deionized water 3 times.
(2) SiO is prepared
2intermediate layer:
The magnetic core Fe obtained by step (1)
3o
4sample is placed in 100mL deionized water, add the dispersant of 30ml0.1mol/L, under 50 DEG C of water-baths, first 200rad/min stirring at low speed plays peptizaiton, then with 1000rad/min rapid stirring, and add 28ml ethyl orthosilicate and 10mL concentrated ammonia liquor successively, after stirring 3h, wash 3 times with ethanol, at 80 DEG C after finish-drying, at temperature is 400 DEG C, calcine 1h; Again temperature is adjusted to 600 DEG C of calcining 2h, obtains SiO
2/ γ-Fe
2o
3;
(3) load TiO
2layer:
By step (2) gained SiO
2/ γ-Fe
2o
3sample is placed in 52ml butyl titanate and 160ml ethanol, after ultrasonic disperse 10min, with 1000rad/min rapid stirring in 40 DEG C of water-baths, slowly drip volumetric concentration with 120/min and be followed successively by the deionized water of 6%, 1%, 93%, the mixed solution of nitric acid and ethanol, in time being hydrolyzed formation colloidal sol, stop stirring; After ageing 1h, through 80 DEG C of finish-dryings, obtain gel, at being then warmed up to 480 DEG C according to 5 DEG C/min, calcine 1.5h, finally grind to obtain magnet carried photocatalyst TiO
2/ SiO
2/γ-Fe
2o
3.
(4) CuO doping:
Adopt infusion process to carry out copper ion doped, get 1gTiO
2/ SiO
2/ γ-Fe
2o
3photochemical catalyst is placed in 100ml deionized water, adds the Cu (NO of 5.04ml0.01mol/L in mixed solution
3)
2solution, ultrasonic disperse 30min, after 104 DEG C of finish-dryings, through 400 DEG C of high-temperature calcination 4h, grinding obtains the magnetic carrying of titanium dioxide photocatalyst CuO/TiO of Copper-cladding Aluminum Bar modification
2/ SiO
2/ γ-Fe
2o
3.
The amount of the ethyl orthosilicate dripped in described step (2) is 1.0 times of Fe element molal quantity.
In described step (3), the amount of butyl titanate is 2.0 times of Fe element molal quantity.
In described step (4), the doping content of CuO is 4%.
Embodiment 3
A preparation method for the recyclable magnetic titanium dioxide photochemical catalyst of fast degradation high concentration bisphenol-A waste water, comprises the following steps:
(1) magnetic core is prepared:
Take 6.0gFe respectively
2(SO
4)
3and 4.2gFeSO
47H
2o is dissolved in the deionized water of same volume respectively; be mixed with each 100ml of the aqueous solution that concentration is 0.15mol/L; then mix, in above-mentioned mixed solution, add 100ml ethanol, 80 DEG C of water-baths; and under nitrogen protection; use paddle to carry out rapid stirring with 1000rad/min, add sodium hydroxide solution and pH value is adjusted to 13, after stirring 1h; ageing 3h at 60 DEG C, with magnet separated product Fe
3o
4, and spend deionized water 3 times.
(2) SiO is prepared
2intermediate layer:
The magnetic core Fe obtained by step (1)
3o
4sample is placed in 100mL deionized water, add the dispersant of 30ml0.1mol/L, under 50 DEG C of water-baths, first 200rad/min stirring at low speed plays peptizaiton, then with 1000rad/min rapid stirring, and add 28ml ethyl orthosilicate and 10mL concentrated ammonia liquor successively, after stirring 3h, wash 3 times with ethanol, at 80 DEG C after finish-drying, at temperature is 400 DEG C, calcine 1h; Again temperature is adjusted to 600 DEG C of calcining 2h, obtains SiO
2/ γ-Fe
2o
3;
(3) load TiO
2layer:
By step (2) gained SiO
2/ γ-Fe
2o
3sample is placed in 52ml butyl titanate and 180ml ethanol, after ultrasonic disperse 10min, with 1000rad/min rapid stirring in 40 DEG C of water-baths, slowly drip volumetric concentration with 120/min and be followed successively by the deionized water of 12%, 2%, 86%, the mixed solution of nitric acid and ethanol, in time being hydrolyzed formation colloidal sol, stop stirring; After ageing 1h, through 80 DEG C of finish-dryings, obtain gel, at being then warmed up to 500 DEG C according to 5 DEG C/min, calcine 2h, finally grind to obtain magnet carried photocatalyst TiO
2/ SiO
2/ γ-Fe
2o
3.
(4) CuO doping:
Adopt infusion process to carry out copper ion doped, get 1gTiO
2/ SiO
2/ γ-Fe
2o
3photochemical catalyst is placed in 100ml deionized water, adds the Cu (NO of 2.52ml0.01mol/L in mixed solution
3)
2solution, ultrasonic disperse 30min, after 104 DEG C of finish-dryings, through 450 DEG C of high-temperature calcination 4h, grinding obtains the magnetic carrying of titanium dioxide photocatalyst CuO/TiO of Copper-cladding Aluminum Bar modification
2/ SiO
2/ γ-Fe
2o
3.
The amount of the ethyl orthosilicate dripped in described step (2) is 1.0 times of Fe element molal quantity.
In described step (3), the amount of butyl titanate is 2.0 times of Fe element molal quantity.
In described step (4), the doping content of CuO is 2%.
The application example of the recyclable magnetic titanium dioxide photochemical catalyst of fast degradation high concentration bisphenol-A waste water prepared by the present invention:
Copper-cladding Aluminum Bar magnetic carries TiO
2the preparation method of photochemical catalyst is directly connected to the catalytic performance of catalyst, and then affects the treatment effect of photochemical catalyst.Adopt the TiO that sol-gel process provided by the invention is obtained
2be evenly distributed, narrow diameter distribution, specific area are large, combine firmly, be specially adapted to the preparation of difformity carrier surface photo-catalysis function film.In order to improve catalytic effect, at TiO
2surface doping copper ion modified.Meanwhile, for intercepting TiO
2with magnetic core generation clinkering, mutual, affect the catalytic activity of catalyst and magnetic and the intermediate layer SiO that adds
2genus polyporus material, surface configuration is various, and therefore, the present invention adopts sol-gel process to prepare TiO
2.
The present invention is directed to the difficult degradation of high concentration bisphenol-A waste water, slow problem of degrading, successfully prepare the recyclable magnetic carrying of titanium dioxide photocatalyst of bisphenol-A in fast degradation waste water, photocatalytic degradation experiment results proved is under the ultraviolet lighting of UV254, and this catalyst has good photocatalytic activity and can magnetic recyclability to bisphenol-A in waste water.
Magnet carried photocatalyst CuO/TiO
2/ SiO
2/ γ-Fe
2o
3catalytic degradation high concentration bisphenol-A gives up water test: according to relevant report, in China's industrial park sewage, bisphenol A concentration is 74.38 ~ 597.07 μ g/L, the concentration of corresponding workshop bisphenol-A can be higher, and it is 10mg/L that this application example selectes bisphenol A concentration in solution.Reaction condition is: pH value is 5, catalyst amounts 4g/L, water temperature 30 DEG C, UV254 UV-irradiation, uviol lamp power P light=25W, uviol lamp wavelength X=254nm, motor machine agitator.By bisphenol-A residual concentration in high performance liquid chromatograph detection reaction liquid, calculate bisphenol-A degradation rate, with the degradation rate of bisphenol-A for evaluating magnetic carrying of titanium dioxide light photochemical catalyst CuO/TiO
2/ SiO
2/ γ-Fe
2o
3the foundation of photocatalytic activity.
Application example concrete operations are: select and add the BPA solution that 100mL initial concentration is 10mg/L in the quartz reactor (Φ × H=80 × 100mm) of 500ml.The uviol lamp level of dominant wavelength 254nm is placed in directly over reactor, distance liquid level 100mm at the bottom of fluorescent tube, liquid level place light intensity 434 μ W/cm2, sampling interval time point is 10min, 30min, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h.Carry out in time after sample preparation well twice centrifugal, centrifugal condition is respectively rotating speed 8000r/min, duration 10min, temperature 4 DEG C and rotating speed 10000r/min, duration 10min, temperature 4 DEG C.Bisphenol A concentration adopts Agilent-1260 type hplc determination, C18 chromatographic column, mobile phase is methyl alcohol: water=80:20, methyl alcohol (HPLC level, Tedia company), experimental water (Milli-Q ultrapure water system, Millipore company), flow velocity 1mL/min, column temperature room temperature, fluorescence detector, excitation wavelength 227nm, emission wavelength 313nm.
Fig. 1 shows the surface structure of the copper-doped titanium dioxide magnet carried photocatalyst that the embodiment of the present invention provides, TiO
2uniform load, on magnetic carrier, links firmly, difficult drop-off.Catalyst outward appearance glomeration particle.Between diameter 100 ~ 300nm, be evenly distributed.
Fig. 2 shows copper-doped titanium dioxide photochemical catalyst that the embodiment of the present invention the provides degradation efficiency for BPA.
After reaction 3h, in reaction system, this catalyst is to the clearance Da Gaoda 67.5% of BPA.Further, after reaction 5h, BPA removal efficiency is basicly stable, and maintain more than 80%, reaction speed is very fast.。Demonstrating the recyclable titanium dioxide optical catalyst of Copper-cladding Aluminum Bar that the embodiment of the present invention provides goes degraded higher to high concentration bisphenol-A waste water.
Wherein, pH value=7, catalyst amounts=4.0g/L, BPA initial concentration=10mg/L, water temperature=30 DEG C, uviol lamp power P
light=25W, uviol lamp wavelength X=254nm
Fig. 3 shows copper-doped titanium dioxide photochemical catalyst that the embodiment of the present invention the provides degradation efficiency for actual bisphenol A epoxide resin factory effluent.Because epoxy resin is that raw material synthesizes in the basic conditions mainly with organic matters such as bisphenol-As, its actual factory effluent water quality is complicated.Investigation finds, current China epoxy resin is produced waste water per year and is about 6,500,000 t, content of organics is high (sometimes more than 5000mg/L, even 15000mg/L), simultaneously because its inorganic salinity is high, hardly degraded organic substance high, very big on the impact of biochemical treatment, processing cost and very difficult.Therefore, urgently develop new technology and effective advanced treating is carried out to such waste water, to avoid its discharge, water environment is threatened.This application example adopts water quality (table 1) to simulate epoxy resin production waste-water, is the application example of recyclable magnetic titanium dioxide photochemical catalyst in epoxy resins factory effluent of fast degradation high concentration bisphenol-A waste water prepared by the present invention.When other pollutants coexist, the removal efficiency change of catalyst of the present invention to BPA is less, and the clearance of 3h, still up to 53%, shows good stability.Further, while removal BPA, also effectively can reduce the concentration of phenol in wastewater, removal efficiency is higher in actual applications.
Wherein: pH value=8.5, catalyst amounts=4.0g/L, water quality situation refers to table 1, water temperature=30 DEG C, uviol lamp power P
light=25W, uviol lamp wavelength X=254nm
Bisphenol wastewater simulated by table 1
Fig. 4 shows the organic efficiency of the titanium dioxide magnet carried photocatalyst that the embodiment of the present invention provides.
Catalyst prepared by the present invention can realize catalyst and being separated of disposing of sewage under the effect of externally-applied magnetic field, reaches recovering effect.When first time reclaims, the rate of recovery of catalyst is 95%, and when second time reclaims, catalyst recovery efficiency reduces to 93%, and when third time reclaims, catalyst recovery yield is that the 89%, four organic efficiency becomes 87%.Repeat recovery four times, the rate of recovery of catalyst all maintains higher level, reclaim the clearance of catalyst to BPA and remain on more than 60%, illustrate that the recyclable photochemical catalyst of Copper-cladding Aluminum Bar that the embodiment of the present invention provides has good recyclability, effectively can reduce the catalyst attrition in engineer applied, reduce the generation of secondary pollution, in containing the Practical Project of bisphenol-A Industrial Wastewater Treatment, there is applications well prospect.
Wherein, pH value=7, catalyst amounts=4.0g/L, BPA initial concentration=10mg/L, water temperature=30 DEG C, uviol lamp power P
light=25W, uviol lamp wavelength X=254nm.
A recyclable magnetic titanium dioxide photochemical catalyst for fast degradation high concentration bisphenol-A waste water, is characterized in that: comprise magnetic core Fe
3o
4, magnetic core Fe
3o
4be wrapped with intermediate layer SiO
2, intermediate layer SiO
2outer also load has TiO
2layer, TiO
2surface doping CuO modification.Catalyst prepared by the present invention all has good application in high concentration bisphenol-A waste water and epoxy resin production waste-water.
Catalyst prepared by the present invention can degrading high concentration bisphenol-A waste water fast and efficiently, and bisphenol A concentration is the TiO of 10mg/L, load
2be mainly the Detitanium-ore-type that catalytic activity is the highest.
The above is only the preferred embodiment of the present invention; be noted that for those skilled in the art; under the premise without departing from the principles of the invention, can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a preparation method for the recyclable titanium dioxide optical catalyst of fast degradation high concentration bisphenol-A waste water, is characterized in that, comprise the following steps:
(1) magnetic core is prepared: by Fe
2(SO
4)
3and FeSO
47H
2o is dissolved in the deionized water of same volume respectively; be mixed with after concentration is the aqueous solution of 0.15mol/L and mix; ethanol is added in above-mentioned mixed solution; 80 DEG C of water-baths; and stirred under nitrogen atmosphere, add sodium hydroxide solution and pH value is adjusted to 11 ~ 13, after stirring 1h; ageing 3h at 60 DEG C, obtains magnetic core Fe
3o
4, use magnet separated product, and spend deionized water 3 times;
(2) SiO is prepared
2intermediate layer: the magnetic core Fe obtained by step (1)
3o
4sample is placed in 100mL deionized water, add the dispersant of 30ml0.1mol/L, under 50 DEG C of water-baths, first stir and play peptizaiton, then continue to stir, and add 28ml ethyl orthosilicate and 10mL concentrated ammonia liquor successively, after stirring 3h, wash 3 times with ethanol, at 80 DEG C after finish-drying, at temperature is 400 DEG C, calcine 1h; Again temperature is adjusted to 600 DEG C of calcining 2h, obtains SiO
2/ γ-Fe
2o
3;
(3) load TiO
2layer: by step (2) gained SiO
2/ γ-Fe
2o
3sample is placed in 52ml butyl titanate and 150 ~ 180ml ethanol, after ultrasonic disperse 10min, 40 DEG C of stirred in water bath, drip volumetric concentration and be followed successively by the deionized water of 6% ~ 24%, 1% ~ 4%, 72% ~ 93%, the mixed solution of nitric acid and ethanol, in time being hydrolyzed formation colloidal sol, stop stirring; After ageing 1h, through 80 DEG C of finish-dryings, obtain gel, then at 460 DEG C ~ 500 DEG C, calcining 1 ~ 2h, finally grinds to obtain magnet carried photocatalyst TiO
2/ SiO
2/ γ-Fe
2o
3.
(4) CuO doping: adopt infusion process to carry out copper ion doped, by TiO
2/ SiO
2/ γ-Fe
2o
3photochemical catalyst is placed in 100ml deionized water, in above-mentioned mixed solution, add Cu (NO
3)
2solution, ultrasonic disperse 30min, after 104 DEG C of finish-dryings, through 350 ~ 450 DEG C of high-temperature calcination 4h, grinding obtains the magnetic carrying of titanium dioxide photocatalyst CuO/TiO of Copper-cladding Aluminum Bar modification
2/ SiO
2/ γ-Fe
2o
3.
2. the preparation method of the recyclable titanium dioxide optical catalyst of fast degradation high concentration bisphenol-A waste water according to claim 1, it is characterized in that: the amount of the ethyl orthosilicate dripped in step (2) is 1.0 times of Fe element molal quantity, in step (3), the amount of butyl titanate is 2.0 times of Fe element molal quantity.
3. the preparation method of the recyclable titanium dioxide optical catalyst of fast degradation high concentration bisphenol-A waste water according to claim 1, it is characterized in that: in step (4), copper ion doped concentration is remembered with CuO, the ratio that CuO content accounts for catalyst total amount is 2 ~ 4%.
4. the preparation method of the recyclable titanium dioxide optical catalyst of fast degradation high concentration bisphenol-A waste water according to claim 1, is characterized in that: use paddle to stir with the speed of 1000rad/min in described step (1).
5. the preparation method of the recyclable titanium dioxide optical catalyst of fast degradation high concentration bisphenol-A waste water according to claim 1, it is characterized in that: first stir with the speed of 200rad/min in described step (2) and play peptizaiton, then stir with the speed of 1000rad/min.
6. the preparation method of the recyclable titanium dioxide optical catalyst of fast degradation high concentration bisphenol-A waste water according to claim 1, it is characterized in that: in described step (3) in 40 DEG C of water-baths, stir with the speed of 1000rad/min, drip volumetric concentration with the speed of 120/min and be followed successively by the deionized water of 6% ~ 24%, 1% ~ 4%, 72% ~ 93%, the mixed solution of nitric acid and ethanol.
7. the preparation method of the recyclable titanium dioxide optical catalyst of fast degradation high concentration bisphenol-A waste water according to claim 1, is characterized in that: in described step (2), dispersant is sodium dodecyl sulfate solution.
8. the preparation method of the recyclable titanium dioxide optical catalyst of fast degradation high concentration bisphenol-A waste water according to claim 1, is characterized in that: the gel of gained in described step (3), is warmed up to 460 DEG C ~ 500 DEG C according to 5 DEG C/min.
9. a recyclable titanium dioxide optical catalyst for fast degradation high concentration bisphenol-A waste water, is characterized in that: comprise magnetic core Fe
3o
4, magnetic core Fe
3o
4be wrapped with intermediate layer SiO
2, intermediate layer SiO
2outer also load has TiO
2layer, TiO
2top layer is doped with CuO.
10. an application for the recyclable titanium dioxide optical catalyst of fast degradation high concentration bisphenol-A waste water, is characterized in that: the recyclable magnetic titanium dioxide photocatalyst applications of fast degradation high concentration bisphenol-A waste water is in process epoxy resin production waste-water; Containing bisphenol-A, phenol and NaCl in described epoxy resin production waste-water, the pH value of described epoxy resin production waste-water is 6 ~ 13; During process epoxy resin production waste-water, the consumption of the recyclable magnetic titanium dioxide photochemical catalyst of fast degradation high concentration bisphenol-A waste water is 4.0g/L.
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