CN101648148B - Preparation method of nanometer photocatalyst film for degrading organic matter in waste water - Google Patents
Preparation method of nanometer photocatalyst film for degrading organic matter in waste water Download PDFInfo
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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
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- 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 relates to a preparation method of a nanometer photocatalyst film for degrading organic matters in waste water, comprising the following steps: firstly, mixing a polymer PVDF or (VDF-HFP) and a plasticizing agent PC and DMC according to a mass ratio of 1:2-4:2-4; adding 10-20 percent of nanometer ZnO powder with a hexagonal system wurtzite structure or/and nanometer TiO2 powder witha pyramidal system anatase structure and evenly mixing; adding 2.5-5.5 times of (polymer mass, plasticizing agent mass and nanometer photocatalyst mass) acetone or acetonitrile; sufficiently mixing to obtain even and ropy suspending liquid; finally, casting the suspending liquid on slide glass to naturally flow and form; and standing, solidifying, drying, cooling anduncovering a film with thickness about 0.12-0.16mm from the slide glass. The nanometer photocatalyst film is even and consistent, has good mechanical property, can effectively degrade organic matters in the waste water and can be repeatedly used.
Description
One, technical field
The present invention relates to a kind of preparation method of functional membrane, the particularly preparation method of semiconductor light-catalyst film, the preparation method of organic nano-catalytic agent film in specifically a kind of degrading waste water.
Two, technical background
Developing rapidly of current industry, pollution on the environment is on the rise, and along with the continuous discharging of industrial wastewater, the water source that the mankind is rely generate is contaminated gradually.For the water source of protecting the mankind to depend on for existence, must handle industrial wastewater.
The nanometer photocatalyst film technology is a kind of green technology of new and effective degradation of organic substances waste water.Wherein the major advantage of semiconductor nano photocatalyst film technology is: oxidability is strong, treatment effeciency is high, energy consumption is lower, reaction condition is gentle, non-secondary pollution, can make great majority be difficult to the toxic organic compound exhaustive oxidation that maybe can not degrade at normal temperatures to decompose, and is easy to be applied to during industrial organic waste water handles.In numerous semiconductor light-catalysts, the TiO that tetragonal crystal system is anatase structured
2With the ZnO of hexagonal crystal system wurtzite structure be more satisfactory semiconductor light-catalyst material, they have catalytic activity height, reaction rate fast, to organic degraded non-selectivity and can make it the characteristics that exhaustive oxidation decomposes, thereby in degradation of organic substances waste water, have a good application prospect.
The principle of semiconductor nano photocatalyst for degrading organic wastewater: nano-photocatalyst especially under UV-irradiation, enters excitation state under solar radiation, the electronics on the valence band is excited on the conduction band, forms the free electron e on the conduction band
-, have strong reducing property, leave hole h in valence band simultaneously
+, have strong oxidizing property, h
+And e
-Form redox system in photocatalyst surface.When the semiconductor nano photochemical catalyst is in the aqueous solution, h
+Can be the OH of photocatalyst surface absorption
-, H
2Materials such as O are oxidized to highly active hydroxyl radical free radical (OH); In addition, O
2Electronics that can the capture catalyst surface generates O
2 -, with H
+With the electronics (e that catches
-) reaction generation hydroxyl radical free radical (OH), at the OH of semiconductor nano photocatalyst surface is strong oxidizer, it can pass through series reaction with phenol, be easy to phenol degrading become adjacent (to) benzenediol, benzoquinones, along intermediate products such as (instead) butene dioic acid, acetate and formic acid, take special device these intermediate products finally can be oxidized to CO
2And H
2O, thus finish organic degraded.
According to experiment as can be known, the catalytic performance of nanometer photocatalyst film is significantly better than the nano-photocatalyst powder.According to the literature, the method for preparing nanometer photocatalyst film at present mainly contains dip-coating method, sedimentation and electrodeposition process etc.Their preparation process is all complicated, be not suitable for suitability for industrialized production, and catalytic efficiency is not very good yet.Therefore be necessary to develop that a kind of preparation technology is simple, cost is lower, be applicable to suitability for industrialized production, photocatalysis efficiency height and the service life technology of preparing of long nanometer photocatalyst film.
Three, summary of the invention
The present invention aims to provide a kind of nanometer photocatalyst film that organic wastewater is used of handling, and technical problem to be solved is the preparation method of this film.
The nanometer photocatalyst film that the present invention is alleged, nano-photocatalyst are selected from semiconductor nano ZnO (hexagonal crystal system wurtzite structure) or/and nano-TiO
2(tetragonal crystal system is anatase structured), nano-ZnO is or/and nano-TiO
2It is the nano-powder for preparing by sol-gel process or microemulsion method or hydro-thermal method etc.; Described film is a thin polymer film, and polymer is selected from polyvinylidene fluoride (PVDF), and molecular weight is 400000～500000, perhaps polyvinylidene fluoride-hexafluoropropylene copolymer P (VDF-HFP), and molecular weight is 600000～700000.
The preparation method of this film: with polymer P VDF or copolymer p (VDF-HFP) and nano-ZnO or/and TiO
2Be raw material, the mixing, moulding and the drying that comprise slide preliminary treatment, raw material, difference with the prior art be described mixing at first to be polymer and plasticizer propene carbonate (PC) and dimethyl carbonate (DMC) mix by 1: 2～4: 2～4 mass ratio, the nano-ZnO that adds 10～20% (mass percents) then is or/and TiO
2Powder stirs, the acetone or the acetonitrile that add 2.5～5.5 mixture gross masses (polymer quality+plasticizer quality+nano-photocatalyst quality) at last, fully stir and obtain the finely dispersed thickness suspension of nano-powder, the suspension of thickness is poured on the wave carrier piece, allow its natural flow casting molding, leave standstill, solidify, dry, cooling back takes film, the thick 0.12～0.16mm of film off on wave carrier piece.
Specific operation process is as follows:
1, wave carrier piece preliminary treatment:
With common slide is substrate, before film forming, at first slide is carried out preliminary treatment, to remove surface contaminant, guarantees the uniformity of film and the bond strength of substrate and film.Preprocessing process comprises that pickling, washing, alcohol are washed and drying.Concrete steps are as follows:
(1) water is cleaned the dust of slide surface and solubility and caducous insoluble matter impurity;
(2) slide is placed the HCl solution of 0.1～0.15mol/L soak 20～24h, wash repeatedly with the running water that flows then, to remove the acid solution of slide surface clean;
(3) again slide is put into absolute ethyl alcohol, clean 30～40min with ultrasonic wave;
(4) use distilled water ultrasonic cleaning slide again, to reach the purpose of slide surface cleaning.Make water to flow down, and only stay the layer of even moisture film, the phenomenon that the globule accumulates in the surface do not occur in slide surface along slide surface;
(5) dry 1～2h in 80～100 ℃ of vacuum tanks, the cooling back is taken out and is placed drier standby.
2, the preparation of nanometer photocatalyst film
The step of preparation nanometer photocatalyst film is as follows:
(1) in polymer: the ratio (mass ratio) of plasticizer (two kinds)=1: 2～4: 2～4, take by weighing a certain amount of PVDF or P (VDF-HFP), PC, DMC, mix the back and add the nano-ZnO of 10～20% (mass fractions) or/and nano-TiO
2Powder also stirs, and adds ZnO and TiO when simultaneously
2The time, both relative scales are any;
(2) in the mixture of (1) preparation, add the solvent acetone of 2.5～5.5 times of amounts (agent quality+nano-photocatalyst quality is moulded in polymer quality+increase) or acetonitrile etc., stir the suspension that obtains the homogeneous thickness after 20～50 minutes;
(3) this suspension is cast on the slide glass, allows it prolong stream naturally and form thin film;
(4) it is left standstill put into 50 ℃～90 ℃ vacuum tank after 15～40 minutes, dry 1～6 hour, after treating that solvent (acetone or acetonitrile) and plasticizer (PC, DME) volatilize fully, allow film naturally cool to room temperature, it is taken off from slide, promptly obtain the nanometer photocatalyst film of uniformity, satisfactory mechanical property, its thickness is 0.12～0.16mm.
Four, description of drawings
Fig. 1, Fig. 2 are respectively the nano-ZnO and the anatase structured nano-TiOs of tetragonal crystal system of homemade hexagonal crystal system wurtzite structure
2The X-ray diffractogram of powder adopts the Japanese D/Max-rB of company type X-ray diffractometer of science (pipe is pressed 40.0KV, tube current 0.100A, 6 °/min of sweep speed, 10 °～80 ° of sweep limits for Cu target, K α=0.1541nm).The position of main crystal face diffraction maximum is consistent with JCPDS card (89-0511) among Fig. 1, and the position of main crystal face diffraction maximum is identical with JCPDS card (89-4921) among Fig. 2.
Fig. 3 is nano-photocatalyst (ZnO and the TiO by embodiment 2 preparations
2Mixture) TEM of film figure.
Fig. 4 is by embodiment 2 prepared nano-photocatalyst (ZnO and TiO
2Mixture) film is to the degradation rate of 100mL phenol solution (phenol content 300mg/L) and the relation curve of light application time.Curve A is not add H in the system among the figure
2O
2Degradation rate during solution and the relation of light application time; Curve B is to add 1ml (30%) H in the system
2O
2Degradation rate during solution and the relation of light application time; Curve C is to add 2ml (30%) H in the system
2O
2Degradation rate during solution and the relation of light application time.The wherein acquisition of phenol degrading rate is to adopt the direct photometry of 4-amino-antipyrine, under the 510nm of ultraviolet-uisible spectrophotometer wavelength, measures the phenol absorbance of differential responses time, calculates.
Five, the specific embodiment
Embodiment 1
In PVDF: PC: DMC=1: 2.5: 2.5 ratio (mass ratio), take by weighing PVDF0.10g, PC0.25g, DMC0.25g, add the homemade nano ZnO powder of 0.070g, mixed evenly back adds 2.5ml acetone, stir the suspension that forms the homogeneous thickness after 30 minutes, it is cast on the slide, form thin film by prolonging stream naturally, leave standstill after 20 minutes and put into vacuum drying oven, at 80 ℃ of following freeze-day with constant temperature 2h, dried film is naturally cooled to room temperature, take off film, promptly obtain uniformity from slide, the nano-ZnO thin film (membrane area is the thick 0.13mm that is about of 2cm * 4cm) that mechanical strength is good.
Get the conical flask that phenol solution that 100ml contains phenol 150mg/L places 250ml, add 1ml (30%) H
2O
2Solution on the phenol solution surface, is located the membrane suspension of preparation for about 5 centimetres under being placed on bottom the conical flask with 2 40W fluorescent lamps, light irradiation 1.5 hours, and degradation rate reaches 39%.
Embodiment 2
In P (VDF-HFP): PC: DMC=1: 3: 3 ratio (mass ratio), take by weighing P (VDF-HFP) 0.10g, PC0.30g, DMC0.30g, add homemade 0.080g nano ZnO powder and 0.0050g nano-TiO
2Powder, be dissolved in the 3ml acetone after mixing evenly, stir the suspension that forms thickness after 40 minutes, it is cast on the slide, form thin film, leave standstill after 15 minutes and put into vacuum drying oven by prolonging stream naturally, at 80 ℃ of following freeze-day with constant temperature 2h, after dried film naturally cooled to room temperature, take off, promptly obtain uniformity, the good semiconductor nano photocatalyst film (membrane area is the thick 0.15mm of being about of 2cm * 4cm) of mechanical strength from slide.
Get the conical flask that phenol solution that 100ml contains phenol 300mg/L places 250ml, with the preparation membrane suspension on the phenol solution surface, locate for about 15 centimetres that are placed under the conical flask bottom with the 300W high-pressure sodium lamp, illumination 4 hours, the phenol degrading rate reaches 40%; The H that in the phenol solution that contains phenol 300mg/L at 100ml, adds 1ml (30%)
2O
2Solution, illumination 4 hours, degradation rate reaches 92%; Add 2ml (30%) H
2O
2Solution, illumination 2.5 hours, degradation rate reaches 100%.
Embodiment 3
In PVDF: PC: DMC=1: 2: 2 ratio (mass ratio), take by weighing PVDF0.1g, PC0.2g, DMC0.2g, add homemade nano-ZnO of 0.070g and the homemade nano-TiO of 0.010g
2Powder, mixed evenly back adds an amount of acetone, stir the suspension that forms thickness after 35 minutes, it is cast on the slide, form thin film by prolonging stream naturally, leave standstill after 25 minutes and put into vacuum drying oven, at 70 ℃ of following freeze-day with constant temperature 3h, take off from slide after dried film naturally cooled to room temperature, promptly obtain uniformity, the good nano-ZnO/TiO of mechanical strength
2(area is 2cm * 4cm) to film.
Get the conical flask that phenol solution that 100ml contains phenol 150mg/L places 250ml, add 1ml (30%) H
2O
2Solution on the phenol solution surface, shines the membrane suspension of preparation 2 hours with 2 40W fluorescent lamps, and degradation rate reaches 42%.
Embodiment 4
In P (VDF-HFP): PC: DMC=1: 4: 4 ratio (mass ratio), take by weighing P (VDF-HFP) 0.1g, PC0.4g, DMC0.4g, add the homemade nano ZnO powder of 0.090g, mixed evenly back adds an amount of acetone, stir the suspension that forms thickness after 35 minutes, it is cast on the slide, form thin film by prolonging stream naturally, leave standstill after 30 minutes and put into vacuum drying oven, at 75 ℃ of following freeze-day with constant temperature 2.5h, dried film is naturally cooled to room temperature, take off, promptly obtain uniformity from slide, (area is 2cm * 4cm) to the good nano-ZnO thin film of mechanical strength.
This film is suspended in the phenol solution surface that 100ml contains phenol 200mg/L, and according to 3 hours, the phenol degrading rate reached 42% with the 300W high-pressure sodium lamp; When in phenol solution, adding 1ml (30%) H
2O
2Solution is used 300W lamp and high pressure mercury 2 hours, and degradation rate reaches 100%.
Embodiment 5
In P (VDF-HFP): PC: DMC=1: 3.5: 3.5 ratio (mass ratio), take by weighing P (VDF-HFP) 0.1g, PC0.35g, DMC0.35g, add homemade nano ZnO powder of 0.080g and the homemade nano TiO 2 powder of 0.010g, mixed evenly back adds an amount of acetone, stir the suspension that forms thickness after 45 minutes, it is cast on the slide, form thin film by prolonging stream naturally, leave standstill after 30 minutes and put into vacuum drying oven, at 85 ℃ of following freeze-day with constant temperature 1.5h, dried film is naturally cooled to room temperature, take off, promptly obtain uniformity from slide, (area is 2cm * 4cm) to the good nano-ZnO thin film of mechanical strength.
Film is suspended in the surface that 100ml contains the phenol solution of phenol 300mg/L, and according to 4 hours, the phenol degrading rate reached 39% with the 300W high-pressure sodium lamp; When in phenol solution, adding 1ml (30%) H
2O
2Solution, illumination 4 hours, degradation rate reaches 91%; Add 2ml (30%) H
2O
2Solution, 2.5 hours degradation rates of illumination reach 100%.
Embodiment 6
In P (VDF-HFP): PC: DMC=1: 2.5: 2.5 ratio (mass ratio), take by weighing P (VDF-HFP) 0.1g, PC0.25g, DMC0.25g, add the homemade nano ZnO powder of 0.090g, mixed evenly back adds an amount of acetone, stir the suspension liquid that forms thickness after 35 minutes, it is cast on the slide, form thin film by prolonging stream naturally, leave standstill after 30 minutes and put into vacuum drying oven, at 65 ℃ of following freeze-day with constant temperature 4.5h, dried film is naturally cooled to room temperature, take off, promptly obtain uniformity from slide, (area is 2cm * 4cm) to the good nano-ZnO thin film of mechanical strength.
This film is suspended in the surface that 100ml contains the phenol solution of phenol 400mg/L, and according to 4 hours, the phenol degrading rate reached 38% with the 300W high-pressure sodium lamp; When in phenol solution, adding 1ml (30%) H
2O
2Solution, illumination 4 hours, degradation rate can reach 88%; Add 2ml (30%) H
2O
2Solution, illumination 3.5 hours, degradation rate can reach 100%.
Embodiment 7
In P (VDF-HFP): PC: DMC=1: 3.5: 3.5 ratio (mass ratio), take by weighing P (VDF-HFP) 0.1g, PC0.35g, DMC0.35g, add the homemade nano ZnO powder of 0.090g, mixed evenly back adds an amount of acetone, stir the suspension liquid that forms thickness after 35 minutes, it is cast on the slide, form thin film by prolonging stream naturally, leave standstill after 30 minutes and put into vacuum drying oven, at 65 ℃ of following freeze-day with constant temperature 4.5h, dried film is naturally cooled to room temperature, take off, promptly obtain uniformity from slide, (area is 2cm * 4cm) to the good nano-ZnO thin film of mechanical strength.
This film is suspended in the surface that 100ml contains the phenol solution of phenol 250mg/L, and according to 2 hours, the phenol degrading rate reached 38% with the 300W high-pressure sodium lamp; When in phenol solution, adding 1ml (30%) H
2O
2Solution, degradation rate can reach 100%.
Embodiment 8
In PVDF: PC: DMC=1: 2.5: 2.5 ratio (mass ratio), take by weighing PVDF0.1g, PC0.25g, DMC0.25g, add the homemade nano-ZnO of 0.080g, mixed evenly back adds an amount of acetone, stir the suspension liquid that forms thickness after 30 minutes, it is cast on the slide, form thin film by prolonging stream naturally, leave standstill after 20 minutes and put into vacuum drying oven, at 70 ℃ of following freeze-day with constant temperature 3h, take off from slide after dried film naturally cooled to room temperature, promptly obtain uniformity, (area is 2cm * 4cm) to the good nano-ZnO thin film of mechanical strength.
Film is suspended in the phenol solution surface that 100ml contains phenol 150mg/L, and according to 0.75 hour, the phenol degrading rate reached 39% with the 300W high-pressure sodium lamp; When in phenol solution, adding 1ml (30%) H
2O
2Solution, degradation rate can reach 100%.
Embodiment 9
In PVDF: PC: DMC=1: 2.5: 2.5 ratio (mass ratio), take by weighing PVDF0.1g, PC0.25g, DMC0.25g, add the homemade nano-TiO of 0.120g
2Mixed evenly back adds an amount of acetone, stir the suspension liquid that forms thickness after 30 minutes, it is cast on the slide, form thin film by prolonging stream naturally, leave standstill after 20 minutes and put into vacuum drying oven, at 80 ℃ of following freeze-day with constant temperature 2h, take off from slide after dried film naturally cooled to room temperature, (area is 2cm * 4cm) promptly to obtain the good nano-ZnO thin film of uniformity, mechanical strength.
Film is suspended in the phenol solution surface that 100ml contains phenol 250mg/L, uses 300W high voltage mercury lamp radiation 4 hours, the phenol degrading rate reaches 30%; When in phenol solution, adding 1ml (30%) H
2O
2Solution, degradation rate can reach 81%.
Photochemical catalyst wurtzite structure nano-ZnO and anatase structured nano-TiO
2The preparation method of powder.
Nano ZnO powder preparation: take by weighing Zinc diacetate dihydrate 6g and be dissolved in the proper amount of deionized water; Taking by weighing oxalic acid 10.48g is dissolved in the absolute ethyl alcohol; Zinc diacetate dihydrate solution is heated to 65 ℃, add an amount of surfactant lauryl sodium sulfate, carry out magnetic agitation, slowly drip oxalic acid solution again, form leucosol, be incubated certain hour down at 70 ℃, make colloidal sol become gel, put it into 80 ℃ of vacuum tank inner drying 15h, with its taking-up and grind to form powder, put into 650 ℃ Muffle furnace roasting 3h then, promptly obtain the nanometer Zinc oxide powder of hexagonal crystal system wurtzite structure (XRD figure confirmation).
Nano-TiO
2The preparation of powder: get the 10g butyl titanate under magnetic agitation, mix with 8.6mL absolute ethyl alcohol and 0.3mL acetylacetone,2,4-pentanedione solution A, and then magnetic agitation 1h; Under magnetic agitation, 8.6mL absolute ethyl alcohol, 1.3mL distilled water and the dense HCl of 0.1mL are mixed, join solution B, magnetic agitation 0.5h; Solution B is added drop-wise in the solution A, obtains yellow sol; Magnetic agitation 1h more at room temperature leaves standstill colloidal sol after making its abundant mixing, and ageing gets wet gel; And behind 100 ℃ of down dry about 10～12h, get xerogel.Be ground into powder and place 300 ℃ of following roasting 1h,, promptly get the nano-titanium dioxide powder of tetragonal crystal system anatase structured (XRD figure confirmation) then at 500 ℃ of following roasting 2h and naturally cool to room temperature to drive away organic matter.
Embodiment 11
The reusable processing method of nanometer photocatalyst film
With used photocatalyst film earlier with 30% H
2O
2Solution soaked 1.5～3 hours, used distilled water immersion again 1.5～3 hours, taking out the back cleans several times repeatedly with distilled water, put into 70-80 ℃ dry 1.5～2 hours of baking oven then, be evaporated completely Deng distilled water, allow it cool off naturally again, the photocatalyst film of gained is promptly reusable, proceeds the degraded of organic matter sewage.
Claims (1)
1. the preparation method of organic photocatalyst film in the degrading waste water, with the nano-ZnO of polymer poly vinylidene fluoride or polyvinylidene fluoride-hexafluoropropylene copolymer and hexagonal crystal system wurtzite structure or/and the anatase structured nano-TiO of tetragonal crystal system
2Be raw material, comprise preparation, moulding and the drying of slide preliminary treatment, suspension, it is characterized in that: to be polymer mix the back with propene carbonate and dimethyl carbonate by 1: 2～4: 2～4 mass ratio adds 10～20% nano-ZnOs or/and nano-TiO in the preparation of described suspension
2Powder stirs, and adds the acetone or the acetonitrile of 2.5～5.5 times of mixture gross masses then, fully stirs the suspension that obtains the homogeneous thickness, at last suspension is cast in natural casting film-forming on the slide.
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| CN104475163A (en) * | 2014-12-18 | 2015-04-01 | 天津理工大学 | Polyvinylidene fluoride film for visible light catalysis and preparation method of polyvinylidene fluoride film |
| CN106731880A (en) * | 2016-12-20 | 2017-05-31 | 济南大学 | Visible light catalytic hollow fiber ultrafiltration membrane and preparation method based on dopen Nano ZnO |
| CN106824271B (en) * | 2017-03-02 | 2019-10-11 | 安徽工业大学 | A kind of PVDF-Ag/AgBr/g-C3N4The preparation method of-BiOCl (001) composite membrane |
| CN112076739A (en) * | 2020-09-10 | 2020-12-15 | 合肥工业大学 | Composite material for efficiently degrading organic dye in wastewater and preparation method thereof |
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| US20040127354A1 (en) * | 2002-12-31 | 2004-07-01 | John Andrews | Photocatalytically-active, self-cleaning aqueous coating compositions and methods |
| CN101091882A (en) * | 2007-04-17 | 2007-12-26 | 哈尔滨工业大学 | TiO2 / PVDF cross blend cation exchange membrane and preparation method |
| CN101220231A (en) * | 2007-12-26 | 2008-07-16 | 华东理工大学 | Bi-component titanium dioxide film forming liquid |
| CN101250273A (en) * | 2008-03-26 | 2008-08-27 | 华东师范大学 | Method for preparing nano ZnO/polyvinyl acetate composite film |
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|---|---|---|---|---|
| US20040127354A1 (en) * | 2002-12-31 | 2004-07-01 | John Andrews | Photocatalytically-active, self-cleaning aqueous coating compositions and methods |
| CN101091882A (en) * | 2007-04-17 | 2007-12-26 | 哈尔滨工业大学 | TiO2 / PVDF cross blend cation exchange membrane and preparation method |
| CN101220231A (en) * | 2007-12-26 | 2008-07-16 | 华东理工大学 | Bi-component titanium dioxide film forming liquid |
| CN101250273A (en) * | 2008-03-26 | 2008-08-27 | 华东师范大学 | Method for preparing nano ZnO/polyvinyl acetate composite film |
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