CN107739116B - Method and device for deeply treating wastewater by PVDF/ZnO piezoelectric ultrafiltration membrane coupling advanced oxidation technology - Google Patents
Method and device for deeply treating wastewater by PVDF/ZnO piezoelectric ultrafiltration membrane coupling advanced oxidation technology Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/30—Organic compounds
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Abstract
The invention discloses a method and a device for deeply treating wastewater by coupling a PVDF/ZnO piezoelectric ultrafiltration membrane with an advanced oxidation technology, wherein wastewater to be treated and ozone pass through the PVDF/ZnO piezoelectric ultrafiltration membrane, the PVDF/ZnO piezoelectric ultrafiltration membrane is connected with an alternating current power supply, transmembrane pressure is provided in a vacuumizing mode, and ultraviolet lamps arranged on two sides of the PVDF/ZnO piezoelectric ultrafiltration membrane are simultaneously turned on; the wastewater is finally purified through the filtering action of a PVDF/ZnO piezoelectric ultrafiltration membrane and the oxidation actions of ozone oxidation, ultraviolet radiation and photocatalysis, and the PVDF/ZnO piezoelectric ultrafiltration membrane realizes the self-cleaning action under the action of an alternating current power supply; the method solves the problems that the membrane filtration technology can not effectively remove small molecular pollutants and the advanced oxidation technology can not effectively oxidize large molecular pollutants, the two technologies are organically coupled and complementary in advantages, and meanwhile, the piezoelectric effect of the PVDF/ZnO piezoelectric ultrafiltration membrane is utilized to effectively inhibit membrane pollution.
Description
Technical Field
The invention belongs to the field of deep water treatment, and particularly relates to a method and a device for deeply treating wastewater by a PVDF/ZnO piezoelectric ultrafiltration membrane coupling advanced oxidation technology.
Background
Along with the promotion of health consciousness, the requirement of people on safety and sanitation of drinking water is higher and higher, and the environmental protection theory is enhanced, the stricter sewage discharge standard is adopted, and the requirement on the quality of discharged water is higher and higher no matter town sewage treatment or tap water plant treatment. The traditional advanced treatment process of coagulation-precipitation-disinfection cannot meet the discharge requirement, and the membrane separation technology becomes an indispensable technology for advanced treatment of drinking water, wherein the ultrafiltration membrane technology is taken as the membrane separation technology and becomes a research hotspot in the field of water treatment due to the advantages that the ultrafiltration membrane technology can intercept colloids, most microorganisms and substances with higher molecular weight in water and the like.
Ultrafiltration is a pressurized membrane separation technique, the core of which is an ultrafiltration membrane made mainly of organic materials including cellulose acetate, polypropylene, polyamide and polysulfone, polyethersulfone, polytetrafluoroethylene and polyvinylidene fluoride. Polyvinylidene fluoride (PVDF) is a main film forming material of the ultrafiltration membrane due to the advantages of low cost, easy film formation, good filtering performance and the like, but the PVDF ultrafiltration membrane is used for advanced treatment of wastewater, has poor hydrophilicity, and is easy to attach microorganisms and organic matters on the surface of the PVDF ultrafiltration membrane to cause irreversible membrane pollution and reduce the flux of the PVDF ultrafiltration membrane, so that the quality of effluent water is poor, the cost is increased, and the quality of the effluent water cannot meet the living requirements of people; membrane fouling is a fundamental problem that limits its development.
The membrane pollution is the common disease of the PVDF ultrafiltration membrane, the ultrafiltration membrane pollution mainly comprises adsorption pollution, blocking pollution, concentration polarization pollution, gel layer pollution, comprehensive pollution and the like, in the face of ultrafiltration membrane pollution, people try to solve the problem by improving water quality, backwashing, changing hydrophilicity, increasing conductivity and the like, for example, CN 106110902A adds zinc oxide into the PVDF filtration membrane to enhance the hydrophilicity of the filtration membrane and has a bacteriostatic action, the method improves the membrane pollution, but cannot prevent other pollutants from polluting the filtration membrane, the application is limited, and the method treats both the symptoms and the root causes.
Advanced oxidation technology is also a commonly used method in advanced wastewater treatment, in order to reduce secondary pollution, chlorination technology is slowly replaced by ozone oxidation technology, in order to improve the quality of effluent water, several advanced oxidation technologies are often used for advanced wastewater treatment in a synergistic manner, for example, CN105314705A uses ozone, ultraviolet radiation and photocatalysis to treat wastewater in a synergistic manner, although the oxidation capacity of the method is strong, the technologies are greatly influenced by the quality of the influent water, and if microorganisms and macromolecular organic matters in the wastewater are more, the technologies cannot meet the process requirements.
Disclosure of Invention
Aiming at the problems, the invention provides a method for deeply treating wastewater by coupling a PVDF/ZnO piezoelectric ultrafiltration membrane with an advanced oxidation technology, namely a method for deeply treating wastewater by coupling a PVDF/ZnO piezoelectric ultrafiltration membrane with ultraviolet radiation, ozone oxidation, photocatalysis and other advanced oxidation technologies; the wastewater to be treated and ozone pass through a PVDF/ZnO piezoelectric ultrafiltration membrane, the PVDF/ZnO piezoelectric ultrafiltration membrane is connected with an alternating current power supply, transmembrane pressure is provided in a vacuumizing mode, and ultraviolet lamps arranged on two sides of the PVDF/ZnO piezoelectric ultrafiltration membrane are turned on; the waste water is finally purified through the filtering action of the PVDF/ZnO piezoelectric ultrafiltration membrane and the oxidation action of advanced oxidation technologies such as ozone oxidation, ultraviolet radiation, photocatalysis and the like, the PVDF/ZnO piezoelectric ultrafiltration membrane generates in-situ high-frequency vibration under the action of an alternating current power supply, pollutants attached to the filter membrane are far away from the filter membrane along with the in-situ vibration of the filter membrane, and the self-cleaning action is realized.
The specific mechanism is as follows: when the PVDF/ZnO piezoelectric ultrafiltration membrane is used for advanced wastewater treatment, macromolecular pollutants in wastewater are intercepted by a membrane, under the action of alternating current, the PVDF/ZnO piezoelectric ultrafiltration membrane generates inverse piezoelectric effect and generates in-situ high-frequency vibration, the pollutants attached to the filter membrane are far away from the filter membrane along with the in-situ vibration of the filter membrane, the pollution of the filter membrane is reduced, and the self-cleaning effect is realized; meanwhile, ultraviolet lamps are arranged on two sides of the filter membrane, ozone is introduced into the front side of the filter membrane, the ozone generates free radicals under the irradiation of the ultraviolet rays, the oxidation capacity is improved, organic pollutants are partially oxidized on the front side of the filter membrane, and the treatment load of the filter membrane is reduced; ZnO embedded in the filter membrane can change the hydrophilicity of the filter membrane and inhibit bacterial pollution, and performs a photocatalytic reaction under ultraviolet radiation to oxidize macromolecular organic pollutants near the filter membrane and micromolecular organic pollutants attached to the filter membrane; the unreacted ozone passes through the filter membrane, so that the micromolecular pollutants attached to the filter membrane are washed away, and the micromolecular organic pollutants penetrating through the filter membrane are oxidized under the radiation of ultraviolet rays at the rear side of the filter membrane.
The voltage of the alternating current power supply connected with the PVDF/ZnO piezoelectric ultrafiltration membrane is 10-60V, and the frequency of the alternating current power supply is 50-500 HZ.
The transmembrane pressure provided by vacuumizing is 150-600 KPa.
The wavelength of the ultraviolet lamp is 200-400 nm, and the concentration of the introduced ozone is 2-8 g/(L.h).
The PVDF/ZnO piezoelectric ultrafiltration membrane is prepared by utilizing nano ZnO and PVDF powder through a conventional phase inversion method, and then is prepared through direct-current high-pressure polarization treatment under a vacuum condition.
When the PVDF/ZnO ultrafiltration membrane is prepared by using a conventional phase inversion method, the mass ratio of PVDF powder to nano ZnO is 0.5-4: 1, the total mass of PVD powder F and nano ZnO accounts for 15-35% of the total mass of a membrane casting solution, NMP, DMF, DMSO, DMAc and the like are adopted as solvents, and absolute ethyl alcohol is adopted as an extracting agent.
The thickness of the PVDF/ZnO piezoelectric ultrafiltration membrane is 150-1000 mu m.
The direct-current high-voltage polarization conditions are as follows: the polarization voltage is 6-25 KV, the polarization time is 30-150 min, and the polarization temperature is 25-60 ℃.
The invention also aims to provide a device for deeply treating wastewater by coupling the PVDF/ZnO piezoelectric ultrafiltration membrane with the advanced oxidation technology, which comprises a water inlet pipe, a buffer tank, a front-end buffer pipe, the PVDF/ZnO piezoelectric ultrafiltration membrane, an alternating-current power supply, a rear-end buffer pipe and a water storage tank; the water inlet pipe is connected with one end of the front buffer pipe through the buffer tank, the other end of the front buffer pipe is connected with the water storage tank through the rear buffer pipe, the PVDF/ZnO piezoelectric ultrafiltration membrane is fixed between the front buffer pipe and the rear buffer pipe and is connected with the alternating current power supply, the ozone inlet pipe and the sludge discharge pipe are arranged on the front buffer pipe, the water stop valve and the pressure gauge are arranged on the ozone inlet pipe, the pressure gauge and the regulating valve are arranged on the sludge discharge pipe, the front ultraviolet lamp is arranged in the front buffer pipe and is positioned on one side of the PVDF/ZnO piezoelectric ultrafiltration membrane, and the rear ultraviolet lamp is arranged in the rear buffer pipe and is positioned on the other side of; the inside funnel formula pipe that is provided with of storage water tank, the storage water tank lower extreme sets up the outlet pipe, is provided with manometer and valve on the outlet pipe, and the storage water tank upper end sets up the evacuation pipe, is provided with the manometer on the vacuum pipe.
The device also comprises an air inlet pipe, the vacuumizing pipe is communicated with the front end buffer pipe through the air inlet pipe, and the air inlet pipe is arranged between the sludge discharge pipe and the PVDF/ZnO piezoelectric ultrafiltration membrane.
Compared with the prior art, the invention has the beneficial effects that:
1. the ultrafiltration can hold back macromolecular substance, overcomes the shortcoming that advanced oxidation can not effectively get rid of macromolecular substance, and the micromolecule refractory organic pollutant that advanced oxidation technique can not get rid of by oxidation ultrafiltration can organically combine when two kinds of techniques are used for waste water advanced treatment, and the advantage is complementary, and oxidation techniques such as ozone oxidation, ultraviolet radiation and photocatalysis simultaneously also can effectively cooperate.
2. PVDF and nano ZnO are piezoelectric materials, have piezoelectric effect after polarization, are prepared into an ultrafiltration membrane, can generate in-situ vibration under the action of an external alternating voltage, reduce membrane pollution and prolong the service life of the membrane, and meanwhile, the nano ZnO is embedded on the filtration membrane as a photocatalyst, generates photocatalytic reaction under the action of ultraviolet radiation, oxidizes organic matters, reduces membrane pollution and improves the quality of effluent water.
3. The ozone used in the invention can be recycled, if the ozone introduced into the device is not reacted, the ozone is vacuumized and then introduced into the device again, so that the filter membrane can be flushed, and meanwhile, the ozone can be fully utilized, thereby saving the cost, reducing the secondary pollution and simultaneously assisting in reducing the membrane pollution.
Drawings
FIG. 1 is a device for advanced wastewater treatment by using PVDF/ZnO piezoelectric ultrafiltration membrane coupled advanced oxidation technology;
FIG. 1-water inlet pipe; 2-a buffer tank; 3-a front buffer tube; 4-ozone inlet pipe; 5-a water stop valve; 6-pressure gauge; 7-front end ultraviolet lamp; 8-adjusting valve; 9-sludge discharge pipe; 10-PVDF/ZnO piezoelectric ultrafiltration membrane; 11-ultrafiltration membrane support; 12-air inlet pipe; 13-an alternating current power supply; 14-ultrafiltration membrane fixer; 15-rear end ultraviolet lamp; 16-a back end buffer tube; 17-evacuation tube; 18-a water outlet pipe; 19-a water storage tank; 20-funnel type conduit.
Detailed Description
The technical solution of the present invention is further described below with reference to specific examples, but the scope of the present invention is not limited to the description.
Example 1: the PVDF/ZnO piezoelectric ultrafiltration membrane is prepared by a conventional phase inversion method to obtain a PVDF/ZnO ultrafiltration membrane with the thickness of 500 mu m, and is obtained by 8KV direct-current high-voltage polarization for 120min under the vacuum condition of 40 ℃, and the specific preparation method is as follows:
adding nano ZnO into an NMP solvent, performing ultrasonic treatment for 1h, and performing magnetic stirring for 1h to uniformly disperse the nano ZnO in the NMP solvent, adding PVDF powder into the NMP solvent mixed with the nano ZnO at the moment, wherein the mass ratio of the PVDF powder to the nano ZnO is 2:1, the total mass of the PVDF powder and the nano ZnO accounts for 15% of the total mass of the casting solution, mechanically stirring for 8h under the condition of 30 ℃ water bath, and then standing for 12h in a vacuum environment for defoaming treatment to obtain the casting solution; uniformly distributing the membrane casting solution on a glass plate by utilizing a membrane scraping machine to form a thin membrane, baking the thin membrane for 1h at the temperature of 80 ℃, and then soaking the thin membrane in an extractant absolute ethyl alcohol for 2h to obtain a PVDF/ZnO ultrafiltration membrane; and placing the obtained PVDF/ZnO ultrafiltration membrane in high-voltage polarization equipment, and carrying out 8KV direct-current high-voltage polarization for 120min at 40 ℃ under a vacuum condition to finally obtain the PVDF/ZnO piezoelectric ultrafiltration membrane.
The method comprises the following steps of utilizing a PVDF/ZnO piezoelectric ultrafiltration membrane to be coupled with an advanced oxidation technology for deeply treating wastewater, enabling wastewater to be treated and ozone to pass through the PVDF/ZnO piezoelectric ultrafiltration membrane, enabling the concentration of the introduced ozone to be 4 g/(L.h), connecting the PVDF/ZnO piezoelectric ultrafiltration membrane with an alternating current power supply, providing transmembrane pressure (the transmembrane pressure is 200 KPa) in a vacuumizing mode, and simultaneously turning on ultraviolet lamps arranged on two sides of the PVDF/ZnO piezoelectric ultrafiltration membrane; the wastewater is finally purified through the filtering action of the PVDF/ZnO piezoelectric ultrafiltration membrane and the oxidation action of ozone oxidation, ultraviolet radiation and photocatalysis, the PVDF/ZnO piezoelectric ultrafiltration membrane generates in-situ high-frequency vibration under the action of an alternating current power supply, and pollutants attached to the filter membrane are far away from the filter membrane along with the in-situ vibration of the filter membrane, so that the self-cleaning action is realized.
Macromolecular pollutants in the wastewater are intercepted by the membrane, under the action of 20V and 100HZ alternating current, the PVDF/ZnO piezoelectric ultrafiltration membrane generates an inverse piezoelectric effect and generates in-situ high-frequency vibration, and pollutants attached to the filter membrane are far away from the filter membrane along with the in-situ vibration of the filter membrane, so that the self-cleaning effect is realized. Under the radiation of an ultraviolet lamp with the wavelength of 240nm, ozone molecules introduced into water are partially converted into free radicals, ZnO on the filter membrane is subjected to photocatalytic reaction to generate free radicals, more and more free radicals promote ozone to generate chain reaction, the oxidation capability of the system is enhanced, and small-molecule organic pollutants on the filter membrane and organic pollutants at the front end and the rear end of the filter membrane can be efficiently oxidized. The ultraviolet radiation, ozone oxidation, photocatalysis and other advanced oxidation technologies cooperate with each other, so that the oxidation capacity is enhanced, organic particles in the wastewater can be oxidized without selectivity, the membrane treatment load is reduced, the pollution caused by concentration polarization is effectively inhibited, and meanwhile, the organic substances which are attached to the membrane and cannot be vibrated down are oxidized, and the membrane pollution is reduced.
As shown in figure 1, the device for completing the method comprises a water inlet pipe 1, a buffer tank 2, a front buffer pipe 3, a PVDF/ZnO piezoelectric ultrafiltration membrane 10, an alternating current power supply 13, a rear buffer pipe 16 and a water storage tank 19; the water inlet pipe 1 is connected with one end of a front buffer pipe 3 through a buffer tank 2, the other end of the front buffer pipe 3 is connected with a water storage tank 19 through a rear buffer pipe 16, a PVDF/ZnO piezoelectric ultrafiltration membrane 10 is fixed between the front buffer pipe 3 and the rear buffer pipe 16 through an ultrafiltration membrane support 11 and an ultrafiltration membrane fixer 14, the PVDF/ZnO piezoelectric ultrafiltration membrane is connected with an alternating current power supply 13, an ozone inlet pipe 4 and a sludge discharge pipe 9 are arranged on the front buffer pipe 3, a water stop valve 5 and a pressure gauge 6 are arranged on the ozone inlet pipe 4, a pressure gauge and a regulating valve 8 are arranged on the sludge discharge pipe 9, a front ultraviolet lamp 7 is arranged in the front ultrafiltration membrane 3 and is positioned on one side of the PVDF/ZnO piezoelectric ultrafiltration membrane, and a rear ultraviolet lamp 15 is arranged in the rear buffer; a funnel type guide pipe 20 is arranged in the water storage tank 19, a water outlet pipe 18 is arranged at the lower end of the water storage tank 19, a pressure gauge and a valve are arranged on the water outlet pipe 18, a vacuumizing pipe 17 is arranged at the upper end of the water storage tank 19, and the pressure gauge is arranged on the vacuumizing pipe 17.
Adopt above-mentioned device to carry out advanced treatment to the city domestic wastewater through the processing of AO technology, waste water enters into baffle-box 2 through inlet tube 1, open front end ultraviolet lamp 7 and rear end ultraviolet lamp 15, let in ozone through ozone lets in pipe 4 simultaneously, the concentration of controlling to let in ozone is 4 g/(L.h), through the evacuation, make the transmembrane pressure 200KPa, waste water passes through the filtration and the advanced oxidation technology oxidation of PVDF/ZnO piezoelectricity milipore filter, the water after finally obtaining the purification passes through funnel formula pipe 20 and enters into storage water tank 19, discharge through outlet pipe 18, waste water that the filter membrane was held back passes through sludge discharge pipe 9.
Referring to the method, the same wastewater is treated by using an unpolarized PVDF/ZnO ultrafiltration membrane under the same conditions, the operation is carried out for 10 hours, and the treatment effects of two different filter membranes are as follows:
the data in the table show that the permeation flux of pure water is obviously increased after the PVDF/ZnO ultrafiltration membrane is subjected to polarization treatment, and the PVDF and ZnO are forced to change the polarization direction by polarization, so that the pore channel distribution of the filter membrane is more uniform, and the permeation flux is increased. Under the same operation condition, the polarized PVDF/ZnO ultrafiltration membrane has a piezoelectric effect, can generate in-situ vibration under the action of an alternating current power supply, can inhibit membrane pollution for a long time, membrane flux is hardly attenuated before and after operation, effluent water quality is higher, the unpolarized PVDF/ZnO ultrafiltration membrane has obvious reduction of permeation flux along with the increase of operation time, although the water quality of wastewater before passing through the filter membrane is improved under the actions of ozone oxidation, ultraviolet radiation and photocatalysis, and gas obtained by vacuumizing is introduced into a device to have a certain scouring action on the filter membrane, mainly because some macromolecular organic matters, inorganic matters and microorganisms in the wastewater can be adsorbed on the surface of the filter membrane and even block pore channels of the filter membrane, irreversible membrane pollution is caused, the permeation flux of the filter membrane is influenced, and further the effluent water quality is influenced.
Example 2: the PVDF/ZnO piezoelectric ultrafiltration membrane is prepared by adopting a conventional phase inversion method to obtain a PVDF/ZnO ultrafiltration membrane with the thickness of 750 mu m, and is obtained by carrying out 15KV direct-current high-voltage polarization for 90min under the vacuum condition of 50 ℃, the specific steps refer to example 1, during preparation, the mass ratio of PVDF powder to nano ZnO is 1.5:1, wherein the total mass of PVDF and nano ZnO accounts for 18% of the total mass of a casting membrane liquid, a solvent adopts DMAc, and an extracting agent is absolute ethyl alcohol.
The method comprises the following steps of utilizing a PVDF/ZnO piezoelectric ultrafiltration membrane to be coupled with an advanced oxidation technology for deeply treating wastewater, enabling wastewater to be treated and ozone to pass through the PVDF/ZnO piezoelectric ultrafiltration membrane, enabling the concentration of the introduced ozone to be 6 g/(L.h), connecting the PVDF/ZnO piezoelectric ultrafiltration membrane with an alternating current power supply, providing transmembrane pressure (the transmembrane pressure is 400 KPa) in a vacuumizing mode, and simultaneously turning on ultraviolet lamps arranged on two sides of the PVDF/ZnO piezoelectric ultrafiltration membrane; the wastewater is finally purified through the filtering action of the PVDF/ZnO piezoelectric ultrafiltration membrane and the oxidation action of ozone oxidation, ultraviolet radiation and photocatalysis, the PVDF/ZnO piezoelectric ultrafiltration membrane generates in-situ high-frequency vibration under the action of an alternating current power supply, and pollutants attached to the filter membrane are far away from the filter membrane along with the in-situ vibration of the filter membrane, so that the self-cleaning action is realized.
Macromolecular pollutants in the wastewater are intercepted by the membrane, under the action of 40V and 150HZ alternating current, the PVDF/ZnO piezoelectric ultrafiltration membrane generates an inverse piezoelectric effect and generates in-situ high-frequency vibration, and pollutants attached to the filter membrane are far away from the filter membrane along with the in-situ vibration of the filter membrane, so that the self-cleaning effect is realized. Under the radiation of an ultraviolet lamp with the wavelength of 280nm, ozone molecules introduced into water are partially converted into free radicals, ZnO on the filter membrane is subjected to photocatalytic reaction to generate free radicals, more and more free radicals promote ozone to generate chain reaction, the oxidation capability of the system is enhanced, and small-molecule organic pollutants on the filter membrane and organic pollutants at the front end and the rear end of the filter membrane can be efficiently oxidized. The ultraviolet radiation, ozone oxidation, photocatalysis and other advanced oxidation technologies cooperate with each other, so that the oxidation capacity is enhanced, organic particles in the wastewater can be oxidized without selectivity, the membrane treatment load is reduced, the pollution caused by concentration polarization is effectively inhibited, and meanwhile, the organic substances which are attached to the membrane and cannot be vibrated down are oxidized, and the membrane pollution is reduced.
As shown in fig. 1, the apparatus for carrying out the above method is the same as that of example 1, except that the apparatus further comprises an air inlet pipe 12, a vacuum-pumping pipe 17 is communicated with the front end buffer pipe 3 through the air inlet pipe 12, and the air inlet pipe 12 is arranged between the sludge discharge pipe 9 and the PVDF/ZnO piezoelectric ultrafiltration membrane 10.
Adopt above-mentioned device to carry out advanced treatment to the urban domestic wastewater through A2O technology processing, waste water enters into buffer tank 2 through inlet tube 1, open front end ultraviolet lamp 7 and rear end ultraviolet lamp 15, let in ozone through ozone admission pipe 4 simultaneously, the concentration of controlling the ozone that lets in is 6 g/(L.h), through the evacuation, make the transmembrane pressure 400KPa, the gas that the evacuation obtained lets in through air admission pipe 12 in front end buffer tube 3, can carry out certain scouring action to PVDF/ZnO piezoelectric ultrafiltration membrane, waste water passes through the filtration and the advanced oxidation technology oxidation of PVDF/ZnO automatically cleaning piezoelectric ultrafiltration membrane, the water that finally obtains after the purification passes through funnel formula pipe 20 and enters into storage water tank 19, discharge through outlet pipe 18, waste water that the filter membrane held back discharges through mud discharge pipe 9.
Referring to the method, the other conditions are unchanged, the polarized PVDF/ZnO ultrafiltration membrane is used for treating the same wastewater without the action of alternating current, the operation is carried out for 12 hours, and the treatment effects under two different operation conditions are as follows:
the data in the above table show that, under the same operating conditions, the PVDF/ZnO piezoelectric ultrafiltration membrane has a better treatment effect on the effluent of the A2O process than that of the PVDF/ZnO piezoelectric ultrafiltration membrane under the unpowered operating conditions under the 40V ac voltage, which indicates that the PVDF/ZnO piezoelectric ultrafiltration membrane can exhibit the piezoelectric effect only under the voltage-applied condition and can perform self-cleaning, while the PVDF/ZnO piezoelectric ultrafiltration membrane under the unpowered conditions has a better effluent quality under the vacuum gas flushing and the assistance of the advanced oxidation technology, but the permeation flux of the filter membrane in the system is obviously reduced, the membrane is seriously polluted, and the anti-pollution effect cannot be achieved.
Example 3: the PVDF/ZnO piezoelectric ultrafiltration membrane is prepared by adopting a conventional phase inversion method to obtain a PVDF/ZnO ultrafiltration membrane with the thickness of 1000 mu m, and is obtained by 20KV direct-current high-voltage polarization for 40min under the vacuum condition of 45 ℃, the specific steps refer to example 1, during preparation, the mass ratio of PVDF powder to nano ZnO is 3:1, wherein the total mass of PVDF and nano ZnO accounts for 30% of the total mass of a casting membrane liquid, a solvent adopts DMF, and an extracting agent is absolute ethyl alcohol.
The method comprises the following steps of utilizing a PVDF/ZnO piezoelectric ultrafiltration membrane to be coupled with an advanced oxidation technology for deeply treating wastewater, enabling wastewater to be treated and ozone to pass through the PVDF/ZnO piezoelectric ultrafiltration membrane, enabling the concentration of the introduced ozone to be 8 g/(L.h), connecting the PVDF/ZnO piezoelectric ultrafiltration membrane with an alternating current power supply, providing transmembrane pressure (the transmembrane pressure is 500 KPa) in a vacuumizing mode, and simultaneously turning on ultraviolet lamps arranged on two sides of the PVDF/ZnO piezoelectric ultrafiltration membrane; the wastewater is finally purified through the filtering action of the PVDF/ZnO piezoelectric ultrafiltration membrane and the oxidation action of ozone oxidation, ultraviolet radiation and photocatalysis, the PVDF/ZnO piezoelectric ultrafiltration membrane generates in-situ high-frequency vibration under the action of an alternating current power supply, and pollutants attached to the filter membrane are far away from the filter membrane along with the in-situ vibration of the filter membrane, so that the self-cleaning action is realized.
Macromolecular pollutants in the wastewater are intercepted by the membrane, under the action of 50V and 200HZ alternating current, the PVDF/ZnO piezoelectric ultrafiltration membrane generates an inverse piezoelectric effect and generates in-situ high-frequency vibration, and pollutants attached to the filter membrane are far away from the filter membrane along with the in-situ vibration of the filter membrane, so that the self-cleaning effect is realized. Under the radiation of an ultraviolet lamp with the wavelength of 350nm, ozone molecules introduced into water are partially converted into free radicals, ZnO on the filter membrane is subjected to photocatalytic reaction to generate free radicals, more and more free radicals promote ozone to generate chain reaction, the oxidation capability of the system is enhanced, and small-molecule organic pollutants on the filter membrane and organic pollutants at the front end and the rear end of the filter membrane can be efficiently oxidized. The ultraviolet radiation, ozone oxidation, photocatalysis and other advanced oxidation technologies cooperate with each other, so that the oxidation capacity is enhanced, organic particles in the wastewater can be oxidized without selectivity, the membrane treatment load is reduced, the pollution caused by concentration polarization is effectively inhibited, and meanwhile, the organic substances which are attached to the membrane and cannot be vibrated down are oxidized, and the membrane pollution is reduced.
The structure of the device for completing the method is the same as that of embodiment 2, the device is adopted to carry out advanced treatment on urban domestic wastewater treated by an MBR process, the wastewater enters a buffer tank 2 through a water inlet pipe 1, a front end ultraviolet lamp 7 and a rear end ultraviolet lamp 15 are opened, ozone is introduced through an ozone introducing pipe 4 at the same time, the concentration of the introduced ozone is controlled to be 8 g/(L.h), the transmembrane pressure is 500KPa through vacuumizing, the gas obtained through vacuumizing is introduced into the device through an air introducing pipe 12, a certain scouring effect can be carried out on the PVDF/ZnO self-cleaning piezoelectric ultrafiltration membrane, the wastewater is filtered by the PVDF/ZnO self-cleaning piezoelectric ultrafiltration membrane and oxidized by an advanced oxidation technology, finally the purified water enters a water storage tank 19 and is discharged through a water outlet pipe 18, and the wastewater intercepted by the filter membrane is discharged through a sludge discharge pipe 9.
Referring to the above method, the above conditions are set as an experimental group a, and control groups B, C and D are provided corresponding to the experimental group, and the operating conditions of the control group B are identical to those of the experimental group a except that the front end ultraviolet lamp 7 and the rear end ultraviolet lamp 15 are not turned on; the operation conditions of the control group C are consistent with those of the experimental group A except that ozone is not introduced; the operation conditions of the control group D are the same as those of the experimental group A except that ozone is not introduced, and the front end ultraviolet lamp 7 and the rear end ultraviolet lamp 15 are not opened. The above 4 groups were run for 24h, and the effect on wastewater treatment is shown in the following table:
from the data in the table, it can be seen that the experimental group A has the best treatment effect, the effluent quality is good, and the flux of the filter membrane is hardly attenuated; secondly, the flux of the filter membrane is reduced a little by the control group C without ozone; the control group B which does not use ultraviolet radiation has better treatment effect than the control group B because the ultraviolet radiation can photolyze water to generate free radicals, further oxidize pollutants in the wastewater, and simultaneously promote zinc oxide embedded on the filter membrane to perform photocatalytic reaction to oxidize the pollutants attached on the filter membrane and reduce membrane pollution; the contrast group D which does not use ozone and ultraviolet radiation has the worst effect, the contrast group only depends on the piezoelectric effect of the PVDF/ZnO piezoelectric ultrafiltration membrane to inhibit membrane pollution, but small molecular organic matters in the wastewater cannot be oxidized, the substances can enter pore channels of the filter membrane along with the in-situ vibration of the filter membrane to block the pore channels, so that the membrane flux is reduced, and the COD of effluent is higher because most of the COD is composed of soluble molecules, the filter membrane can only filter the large molecular organic matters, and the small molecular organic matters can pass through the filter membrane, so that the COD of the effluent is higher; and experiment group A, ultraviolet radiation impels some ozone to turn into the free radical, improves the oxidability, reduces the load of waste water and impels to take place the photocatalytic reaction on the filter membrane simultaneously, the oxidation adheres to the pollutant on the filter membrane, and PVDF ZnO piezoelectricity milipore filter takes place the normal position vibration simultaneously, and most pollutant can't be close to the filter membrane, can reduce the membrane pollution that concentration polarization caused like this, and the ozone that has not reacted passes through the filter membrane, can wash the filter membrane, prevents the pore canal jam, can also continue to oxidize the pollutant that does not degrade simultaneously.
Claims (5)
1. A PVDF/ZnO piezoelectric ultrafiltration membrane coupling advanced oxidation technology advanced wastewater treatment method is characterized in that: the wastewater to be treated and ozone pass through a PVDF/ZnO piezoelectric ultrafiltration membrane, the PVDF/ZnO piezoelectric ultrafiltration membrane is connected with an alternating current power supply, transmembrane pressure is provided in a vacuumizing mode, and ultraviolet lamps arranged on two sides of the PVDF/ZnO piezoelectric ultrafiltration membrane are turned on; the wastewater is finally purified through the filtering action of a PVDF/ZnO piezoelectric ultrafiltration membrane and the oxidation action of ozone oxidation, ultraviolet radiation and photocatalysis, the PVDF/ZnO piezoelectric ultrafiltration membrane generates in-situ high-frequency vibration under the action of an alternating current power supply, and pollutants attached to the filter membrane are far away from the filter membrane along with the in-situ vibration of the filter membrane, so that the self-cleaning action is realized;
the PVDF/ZnO piezoelectric ultrafiltration membrane is prepared by preparing a PVDF/ZnO ultrafiltration membrane by using nano ZnO and PVDF powder through a phase inversion method and then performing direct-current high-pressure polarization treatment under a vacuum condition, wherein the mass ratio of the PVDF powder to the nano ZnO is 0.5-4: 1, and the total mass of the PVDF powder and the nano ZnO accounts for 15-35% of the total mass of the membrane casting solution; the polarization voltage in the direct-current high-voltage polarization is 6-25 KV, the polarization time is 30-150 min, and the polarization temperature is 25-60 ℃;
the voltage of an alternating current power supply connected with the PVDF/ZnO piezoelectric ultrafiltration membrane is 10-60V, and the frequency of the alternating current power supply is 50-500 HZ;
the transmembrane pressure provided by vacuumizing is 150-600 KPa.
2. The PVDF/ZnO piezoelectric ultrafiltration membrane coupling advanced oxidation technology advanced wastewater treatment method according to claim 1, is characterized in that: the wavelength of the ultraviolet lamp is 200-400 nm, and the concentration of the introduced ozone is 2-8 g/(L.h).
3. The PVDF/ZnO piezoelectric ultrafiltration membrane coupling advanced oxidation technology advanced wastewater treatment method according to claim 1, is characterized in that: the thickness of the PVDF/ZnO piezoelectric ultrafiltration membrane is 150-1000 mu m.
4. The device for completing the PVDF/ZnO piezoelectric ultrafiltration membrane coupling advanced oxidation technology advanced wastewater treatment method of claim 1 is characterized in that: comprises a water inlet pipe (1), a buffer tank (2), a front end buffer pipe (3), a PVDF/ZnO piezoelectric ultrafiltration membrane (10), an alternating current power supply (13), a rear end buffer pipe (16) and a water storage tank (19); the water inlet pipe (1) is connected with one end of a front buffer pipe (3) through a buffer box (2), the other end of the front buffer pipe (3) is connected with a water storage tank (19) through a rear buffer pipe (16), a PVDF/ZnO piezoelectric ultrafiltration membrane (10) is fixed between the front buffer pipe (3) and the rear buffer pipe (16), the PVDF/ZnO piezoelectric ultrafiltration membrane is connected with an alternating current power supply (13), the front buffer pipe (3) is provided with an ozone inlet pipe (4), a sludge discharge pipe (9), wherein a water stop valve (5) and a pressure gauge (6) are arranged on the ozone inlet pipe (4), the pressure gauge and a regulating valve (8) are arranged on the sludge discharge pipe (9), a front end ultraviolet lamp (7) is arranged in the front end buffer pipe (3) and is positioned on one side of the PVDF/ZnO piezoelectric ultrafiltration membrane, and a rear end ultraviolet lamp (15) is arranged in the rear end buffer pipe (16) and is positioned on the other side of the PVDF/ZnO piezoelectric ultrafiltration membrane; a funnel type guide pipe (20) is arranged in the water storage tank (19), a water outlet pipe (18) is arranged at the lower end of the water storage tank (19), a pressure gauge and a valve are arranged on the water outlet pipe (18), a vacuumizing pipe (17) is arranged at the upper end of the water storage tank (19), and the pressure gauge is arranged on the vacuumizing pipe (17).
5. The apparatus of claim 4, wherein: the device also comprises an air inlet pipe (12), the vacuumizing pipe (17) is communicated with the front end buffer pipe (3) through the air inlet pipe (12), and the air inlet pipe (12) is arranged between the sludge discharge pipe (9) and the PVDF/ZnO piezoelectric ultrafiltration membrane (10).
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