CN115745135B - Self-cleaning photoelectric integrated sewage treatment device and sewage treatment method - Google Patents
Self-cleaning photoelectric integrated sewage treatment device and sewage treatment method Download PDFInfo
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Water Treatment By Electricity Or Magnetism (AREA)
- Physical Water Treatments (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention provides a self-cleaning photoelectric integrated sewage treatment device, which comprises a reaction tank, a spiral piezoelectric cyclone tube anode, an annular aeration cathode and a light source which are positioned in the reaction tank, and further comprises a power supply and an aeration device; the spiral piezoelectric swirl tube anode consists of a spiral tube and a hydrophobic piezoelectric photocatalysis lining layer on the inner wall of the spiral tube, the spiral piezoelectric swirl tube anode is conductive and transparent, the inlet of the spiral piezoelectric swirl tube anode is communicated with a water inlet on the reaction tank, and the outlet of the spiral piezoelectric swirl tube anode is positioned at the lower part in the reaction tank shell; the annular aeration cathode comprises an annular conductive pipeline and a plurality of aeration discs communicated with the annular conductive pipeline, and is arranged around the anode of the spiral piezoelectric swirl tube; the anode and the annular aeration cathode of the spiral piezoelectric cyclone tube are respectively connected with the anode and the cathode of the power supply. The invention also provides a sewage treatment method based on the device. The invention combines photocatalysis, electrocatalysis and piezocatalysis, even ozone oxidation, and has the characteristics of simple process and high sewage treatment efficiency.
Description
Technical Field
The invention belongs to the field of sewage treatment, relates to a sewage treatment device and a sewage treatment method, and in particular relates to a self-cleaning photoelectric integrated sewage treatment device and a sewage treatment method.
Background
Along with the acceleration of the industrialization process in China, the industrial wastewater quantity and the types of pollutants are increased rapidly, and serious challenges are brought to ecological environment safety and human health. Industrial processRefractory organic matters and toxic substances in the wastewater cannot be removed by a traditional biological method. Advanced Oxidation (AOP) such as electrochemical oxidation, photocatalytic oxidation, fenton, chemical oxidation, etc., can generate strong oxidative free Radicals (ROS) to degrade organic matter into CO without selectivity 2 And H 2 O becomes the most universal and promising technology for industrial wastewater treatment. However, single advanced oxidation techniques often have limitations, such as high energy consumption of electrochemical oxidation processes, and susceptibility of electrodes to corrosion and passivation; the Fenton method is carried out under the condition of acidic pH, the low circulating reaction rate of ferrous iron causes low Fenton treatment efficiency, and a large amount of iron mud is inevitably produced after the reaction; the electron-hole separation efficiency generated by the photocatalytic oxidation method is low, the light energy utilization rate is low, the treatment effect is influenced by the water transmittance, and the photocatalyst is difficult to recycle; the chemical oxidation method needs to continuously and additionally add a large amount of medicaments to cause secondary pollution; in addition, ROS generated by a single AOP technique, while highly oxidizing, have a short lifetime, e.g., hydroxyl radicals have a lifetime of only 10 -9 s, limited by mass transfer of the contaminant, is often difficult to thoroughly degrade the contaminant.
The serial use of multiple advanced oxidation techniques is one of the effective means for enhancing wastewater treatment. However, the combined process flow of multiple AOP technologies is complex, so that the problems of large occupied area, large equipment investment, high energy consumption, high operation and maintenance costs and the like are easily caused, and the popularization of the advanced oxidation technology in actual wastewater treatment is limited. In view of the above, development of wastewater treatment technology with high efficiency, low consumption, small occupied area and no secondary pollution has great value and practical significance for development of environmental protection industry.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a self-cleaning photoelectric integrated sewage treatment device, and provides a sewage treatment method based on the integrated sewage treatment device, so as to improve the degradation efficiency and degradation effect on sewage on the basis of reducing the occupied area of equipment and the operation and maintenance cost of the equipment and simplify the sewage treatment process.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the self-cleaning photoelectric integrated sewage treatment device comprises a reaction tank, a spiral piezoelectric cyclone tube anode, an annular aeration cathode and a light source which are positioned in the reaction tank, and also comprises a power supply and an aeration device;
the shell of the reaction tank is provided with a water inlet, a water outlet and a circulating water outlet, the water inlet and the water outlet are positioned at the upper part of the shell of the reaction tank, the circulating water outlet is positioned at the lower part of the shell of the reaction tank, the circulating water outlet is communicated with the water inlet through a reflux pump and a circulating water pipe, and the shell of the reaction tank is non-conductive;
the spiral piezoelectric cyclone tube anode consists of a spiral tube and a hydrophobic piezoelectric photocatalysis lining layer attached in the spiral tube, the spiral piezoelectric cyclone tube anode is conductive and transparent, the spiral piezoelectric cyclone tube anode is a spiral pipeline with an outlet end positioned below an inlet end, the inlet of the spiral piezoelectric cyclone tube anode is communicated with a water inlet, and the outlet of the spiral piezoelectric cyclone tube anode is positioned at the lower part in the reaction tank shell;
the annular aeration cathode comprises an annular conductive pipeline and a plurality of aeration discs which are distributed on the annular conductive pipeline and are communicated with the annular conductive pipeline, the annular conductive pipeline is communicated with aeration equipment positioned outside the reaction tank through an aeration pipe, and the annular aeration cathode is arranged around the anode of the spiral piezoelectric cyclone tube;
the anode of the spiral piezoelectric cyclone tube and the annular aeration cathode are respectively connected with the anode and the cathode of the power supply through wires; the irradiation range of the light rays emitted by the light source covers the anode of the spiral piezoelectric cyclone tube, and the wavelength of the light rays emitted by the light source is in the range of 80-2000 nm.
In the technical scheme of the self-cleaning photoelectric integrated sewage treatment device, the inclined plate is also arranged in the reaction tank and used for inclined plate sedimentation, and the inclined plate is positioned below the anode outlet of the spiral piezoelectric cyclone tube. The inclined plate has the function of efficiently precipitating the solid piezoelectric reinforced material in the sewage treatment process, so that the solid piezoelectric reinforced material can be efficiently recycled. The inclined plate refers to a combined structure formed by a group of mutually parallel flat plates with uniform intervals, namely a common structure in an inclined plate sedimentation tank in the field of sewage treatment.
Further, in the technical scheme of the self-cleaning photoelectric integrated sewage treatment device, the height of the inclined plate arranged in the reaction tank is 10% -40% of the height of the anode of the spiral piezoelectric cyclone tube.
Furthermore, in the technical scheme of the self-cleaning photoelectric integrated sewage treatment device, the inclination range of the inclined plate is 35-50 degrees, namely, the included angle between the inclined plate and the horizontal plane is 35-50 degrees.
In the technical scheme of the self-cleaning photoelectric integrated sewage treatment device, the helix angle of the anode of the spiral piezoelectric swirl tube is 20-45 degrees.
In the technical scheme of the self-cleaning photoelectric integrated sewage treatment device, the height of the anode of the spiral piezoelectric cyclone tube is 30% -70% of the height of the inside of the reaction tank; further, in order to gradually increase the flow velocity of the water flow in the spiral-shaped piezoelectric swirl tube anode, that is, the flow velocity of the water flow gradually increases from the inlet end to the outlet end of the spiral-shaped piezoelectric swirl tube anode, thereby enhancing the piezoelectric catalysis, it is preferable that the spiral surrounding diameter of the spiral-shaped piezoelectric swirl tube anode sequentially decreases from top to bottom.
Further, in the technical scheme of the self-cleaning photoelectric integrated sewage treatment device, the axis of the anode of the spiral piezoelectric cyclone tube is preferably coincident with the axis of the reaction tank.
In the technical scheme of the self-cleaning photoelectric integrated sewage treatment device, the hydrophobic piezoelectric photocatalysis inner liner is a light-transmitting hydrophobic film containing piezoelectric photocatalysis material, the light-transmitting hydrophobic film can be a polyimide film or a polytetrafluoroethylene film, for example, the feasible polyimide film can be a film with the trade name of Kapton or a PTFE film, the piezoelectric photocatalysis material is at least one of photo-responsive catalysts such as perovskite, iron oxide, bismuth oxide, titanate and the like, or is a compound of at least one of perovskite, iron oxide, bismuth oxide and titanate and titanium dioxide or zinc oxide, and the common piezoelectric photocatalysis material comprises lanthanum ferrite, strontium bismuth oxide, titanium dioxide composite bismuth titanate and the like.
In the technical scheme of the self-cleaning photoelectric integrated sewage treatment device, the anode of the spiral piezoelectric cyclone tube is conductive, the hydrophobic piezoelectric photocatalysis inner liner attached in the spiral tube is conductive, and the hydrophobic piezoelectric photocatalysis inner liner is conductive because the piezoelectric photocatalysis material in the light-transmitting hydrophobic film is conductive, so that the content of the piezoelectric photocatalysis material in the light-transmitting hydrophobic film ensures that the hydrophobic piezoelectric photocatalysis inner liner can conduct continuously and uniformly.
In the technical scheme of the self-cleaning photoelectric integrated sewage treatment device, the spiral pipe is made of a light-transmitting material, and the feasible material for manufacturing the spiral pipe comprises quartz, soft glass or light-transmitting glass and the like.
In the technical scheme of the self-cleaning photoelectric integrated sewage treatment device, when more than one annular aeration cathode is arranged, the annular aeration cathodes are arranged at different height positions on the inner wall of the reaction tank, the arrangement position of the annular aeration cathode is not lower than the outlet end of the spiral piezoelectric cyclone tube anode and not higher than the inlet end of the spiral piezoelectric cyclone tube, for example, the annular aeration cathode can be arranged around the middle lower part of the spiral piezoelectric cyclone tube anode, and the annular aeration cathode can be arranged between the outlet end of the spiral piezoelectric cyclone tube anode and 1/2 of the height of the spiral piezoelectric cyclone tube anode.
In the technical scheme of the self-cleaning photoelectric integrated sewage treatment device, the annular conductive pipeline of the annular aeration cathode is fixed on the inner wall of the reaction tank through the fixing clamp arranged on the inner wall of the reaction tank.
In the technical scheme of the self-cleaning photoelectric integrated sewage treatment device, the conductive components of the annular conductive pipeline of the annular aeration cathode are usually stainless steel, titanium, graphite and the like, such as stainless steel pipelines, titanium pipelines, graphene pipelines and the like.
In the technical scheme of the self-cleaning photoelectric integrated sewage treatment device, the annular conductive pipeline is provided with a plurality of aeration discs, and preferably, the distance between every two adjacent aeration discs is preferably 1-50 cm.
According to the technical scheme of the self-cleaning photoelectric integrated sewage treatment device, the annular aeration cathode can synchronously realize corrosion prevention of the annular conductive pipeline, stirring of water in the reaction tank and self-cleaning of the aeration head and the annular conductive pipeline through aeration.
In the technical scheme of the self-cleaning photoelectric integrated sewage treatment device, the light source preferably adopts a tubular or strip-shaped light source, one or more light sources can be arranged on the axis of the reaction tank or the light sources are uniformly arranged around the axis of the reaction tank, and the light source is preferably arranged in the spiral of the anode of the spiral piezoelectric cyclone tube.
In the technical scheme of the self-cleaning photoelectric integrated sewage treatment device, a feasible light source comprises a xenon lamp, an LED lamp, a near infrared lamp, an ultraviolet lamp and the like.
In the technical scheme of the self-cleaning photoelectric integrated sewage treatment device, the shell of the reaction tank is non-conductive, namely the shell of the reaction tank is made of non-conductive materials (such as high polymer materials), or the shell of the reaction tank is made of conductive materials (such as stainless steel) and is provided with an insulating lining layer.
In the technical scheme of the self-cleaning photoelectric integrated sewage treatment device, the sealing cover can be arranged above the reaction tank.
In the technical scheme of the self-cleaning photoelectric integrated sewage treatment device, the power supply connected with the anode of the spiral piezoelectric cyclone tube and the annular aeration cathode is a direct current power supply or a pulse power supply, and a polycrystalline silicon solar photovoltaic panel can also be used as the power supply.
Based on the self-cleaning photoelectric integrated sewage treatment device, the invention also provides a sewage treatment method, which uses the integrated sewage treatment device and comprises the following steps:
introducing sewage and a piezoelectric reinforcement material into a reaction tank through a water inlet by a spiral piezoelectric cyclone tube anode, and treating the sewage under the conditions of starting a reflux pump, a light source, a power supply connected with the spiral piezoelectric cyclone tube anode and an annular aeration cathode and aeration by an aeration disc, wherein the treated sewage is discharged from a water outlet to the reaction tank; the piezoelectric reinforced material is at least one of modified zeolite, zeolite compound, carbon-based material and persulfate; the gas introduced through the aeration disc is at least one of air and ozone;
in the process that sewage descends in the spiral piezoelectric cyclone tube anode, potential energy of water flow and piezoelectric reinforcing materials in the sewage excite piezoelectric catalytic effect, free radicals are generated under the effects of photocatalysis and electrocatalytic effect to degrade pollutants in the sewage, and after the sewage flows out of the spiral piezoelectric cyclone tube anode, the pollutants in the sewage are further degraded under aeration and illumination conditions.
In the technical scheme of the sewage treatment method, the piezoelectric reinforcing material is used for contacting electrification or capturing electrons, promoting charge transfer, reinforcing generation of strong oxidative free Radicals (ROS), and promoting degradation performance on pollutants. The particle size of the piezoelectric reinforcing material is preferably not more than 300 μm; the addition amount of the piezoelectric reinforcing material is controlled so that each liter of sewage contains 0.005-1 g of the piezoelectric reinforcing material.
In the technical scheme of the sewage treatment method, when aeration is performed through the aeration disc, the aeration intensity is controlled to be not more than 0-20 m 3 /m 2 ·h。
In the technical scheme of the sewage treatment method, the hydraulic retention time of sewage in the reaction tank is controlled to be 0.3-2 h.
In the technical scheme of the sewage treatment method, the voltage of the power supply is controlled to be 2-20V in the sewage treatment process.
In the technical scheme of the sewage treatment method, according to the condition of the electrolyte content in the sewage to be treated, before a power supply is started, the electrolyte may need to be added into the sewage, specifically whether the electrolyte needs to be added or not and the addition amount of the electrolyte are determined according to the water quality condition of the actual sewage, and the electrolyte content in the sewage is based on the principle of ensuring that the electrolysis reaction generates stable required current.
In the technical scheme of the sewage treatment method, the pH value of the sewage to be treated is not particularly required, and the sewage treatment method is generally applicable to sewage with the pH value of 2-10.
Compared with the prior art, the technical scheme provided by the invention has the following beneficial technical effects:
1. the invention provides a self-cleaning photoelectric integrated sewage treatment device, which comprises a reaction tank, a spiral piezoelectric cyclone tube anode, an annular aeration cathode, a light source, a power supply and aeration equipment, wherein the spiral piezoelectric cyclone tube anode is arranged on the reaction tank; the spiral piezoelectric swirl tube anode consists of a spiral tube and a hydrophobic piezoelectric photocatalysis lining layer attached in the spiral tube, the spiral piezoelectric swirl tube anode is conductive and transparent, the spiral piezoelectric swirl tube anode is a spiral pipeline with an outlet end positioned below an inlet end, and the inlet of the spiral piezoelectric swirl tube anode is communicated with a water inlet; the annular aeration cathode comprises an annular conductive pipeline and a plurality of aeration discs which are distributed on the annular conductive pipeline and are communicated with the annular conductive pipeline, the annular conductive pipeline is communicated with aeration equipment positioned outside the reaction tank through an aeration pipe, and the annular aeration cathode is arranged around the anode of the spiral piezoelectric cyclone tube; the anode of the spiral piezoelectric cyclone tube and the annular aeration cathode are respectively connected with the anode and the cathode of the power supply through wires; the irradiation range of the light rays emitted by the light source covers the anode of the spiral piezoelectric cyclone tube. The device combines photocatalysis, electrocatalysis, piezocatalysis and even ozone oxidation into a whole, and compared with the mode of using a plurality of advanced oxidation technologies in series in the prior art, the device has the characteristic of small occupied area, is beneficial to reducing equipment investment and saves operation and maintenance cost.
2. The self-cleaning photoelectric integrated sewage treatment device provided by the invention utilizes the directional momentum shearing principle to generate high-speed rotational flow fluid in the anode of the spiral piezoelectric rotational flow tube, so that mechanical energy is recovered in situ, the mechanical energy is converted into chemical energy to promote the generation of free radicals, and meanwhile, the self-cleaning of the anode can be realized by the hydrophobic piezoelectric photocatalysis lining layer; the anode of the spiral piezoelectric cyclone tube is conductive and transparent at the same time, can couple piezoelectric catalysis, electrochemical oxidation and photocatalysis, and can cooperate to promote the efficient generation of free radicals in the wastewater treatment process; the device is also provided with the sloping plate so as to realize the efficient recycling of the solid piezoelectric reinforced material, thereby being beneficial to reducing the treatment cost; by utilizing the annular aeration cathode aeration, the self-cleaning of the cathode is realized, and meanwhile, the dissolved oxygen (or ozone) rate and the oxygen (or ozone) utilization rate are increased, so that the hydraulic retention time of the obtained sewage is prolonged. Through the mutual synergistic effect of the above aspects, the invention can effectively shorten the process flow of sewage treatment, is beneficial to reducing the sewage treatment cost, and effectively shortens and simplifies the process flow compared with the mode of using a plurality of advanced oxidation technologies in series in the prior art.
3. Based on the self-cleaning photoelectric integrated sewage treatment device, the invention also provides a sewage treatment method which has the advantages of simple process operation, good stability, high sewage treatment efficiency and high pollutant removal rate, and is beneficial to popularization and application.
4. Experiments prove that the method disclosed by the invention is used for treating antibiotic pollutants, the TOC removal rate in sewage is as high as 99%, and compared with a method which mainly uses electrocatalytic or photo-catalytic alone and a method which combines piezocatalysis with photo-catalytic and aeration, the method disclosed by the invention can be used for remarkably improving the removal rate of organic matters in sewage. Experiments prove that the method disclosed by the invention can be used for treating the hospital sewage, so that the ciprofloxacin concentration in the hospital sewage can be completely removed, and the removal rate of TOC in the hospital sewage is as high as more than 95%. The method of the invention is adopted to treat the secondary effluent of the petrochemical plant, and the TOC removal rate can reach 98%. The experimental results show that the method provided by the invention has high-efficiency degradation capability on sewage.
Drawings
Fig. 1 is a schematic structural view of a self-cleaning photoelectric integrated sewage treatment device of the invention.
Fig. 2 is a schematic structural view of the annular aerated cathode.
In FIGS. 1-2, 1-reaction tank, 1-water inlet, 1-2-water outlet, 1-3-circulating water outlet, 1-4-reflux pump, 1-5-sealing cover, 2-spiral piezoelectric cyclone anode, 3-annular aeration cathode, 3-1-annular conductive pipeline, 3-2-aeration disk, 4-light source, 5-power supply, 6-aeration equipment and 7-sloping plate.
FIG. 3 shows the change with time of the removal rate of ciprofloxacin as an antibiotic pollutant in example 7 and comparative examples 1 to 3.
Detailed Description
The self-cleaning photoelectric integrated sewage treatment device and the sewage treatment method provided by the invention are further described by the following embodiments. It is to be noted that the following examples are given solely for the purpose of illustration and are not to be construed as limitations of the present invention, since numerous insubstantial modifications and variations of the present invention may be made by those skilled in the art in light of the above teachings, and still fall within the scope of the invention.
In the examples below, the chemicals and materials used were commercially available or prepared by reference to the literature.
Example 1
In this embodiment, a self-cleaning photoelectric integrated sewage treatment device is provided, and the sewage treatment device has a structural schematic diagram shown in fig. 1, and comprises a reaction tank 1, a spiral piezoelectric cyclone tube anode 2, an annular aeration cathode 3 and a light source 4 which are positioned in the reaction tank 1, and further comprises a power supply 5, an aeration device 6 and an inclined plate 7.
The main body of the reaction tank 1 is cylindrical, the lower end of the reaction tank is conical, and the upper end of the reaction tank is provided with a sealing cover 1-5. The shell of the reaction tank 1 is provided with a water inlet 1-1, a water outlet 1-2 and a circulating water outlet 1-3, the water inlet 1-1 is positioned at the upper part of the shell of the reaction tank, the circulating water outlet 1-3 is positioned at the lower part of the shell of the reaction tank, the circulating water outlet 1-3 is communicated with the water inlet 1-1 through a reflux pump 1-4 and a circulating water pipe, and insulating inner liners are arranged in the shell of the reaction tank and the inner layer of the sealing cover, so that the shell of the reaction tank and the sealing cover are not conductive. The outer wall of the reaction tank is provided with a foot rest, and the reaction tank is installed on the ground through the support of the foot rest.
The spiral piezoelectric swirl tube anode 2 consists of a spiral tube and a hydrophobic piezoelectric photocatalysis lining layer attached in the spiral tube, the spiral piezoelectric swirl tube anode 2 is conductive and transparent, the outlet end of the spiral piezoelectric swirl tube anode 2 is a spiral pipeline with the outlet end positioned below the inlet end, in order to gradually increase the flow velocity of water in the spiral piezoelectric swirl tube anode 2, namely the flow velocity of water gradually increases from the inlet end to the outlet end of the spiral piezoelectric swirl tube anode, so that the piezoelectric catalysis is enhanced, and the spiral surrounding diameter of the spiral piezoelectric swirl tube anode 2 is sequentially reduced from top to bottom. The height of the spiral piezoelectric cyclone tube anode 2 is 60% of the height of the inside of the reaction tank, the helix angle of the spiral piezoelectric cyclone tube anode 2 is 25 degrees, and the axis of the spiral piezoelectric cyclone tube anode 2 is preferably coincident with the axis of the reaction tank. The inlet of the spiral piezoelectric cyclone tube anode 2 is communicated with the water inlet 1-1, and the outlet of the spiral piezoelectric cyclone tube anode 2 is positioned at the lower part in the reaction tank shell. The spiral tube is made of quartz. The hydrophobic piezoelectric photocatalysis inner liner is a light-transmitting hydrophobic film containing piezoelectric photocatalysis material, in particular to a PTFE film containing strontium bismuth oxide, and the content of the strontium bismuth oxide in the PTFE film ensures that the hydrophobic piezoelectric photocatalysis inner liner can conduct electricity continuously and uniformly.
In order to efficiently precipitate the solid piezoelectric reinforced material in the sewage treatment process, thereby realizing the efficient recycling of the solid piezoelectric reinforced material, the reaction tank is internally provided with the inclined plate 7, the inclined plate 7 is arranged in the cone frustum cylinder body of the reaction tank and is positioned below the outlet of the anode 2 of the spiral piezoelectric cyclone tube, the height of the inclined plate 7 is 40% of the height of the anode 2 of the spiral piezoelectric cyclone tube, the inclination of the inclined plate is 45 degrees, namely, the inclined angle between the inclined plate and the horizontal plane is 45 degrees.
The annular aeration cathode 3 comprises an annular conductive pipeline 3-1 and a plurality of aeration discs 3-2 which are distributed on the annular conductive pipeline and are communicated with the annular conductive pipeline, as shown in figure 2. The annular conductive pipeline is communicated with an aeration device 6 positioned outside the reaction tank through an aeration pipe 3-3, one annular aeration cathode 3 is arranged and surrounds the spiral piezoelectric cyclone pipe anode 2, the annular conductive pipeline of the annular aeration cathode 3 is fixed on the inner wall of the reaction tank through a fixing clamp arranged on the inner wall of the reaction tank, and the annular aeration cathode 3 is arranged at 1/2 height of the spiral piezoelectric cyclone pipe anode. The annular conductive pipeline of the annular aeration cathode 3 is a stainless steel pipeline. A plurality of aeration discs are arranged on the annular conductive pipeline, and the distance between the adjacent aeration discs is preferably 5-30 cm. The annular aeration cathode can synchronously realize the corrosion prevention of the annular conductive pipeline, the stirring of the water body in the reaction tank and the self-cleaning of the aeration head and the annular conductive pipeline through aeration.
The light source is a tubular light source, namely a tubular ultraviolet lamp, the light source is arranged on the axis of the reaction tank through a fixing piece, the light source is connected with a light source power supply positioned outside the reaction tank through a wire, the length of the light source is equal to the height of the anode of the spiral piezoelectric cyclone tube, the irradiation range of light rays emitted by the light source 4 at least completely covers the anode of the spiral piezoelectric cyclone tube, and the power of the light source is 200W.
The spiral piezoelectric cyclone tube anode 2 and the annular aeration cathode 3 are respectively connected with the anode and the cathode of the power supply 5 through wires, the power supply 5 is a direct current power supply, and the parts of the wires connecting the spiral piezoelectric cyclone tube anode, the annular aeration cathode and the power supply, which are positioned in the reaction tank, are led to the spiral piezoelectric cyclone tube anode and the annular aeration cathode through insulating pipelines arranged on the inner wall of the reaction tank and are connected with the spiral piezoelectric cyclone tube anode and the annular aeration cathode.
Example 2
In this embodiment, a self-cleaning photoelectric integrated sewage treatment apparatus is provided, which has substantially the same structure as the sewage treatment apparatus of embodiment 1, except that:
the height of the anode of the spiral piezoelectric cyclone tube is 50% of the height of the inside of the reaction tank, and the helix angle of the anode of the spiral piezoelectric cyclone tube is 20 degrees; the height of the inclined plate is 30% of the height of the anode of the spiral piezoelectric cyclone tube, the inclination of the inclined plate is 30 degrees, namely the included angle between the inclined plate and the horizontal plane is 30 degrees; the hydrophobic piezoelectric photocatalysis inner liner of the anode of the spiral piezoelectric cyclone tube is a PTFE film containing titanium dioxide and lanthanum ferrite; the annular aeration cathode is arranged at 1/3 height of the anode of the spiral piezoelectric cyclone tube (calculated from the outlet end of the anode of the spiral piezoelectric cyclone tube), the annular conductive pipeline of the annular aeration cathode is a graphite pipeline, and the light source is a visible light xenon lamp.
Example 3
In this embodiment, a self-cleaning photoelectric integrated sewage treatment apparatus is provided, which has substantially the same structure as the sewage treatment apparatus of embodiment 1, except that:
the height of the anode of the spiral piezoelectric cyclone tube is 40% of the height of the inside of the reaction tank, and the helix angle of the anode 2 of the spiral piezoelectric cyclone tube is 35 degrees; the height of the inclined plate is 35% of the height of the anode of the spiral piezoelectric cyclone tube, the inclination of the inclined plate is 30 degrees, namely, the included angle between the inclined plate and the horizontal plane is 30 degrees; the hydrophobic piezoelectric photocatalysis inner liner of the anode of the spiral piezoelectric cyclone tube is a PTFE film containing bismuth titanate; the power supply is a pulse power supply.
Example 4
In this embodiment, a self-cleaning photoelectric integrated sewage treatment apparatus is provided, which has substantially the same structure as the sewage treatment apparatus of embodiment 1, except that:
the height of the anode of the spiral piezoelectric cyclone tube is 50% of the height of the inside of the reaction tank, and the helix angle of the anode of the spiral piezoelectric cyclone tube is 25 degrees; the height of the inclined plate is 10% of the height of the anode of the spiral piezoelectric cyclone tube, the inclination of the inclined plate is 20 degrees, namely the included angle between the inclined plate and the horizontal plane is 20 degrees; the annular aeration cathode is arranged at the 2/5 height of the anode of the spiral piezoelectric cyclone tube (calculated from the outlet end of the anode of the spiral piezoelectric cyclone tube), and the annular conductive pipeline of the annular aeration cathode is a titanium pipeline; the hydrophobic piezoelectric photocatalysis inner liner of the anode of the spiral piezoelectric cyclone tube is a Kapton film containing zinc oxide composite perovskite; the power supply is a polycrystalline silicon solar photovoltaic panel.
Example 5
In this embodiment, a self-cleaning photoelectric integrated sewage treatment apparatus is provided, which has substantially the same structure as the sewage treatment apparatus of embodiment 1, except that: no sloping plate is arranged in the reaction tank. In the actual sewage treatment process, the added piezoelectric strengthening material is a water-soluble piezoelectric strengthening material, such as peroxodisulfate.
Example 6
In this embodiment, a self-cleaning photoelectric integrated sewage treatment apparatus is provided, which has substantially the same structure as the sewage treatment apparatus of embodiment 1, except that: the reaction tank is internally provided with two identical annular aeration cathodes, the two annular aeration cathodes are positioned at different height positions on the inner wall of the reaction tank, and the distance between the two annular aeration cathodes and the outlet end of the spiral piezoelectric cyclone tube anode is 0.3 times and 0.6 times of the height of the spiral piezoelectric cyclone tube anode respectively.
Example 7
In this example, the self-cleaning photoelectric integrated sewage treatment device described in example 2 was used for sewage treatment, and the sewage used was sewage containing ciprofloxacin as an antibiotic pollutant, wherein the concentration of ciprofloxacin was 20mg/L.
The method comprises the steps of mixing sewage and a piezoelectric reinforcement material, introducing the mixed sewage into a reaction tank through a water inlet by using a spiral piezoelectric cyclone tube anode, ensuring that the spiral piezoelectric cyclone tube anode is completely submerged, starting a reflux pump, a light source, a power supply connected with the spiral piezoelectric cyclone tube anode and an annular aeration cathode, and treating the sewage under the condition of aeration by an aeration disc, controlling the sewage treatment time to be 20min, and discharging the treated sewage from a water outlet to the reaction tank after the sewage is treated for 20 min.
The gas introduced through the aeration disc is air, and the aeration intensity is controlled to be 5m 3 /m 2 H; controlling the addition amount of the piezoelectric reinforcing material so that each liter of sewage contains 0.15g of the piezoelectric reinforcing material; the voltage of the control power supply was 2.5V.
In the process that sewage descends in the spiral piezoelectric cyclone tube anode, potential energy of water flow and piezoelectric reinforcing materials in the sewage excite piezoelectric catalytic effect, free radicals are generated under the effects of photocatalysis and electrocatalytic effect to degrade pollutants in the sewage, and after the sewage flows out of the spiral piezoelectric cyclone tube anode, the pollutants in the sewage are further degraded under aeration and illumination conditions.
During the sewage treatment, sampling is carried out every 5min, the concentration of ciprofloxacin in the sewage is measured, the removal rate of ciprofloxacin is calculated, and the result is shown as the data of the photo-electric coupling piezoelectric reinforced material group in figure 3, and as can be seen from figure 3, the removal rate of ciprofloxacin in the sewage can reach 98% after the sewage is treated for 20min by adopting the method of the invention.
Comparative example 1
The sewage used in this comparative example was the same as in example 7, and the operation of this comparative example was substantially the same as in example 2, except that the spiral-shaped piezoelectric cyclone anode and the annular aeration cathode were not connected to a power source during the wastewater treatment, i.e., the sewage treatment was performed without electrocatalytic action.
During the sewage treatment, samples were taken at 5-minute intervals, the concentration of ciprofloxacin in the sewage was measured, and the removal rate of ciprofloxacin was calculated, and as a result, as shown in the data of the "photo-coupled piezoelectric reinforcing material" group in fig. 3, it was found from fig. 3 that the same sewage as in example 6 was treated for 20 minutes without turning on the power supply (i.e., without applying the electrocatalytic effect), and the removal rate of ciprofloxacin in the sewage was only about 30%.
Comparative example 2
The sewage used in this comparative example was the same as in example 7, and the operation of this comparative example was substantially the same as in example 2, except that the spiral-shaped piezoelectric cyclone anode and the annular aeration cathode were not connected to a power source, aeration was not performed, and no piezoelectric reinforcing material was added, i.e., sewage treatment was performed without electrocatalytic, aeration, and no piezoelectric reinforcing material addition, during the wastewater treatment.
During the sewage treatment, samples were taken at 5-minute intervals, the ciprofloxacin concentration of the sewage was measured, and the ciprofloxacin removal rate was calculated, and as a result, as shown in the data of the "light" group in fig. 3, it was found from fig. 3 that when the sewage treatment was performed without electrocatalytic, aeration and addition of a piezoelectric reinforcing material, the sewage was treated for 20 minutes in the same manner as in example 6, and the ciprofloxacin removal rate was only about 10%.
Comparative example 3
The sewage used in this comparative example was the same as in example 7, and the operation of this comparative example was substantially the same as in example 1, except that the light source was not turned on, aeration was not performed, and the piezoelectric reinforcing material was not added, that is, the sewage treatment was performed without photocatalysis, aeration, and piezoelectric reinforcing material addition during the wastewater treatment.
During the sewage treatment, samples were taken at 5-minute intervals, the ciprofloxacin concentration of the sewage was measured, and the ciprofloxacin removal rate was calculated, and as a result, as shown in the data of the "electric" group in fig. 3, it was found from fig. 3 that when the sewage treatment was performed without photocatalysis, aeration and without the addition of a piezoelectric reinforcing material, the sewage was treated for 20 minutes in the same manner as in example 6, and the ciprofloxacin removal rate was only about 20%.
From the experimental data of comparative example 7 and comparative examples 1 to 3, it is understood that the removal rate of contaminants is very limited by only electrocatalytic or photocatalytic processes; the piezoelectric catalysis and the photocatalysis are combined, so that the improvement degree of the pollutant removal rate is still very limited even under the action of aeration; the invention combines piezocatalysis, photocatalysis, electrocatalytic and aeration, thus remarkably improving the pollutant removal rate.
Example 8
In this embodiment, the self-cleaning photoelectric integrated sewage treatment device described in embodiment 1 is used for sewage treatment, and the adopted sewage is a certain hospital sewage, and has the characteristics of sewage: the TOC concentration of the sewage is 20mg/L, and the pH value is 6.2.
The method comprises the steps of mixing sewage and piezoelectric reinforcement materials by taking iron-carrying zeolite particles with the particle size of 500nm as the piezoelectric reinforcement materials, continuously introducing the mixture into a reaction tank through a water inlet by using a spiral piezoelectric cyclone tube anode, starting a reflux pump, a light source, a power supply connected with the spiral piezoelectric cyclone tube anode and an annular aeration cathode, treating the sewage under the condition of aeration by an aeration disc, controlling the hydraulic retention time of the sewage in the reaction tank to be 30min, and continuously discharging the treated sewage out of the reaction tank through a water outlet.
The gas introduced through the aeration disc is air, and the aeration intensity is controlled to be 1m 3 /m 2 H; controlling the addition amount of the piezoelectric reinforcing material so that each liter of sewage contains 0.3g of the piezoelectric reinforcing material; the voltage of the control power supply is 4V.
In the process that sewage descends in the spiral piezoelectric cyclone tube anode, potential energy of water flow and piezoelectric reinforcing materials in the sewage excite piezoelectric catalytic effect, free radicals are generated under the effects of photocatalysis and electrocatalytic effect to degrade pollutants in the sewage, and after the sewage flows out of the spiral piezoelectric cyclone tube anode, the pollutants in the sewage are further degraded under aeration and illumination conditions.
The TOC concentration of the outlet water of the water outlet is tested, and the TOC removal rate is calculated, so that the TOC removal rate by the method of the embodiment is 95% under the condition that the hydraulic retention time is 30 min.
Example 9
In this embodiment, the self-cleaning photoelectric integrated sewage treatment device described in embodiment 1 is utilized to treat sewage, and the adopted sewage is secondary effluent of petrochemical plants, and has the characteristics of sewage: the TOC concentration of the sewage is 20mg/L, and the initial pH value is 8.5.
Carbon particles with the particle size of 800nm and sodium peroxodisulfate are used as piezoelectric reinforcement materials, sewage and the piezoelectric reinforcement materials are mixed and then continuously introduced into a reaction tank through a water inlet by a spiral piezoelectric cyclone tube anode, a reflux pump, a light source, a power supply connected with the spiral piezoelectric cyclone tube anode and an annular aeration cathode are started, the sewage is treated under the condition of aeration by an aeration disc, the hydraulic retention time of the sewage in the reaction tank is controlled to be 20min, and the treated sewage is continuously discharged out of the reaction tank through a water outlet.
The gas introduced through the aeration disc is the mixed gas of air and ozone (the volume ratio of air to ozone is 1:1), and the aeration intensity is controlled to be 3m 3 /m 2 H; controlling the addition amount of the carbon particles so that 0.2g of the carbon particles are contained in each liter of sewage, and controlling the addition amount of the sodium peroxodisulfate so that 0.2g of the sodium peroxodisulfate is contained in each liter of sewage; the voltage of the control power supply is 3V.
In the process that sewage descends in the spiral piezoelectric cyclone tube anode, potential energy of water flow and piezoelectric reinforcing materials in the sewage excite piezoelectric catalytic effect, free radicals are generated under the effects of photocatalysis and electrocatalytic effect to degrade pollutants in the sewage, and after the sewage flows out of the spiral piezoelectric cyclone tube anode, the pollutants in the sewage are further degraded under aeration and illumination conditions.
The effluent from the water outlet is taken out to test the TOC concentration and the phenolic substance concentration, and the removal rate of the TOC and the phenolic substances is calculated, so that the result shows that the removal rate of the phenolic substances is 100% and the removal rate of the TOC is 98% under the condition that the hydraulic retention time is 20 min.
Claims (10)
1. The self-cleaning photoelectric integrated sewage treatment device is characterized by comprising a reaction tank (1), a spiral piezoelectric cyclone tube anode (2), an annular aeration cathode (3) and a light source (4) which are positioned in the reaction tank (1), a power supply (5) and an aeration device (6);
the shell of the reaction tank (1) is provided with a water inlet (1-1), a water outlet (1-2) and a circulating water outlet (1-3), the water inlet (1-1) and the water outlet (1-2) are positioned at the upper part of the shell of the reaction tank, the circulating water outlet (1-3) is positioned at the lower part of the shell of the reaction tank, the circulating water outlet (1-3) is communicated with the water inlet (1-1) through a reflux pump (1-4) and a circulating water pipe, and the shell of the reaction tank is non-conductive;
the spiral piezoelectric cyclone tube anode (2) consists of a spiral tube and a hydrophobic piezoelectric photocatalysis lining layer attached in the spiral tube, the spiral piezoelectric cyclone tube anode (2) is conductive and transparent, the spiral piezoelectric cyclone tube anode (2) is a spiral pipeline with an outlet end positioned below an inlet end, the inlet of the spiral piezoelectric cyclone tube anode (2) is communicated with the water inlet (1-1), and the outlet of the spiral piezoelectric cyclone tube anode (2) is positioned at the lower part in the reaction tank shell;
the annular aeration cathode (3) comprises at least one annular conductive pipeline (3-1) and a plurality of aeration discs (3-2) which are distributed on the annular conductive pipeline and are communicated with the annular conductive pipeline, the annular conductive pipeline is communicated with aeration equipment (6) positioned outside the reaction tank through an aeration pipe (3-3), and the annular aeration cathode (3) is arranged around the spiral piezoelectric cyclone pipe anode (2);
the spiral piezoelectric cyclone tube anode (2) and the annular aeration cathode (3) are respectively connected with the anode and the cathode of the power supply (5) through wires; the irradiation range of the light rays emitted by the light source (4) covers the anode (2) of the spiral piezoelectric cyclone tube, and the wavelength of the light rays emitted by the light source (4) is within the range of 80-2000 nm.
2. The self-cleaning photoelectric integrated sewage treatment device according to claim 1, wherein an inclined plate (7) is further arranged in the reaction tank (1), and the inclined plate (7) is positioned below an outlet of the spiral piezoelectric cyclone tube anode (2).
3. The self-cleaning photoelectric integrated sewage treatment device according to claim 2, wherein the height of the inclined plate (7) arranged in the reaction tank is 10% -40% of the height of the spiral piezoelectric cyclone tube anode (2).
4. A self-cleaning photoelectric integrated sewage treatment device according to any one of claims 1 to 3, characterized in that the helix angle of the anode (2) of the spiral piezoelectric swirl tube is 20 ° to 45 °.
5. The self-cleaning photoelectric integrated sewage treatment device according to any one of claims 1 to 3, wherein the height of the spiral piezoelectric swirl tube anode (2) is 30% -70% of the height of the inside of the reaction tank, and the spiral surrounding diameter of the spiral piezoelectric swirl tube anode (2) is sequentially reduced from top to bottom.
6. A self-cleaning photoelectric integrated sewage treatment device according to any one of claims 1 to 3, wherein the hydrophobic piezoelectric photocatalytic inner liner is a light-transmitting hydrophobic film containing a piezoelectric photocatalytic material, and the piezoelectric photocatalytic material is at least one of perovskite, iron oxide, bismuth oxide and titanate, or a compound of titanium dioxide or zinc oxide and at least one of perovskite, iron oxide, bismuth oxide and titanate; the spiral tube is made of light-transmitting materials.
7. A method of sewage treatment, characterized in that it uses the integrated sewage treatment apparatus according to any one of claims 1 to 6, comprising the steps of:
introducing sewage and a piezoelectric reinforcement material into a reaction tank through a water inlet by a spiral piezoelectric cyclone tube anode, and treating the sewage under the conditions of starting a reflux pump, a light source, a power supply connected with the spiral piezoelectric cyclone tube anode and an annular aeration cathode and aeration by an aeration disc, wherein the treated sewage is discharged from a water outlet to the reaction tank; the piezoelectric reinforced material is at least one of modified zeolite, zeolite compound, carbon-based material and persulfate; the gas introduced through the aeration disc is at least one of air and ozone; controlling the hydraulic retention time of the sewage in the reaction tank to be 0.3-2 h;
in the process that sewage descends in the spiral piezoelectric cyclone tube anode, potential energy of water flow and piezoelectric reinforcing materials in the sewage excite piezoelectric catalytic effect, free radicals are generated under the effects of photocatalysis and electrocatalytic effect to degrade pollutants in the sewage, and after the sewage flows out of the spiral piezoelectric cyclone tube anode, the pollutants in the sewage are further degraded under aeration and illumination conditions.
8. The wastewater treatment method according to claim 7, wherein the particle size of the piezoelectric reinforcing material is not more than 300. Mu.m.
9. The wastewater treatment method according to claim 7, wherein the amount of the piezoelectric reinforcing material added is controlled so that 0.005 to 1g of the piezoelectric reinforcing material is contained in each liter of wastewater.
10. A sewage treatment method according to any one of claims 7 to 9, wherein the aeration intensity is controlled to not more than 20m when aeration is performed by the aeration disc 3 /m 2 ·h。
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