CN117430215B - Device for treating sewage and wastewater by electric flocculation and application - Google Patents

Device for treating sewage and wastewater by electric flocculation and application Download PDF

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Publication number
CN117430215B
CN117430215B CN202311780761.9A CN202311780761A CN117430215B CN 117430215 B CN117430215 B CN 117430215B CN 202311780761 A CN202311780761 A CN 202311780761A CN 117430215 B CN117430215 B CN 117430215B
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cathode
hollow fiber
sewage
anode
water
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CN117430215A (en
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祝海涛
吴雅琴
杨波
熊威
吴思梵
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Hangzhou Water Treatment Technology Development Center Co Ltd
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Hangzhou Water Treatment Technology Development Center Co Ltd
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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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/463—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrocoagulation
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46119—Cleaning the electrodes
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C02F2001/46138—Electrodes comprising a substrate and a coating
    • C02F2001/46142—Catalytic coating
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46152—Electrodes characterised by the shape or form
    • C02F2001/46171—Cylindrical or tubular shaped
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/46115—Electrolytic cell with membranes or diaphragms

Abstract

The invention relates to a device for treating sewage and wastewater by electric flocculation and application thereof, belonging to the field of treatment of water, wastewater, sewage or sludge. The device comprises a shell, an electrode device is arranged in the shell, the electrode device comprises a hollow columnar anode, a cathode and a hollow fiber membrane component, the hollow columnar anode is sleeved outside the cathode, a cavity is formed between the hollow columnar anode and the cathode, and the hollow fiber membrane component is arranged in the cavity. The hollow columnar anode, the cathode and the hollow fiber membrane component surfaces are modified, and the hollow columnar anode is lined with the charged membrane, so that the electrode reaction efficiency is effectively improved, the pollutant adsorption and removal of the device are enhanced, the water quality of treated produced water and the pollution resistance and operation stability of the device are greatly improved, and the problems of unstable long-term treatment effect, high content of residual metal ions of produced water, poor pollution resistance of the device and the like in the electric flocculation treatment of the polluted wastewater are solved.

Description

Device for treating sewage and wastewater by electric flocculation and application
Technical Field
The invention relates to the field of treatment of water, wastewater, sewage or sludge, in particular to an electric flocculation sewage treatment device and application.
Background
The electric flocculation is a water treatment technology for generating cations through electrolysis of an anode under the action of direct current and removing pollutants in the solution through condensation, flotation, oxidation reduction and the like, and has the advantages of simple operation, small sludge generation amount, no need of chemical agent addition, easiness in realization of automation and the like. However, the electric flocculation device has poor effect of removing organic pollutants in the sewage and wastewater, and more metal ions generated by anodic electrolysis remain in the produced water after the electric flocculation treatment, so that the produced water cannot be directly recycled. In addition, the reaction efficiency of the polar plate in the electric flocculation operation is reduced due to the pollution of impurities, and the treatment effect of the device is greatly reduced due to the passivation of the surface of the polar plate. At present, a pulse power supply is adopted to reduce the power-on time and relieve passivation phenomena, such as CN103304075A; or by adding an electrolytic tank, a filtering device and the like, the water quality of the electroflocculation produced water is improved, such as CN112759146A, but the pollutant removing effect and stability are not obviously improved, and the problems of device pollution and treatment energy efficiency reduction are not fundamentally solved. Therefore, the existing electric flocculation device still has the problems of low pollutant removal rate, poor pollution resistance of the device, high content of residual metal ions in the treated produced water, unstable operation of the device and the like in the treatment of sewage and wastewater.
Disclosure of Invention
First, the technical problem to be solved
In view of the defects and shortcomings of the prior art, the invention provides the device for treating the sewage and the wastewater by the electric flocculation and the application thereof, which can efficiently remove pollutants in the sewage and the wastewater, and has the advantages of high product quality, good pollution resistance of the device and stable long-term operation treatment effect.
(II) technical scheme
In order to achieve the above purpose, the main technical scheme adopted by the invention comprises the following steps:
in a first aspect, the invention provides an electric flocculation sewage treatment device, which comprises a shell, wherein an electrode device is arranged in the shell, the electrode device comprises a hollow columnar anode, a cathode and a hollow fiber membrane component, the hollow columnar anode is sleeved outside the cathode, a cavity is formed between the hollow columnar anode and the cathode, and the hollow fiber membrane component is arranged in the cavity;
the inner surface of the hollow columnar anode is subjected to hydrophobic modification;
the surface of the cathode is provided with a metal catalyst coating;
the hollow fiber membrane module is as follows: the method comprises the steps of preparing a hollow fiber mixed matrix membrane by taking hydrophilic nano particles and polysulfone or polyether sulfone as raw materials, and generating a positively charged membrane layer on the surface of the hollow fiber mixed matrix membrane by adopting polyamine, polybasic acyl chloride, chitosan quaternary ammonium salt and zwitterionic polyacrylamide through interfacial polymerization reaction.
Preferably, the cathode is a solid cylindrical cathode.
According to the invention, the hydrophilic nano particles and polysulfone or polyether sulfone are used as raw materials by a dry-wet spinning technology, and the prepared hollow fiber mixed matrix membrane is beneficial to regulating and controlling the pore structure of the membrane and improving the hydrophilicity of the membrane, so that the permeation flux of the membrane can be effectively improved. The positively charged hydrophilic-low surface energy hollow fiber membrane layer generated on the surface of the hollow fiber mixed matrix membrane can effectively intercept the residual metal ions (Al 3+ 、Fe 2+ 、Fe 3+ ) Meanwhile, the hydrophilic-low surface energy area formed on the membrane layer can weaken the adsorption effect of the membrane on pollutants, and improve the anti-pollution performance of the hollow fiber membrane.
Optionally, the hollow columnar anode is iron or aluminum with the inner surface hydrophobically modified.
Optionally, the method for hydrophobically modifying the inner surface of the hollow columnar anode comprises the following steps: and (3) carrying out grafting reaction on the inner surface of the hollow columnar anode by using styrene or polybutadiene.
After grafting modification, the hollow columnar anode has self-cleaning performance, can effectively prevent or slow down the reduction of treatment efficiency caused by pollution on the surface of the electrode, can lead the distribution of metal ions generated by anode electrolysis to be more uniform, and strengthens the processes of adsorption, bridging, net capturing and the like of pollutants in sewage and wastewater, thereby improving the treatment efficiency.
Optionally, the hollow columnar anode is lined with a charged membrane.
Optionally, the preparation method of the charged membrane comprises the following steps: adopting polyamine, polybasic acyl chloride and a fatty acid anionic surfactant to react on the surface of the porous membrane facing the cathode to generate a negatively charged membrane layer; the fatty acid anionic surfactant is at least one of sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, sodium hexadecyl sulfonate and sodium hexadecyl benzene sulfonate. The negative charged film layer can effectively prevent oxygen anions from forming oxides with metal at the anode interface in the electro-flocculation electrochemical reaction process, thereby preventing the generation of an electrode passivation film.
During the reaction, the mass concentration of the polybasic acyl chloride in the oil phase is 0.1-0.8%, the mass concentration of the polybasic amine in the water phase is 0.15-1%, and the mass concentration of the fatty acid anionic surfactant is 0.05-0.5%;
and spraying a polyacrylic acid copolymer containing at least one of titanate, tungstate and vanadate on the surface of the porous membrane facing the anode. The anode has a catalytic effect on anode electrolysis, and solves the problem that the anode has a reduced anode electrolysis rate along with the increase of reaction activation energy in the electric flocculation operation process; meanwhile, the method can promote hydroxyl ions and the like in the sewage and wastewater to lose electrons and generate oxide substances with stronger activity, and the pollutant removal effect is improved; in addition, the electrolytic catalyst is uniformly fixed on the lining diaphragm, so that the catalytic active site of the electrolytic catalyst is effectively increased, and the risk of water quality pollution caused by catalyst loss is avoided.
Optionally, the polyacrylic acid copolymer is one of polyethylene glycol-polyacrylic acid, polyvinylpyrrolidone-polyacrylic acid and polyethyleneimine-polyacrylic acid.
Optionally, the hydrophilic nanoparticle is SiO 2 Or a metal oxide; the polyamine is one or more of piperazine, m-phenylenediamine, p-phenylenediamine, piperazine, o-phenylenediamine, diaminotoluene and 2, 5-dimethylpiperazine; the polybasic acyl chloride is one or more of trimesoyl chloride, phthaloyl chloride, isophthaloyl chloride, 3', 5' -biphenyl tetra-formyl chloride, terephthaloyl chloride and adipoyl chloride;
in the interfacial polymerization reaction, the mass concentration of the polybasic acyl chloride in the oil phase is 0.2-1.5%, the mass concentration of the polybasic amine in the water phase is 0.5-2%, and the mass concentration of the chitosan quaternary ammonium salt is 0.1-1%.
Optionally, the cathode is stainless steel with a metal catalyst coating on the surface.
Optionally, the surface of the cathode has uniform roughness, and a metal catalyst coating is arranged on the surface with uniform roughness; the metal catalyst is one or more of nickel, cobalt, platinum, rhodium and palladium.
The rough surface of the cathode surface can obviously improve the generation rate of bubbles on the cathode, increase the contact and adsorption of the bubbles and flocculate, optimize the particle size and distribution of the bubbles through the rough surface structure and strengthen the air floatation effect of electric flocculation.
Optionally, the hollow cylindrical anode and the cathode are connected to a power source external to the device.
Optionally, the device further comprises a water inlet, a water producing port and a sewage draining outlet, wherein the water inlet and the sewage draining outlet are connected with the cavity at the bottom of the electrode device, and the water producing port is connected with an inner hole of a membrane bundle of the hollow fiber membrane assembly at the top of the electrode device.
Optionally, the device also comprises a water outlet cavity, wherein one end of the water outlet cavity is communicated with an inner hole of the membrane bundle of the hollow fiber membrane component, and the other end of the water outlet cavity is communicated with a water producing port.
Optionally, the two ends of the hollow fiber membrane component are bonded and fixed by epoxy resin. The upper end in the casing is equipped with the water outlet chamber, and the water outlet chamber links to each other with producing the mouth of a river. The inner hole of the membrane bundle at the top of the hollow fiber membrane component is not bonded by epoxy resin, and the treated water enters the water outlet cavity through the inner hole of the membrane bundle at the top of the hollow fiber membrane component and further passes through the water outlet discharge device. The water inlet and the sewage outlet are respectively connected with the cavity at the bottom of the electrode device, namely, the cavity between the adjacent hollow fiber membranes.
Optionally, the water inlet is connected with a sewage and wastewater storage device, the water producing port is connected with a purified water collecting device, and the sewage draining port is connected with a flocculate collecting device.
In a second aspect, the invention provides the use of an apparatus for the electroflocculation treatment of waste water, said apparatus being operated at a current density of from 10 to 150A/m 2 The operating pressure is 0.05-1MPa.
(III) beneficial effects
The beneficial effects of the invention are as follows: in the device for treating the sewage and the wastewater by the electric flocculation, the inner surface of the hollow columnar anode has self-cleaning performance after being subjected to hydrophobic modification, so that the reduction of the treatment efficiency caused by pollution on the surface of the electrode is effectively prevented, the distribution of metal ions generated by the electrolysis of the anode is more uniform, the processes of adsorbing, bridging, capturing and the like of pollutants in the sewage and the wastewater are enhanced, and the pollutant removal efficiency is improved.
On one hand, the hollow columnar anode lining charge diaphragm can effectively prevent oxygen anions from migrating to an anode interface to form metal oxides in the electro-flocculation electrochemical reaction process, inhibit the generation of an electrode passivation film and improve the long-term operation stability of the device; on the other hand, the polyacrylic acid copolymer containing the catalyst realizes the uniform fixation of the electrolytic catalyst on the lining diaphragm, effectively increases the catalytic active site of the electrolytic catalyst, enhances the catalytic effect of the electrolytic catalyst on anode electrolysis, reduces the activation energy of electrode reaction, avoids the risk of water pollution caused by catalyst loss, can promote hydroxyl ions and the like in sewage to lose electrons to generate oxidized substances with stronger activity, and improves the pollutant removal effect.
The cathode is subjected to surface roughening and metal spraying catalyst treatment, so that not only are the particle size and distribution of bubbles optimized, but also the generation of bubbles on the cathode can be accelerated, the mass transfer, adsorption and air floatation effects in the electric flocculation process are enhanced, and the pollutant removal effect is effectively promoted.
The hydrophilic-low surface energy hollow fiber membrane regulates and controls the pore structure and the hydrophilicity of the membrane by introducing hydrophilic nano particles, so that the membrane permeation flux is improved; the surface of the membrane is positively charged, so that metal ions remained in the solution after the electric flocculation reaction can be effectively trapped, and the formed hydrophilic-low surface energy area can weaken the adsorption effect of the membrane on pollutants, so that the anti-pollution performance of the hollow fiber membrane is obviously improved, and the device is kept in a stable state in long-term operation.
The operating conditions of the apparatus according to the invention were chosen (current density of 10-150A/m 2 The operating pressure is 0.05-1 MPa), pollutants in the polluted wastewater can be removed efficiently and at low cost, if the current or the operating pressure is too small, the reaction efficiency is reduced, the bubble particle size distribution is uneven, the removal effect is affected, if the current is too large, the electrode is damaged, the operation energy consumption is increased, and if the operating pressure is too large, the hollow fiber membrane is damaged, and the device stability is reduced.
Drawings
FIG. 1 is a schematic view of the appearance structure of the device for treating sewage and wastewater by electric flocculation.
FIG. 2 is a schematic view of the longitudinal sectional perspective structure of the device for treating sewage and wastewater by electroflocculation of the invention.
FIG. 3 is a top cross-sectional view of the apparatus for treating sewage and wastewater by electroflocculation according to the present invention.
[ reference numerals description ]
1: a housing; 2: an electrode device; 21: a hollow columnar anode; 22: a cathode; 23: a hollow fiber membrane module; 24: a charged separator; 3: a water inlet; 4: a water producing port; 5: a sewage outlet; 6: a water outlet cavity; 7: a supporting part.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments for better explaining the present invention. While exemplary embodiments of the invention are shown below, it should be understood that the invention may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
The device for treating sewage and wastewater by electric flocculation provided by the embodiment of the invention is specifically described below.
Referring to fig. 1-3, the device for treating sewage and wastewater by electroflocculation provided by the embodiment of the invention comprises a columnar shell 1, an electrode device 2 arranged in the columnar shell 1, wherein the electrode device 2 comprises a hollow columnar anode 21, a cathode 22 and a hollow fiber membrane component 23, the hollow columnar anode 21 is sleeved outside the cathode 22, a cavity is formed between the hollow columnar anode 21 and the cathode 22, and a hydrophilic-low surface energy hollow fiber membrane component 23 is vertically arranged in the formed cavity. The hollow cylindrical anode 21 and cathode 22 are connected to a power supply external to the device. The electric flocculation sewage treatment device also comprises a water inlet 3, a water producing port 4 and a sewage draining port 5, wherein the water inlet 3 is positioned on the side wall of the lower end of the shell 1 and is connected with the cavity at the bottom of the electrode device 2, and is used for conveying sewage to be treated into the electrode device 2; the water producing port 4 is positioned on the upper side wall of the shell 1 and is connected with the inner hole of the membrane bundle of the hollow fiber membrane module 23 at the top of the electrode device 2, and is used for outputting the produced water after being treated by the electrode device 2. The hydrophilic-low surface energy hollow fiber membrane module 23 is positioned below the water producing port 4, and a supporting part 7 is arranged at the bottom of the electrode device 2, and the supporting part 7 is used for supporting the electrode device 2 so as to ensure that the electrode device 2 is stable in the shell 1. The upper end of the shell 1 is internally provided with a water outlet cavity 6, one end of the water outlet cavity 6 is communicated with an inner hole of a membrane bundle of the hollow fiber membrane module 23, and the other end of the water outlet cavity 6 is communicated with a water producing port. A drain outlet 5 is arranged on the side wall of the lower end of the shell 1, and the drain outlet 5 is also connected with a cavity at the bottom of the electrode device 2 and is used for discharging flocculate generated in the electrode device. The sewage outlet 5 is provided with a valve. Valves can also be arranged on the water inlet 3 and the water outlet 4.
The hollow fiber membrane assembly 23 is formed by arranging a plurality of hollow fiber membranes in parallel, and two ends of the hollow fiber membrane assembly 23 are bonded and fixed by adopting epoxy resin, wherein the inner hole of the upper end membrane bundle of the hollow fiber membrane is not sealed by the epoxy resin and is connected with the water outlet 4 through the water outlet cavity 6; the lower ends of the hollow fiber membranes are sealed with epoxy resin, and a water inlet 3 and a drain 5 are provided at the place where the hollow fiber membranes are not provided (i.e., at the cavity).
The water producing port 4 passes through the side wall of the upper end of the shell 1 through a pipeline and is connected with an external purified water collecting device; the water inlet 3 passes through the side wall of the lower end of the shell 1 through a pipeline and is connected with an external sewage and wastewater storage device; the sewage outlet 5 passes through the side wall of the lower end of the shell 1 through a pipeline and is connected with an external flocculate collecting device.
The hollow columnar anode 21 is iron or aluminum, and the inner surface of the hollow columnar anode 21 is subjected to hydrophobic modification through a grafting reaction, wherein the hydrophobic modification method comprises the following steps: styrene or polybutadiene is adopted to carry out grafting reaction on the inner surface of the anode, and the specific method is that a styrene solution is coated on the inner surface of a hollow columnar anode and gamma rays or ultraviolet light are used for carrying out irradiation grafting reaction, so that a hydrophobic layer of the surface graft copolymer is formed. The anode has self-cleaning performance after grafting modification, can effectively prevent or slow down the reduction of treatment efficiency caused by the pollution of the surface of the electrode, can lead the distribution of metal ions generated by anode electrolysis to be more uniform, strengthen the processes of adsorption, bridging, net capturing and the like of pollutants in sewage and wastewater, and further improve the treatment efficiency.
The hollow columnar anode 21 is lined with a charged diaphragm 24, and the preparation method of the charged diaphragm 24 comprises the following steps: the method comprises the steps of coating a mixed solution of a fatty acid anionic surfactant and polyamine on a porous membrane (such as polypropylene, polyvinylidene fluoride, polysulfone, polyethersulfone or polyimide and the like, wherein the surface of the porous membrane (the surface facing a cathode) is 10-100 nm) by adopting polyamine, polybasic acyl chloride and the fatty acid anionic surfactant, the reaction steps are that the concentration of the fatty acid anionic surfactant in the mixed solution is 0.05-0.5wt%, the concentration of the polybasic amine is 0.15-1wt%, the residual solution is removed after standing for 30-120s, the residual solution is removed after the polybasic acyl chloride solution with the concentration of 0.1-0.8wt% is coated for 5-60s, and the drying is carried out, so that a negatively charged polyamide membrane layer is generated. The other surface (the surface facing the anode) of the porous membrane is controllably sprayed (can be sprayed with a full or any area) by micro liquid drops, and at least one of titanate, tungstate and vanadate is contained in a polyacrylic acid copolymer (polyethylene glycol-polyacrylic acid, polyvinylpyrrolidone-polyacrylic acid, polyethyleneimine-polyacrylic acid and the like), wherein the proportion of at least one of titanate, tungstate and vanadate in the polyacrylic acid copolymer is 0.5-10wt%, so that the porous membrane has a catalytic effect on anodic electrolysis, and the problems that the activation energy of the anode is increased along with the reaction in the electroflocculation operation process and the anodic electrolysis rate is reduced are solved; meanwhile, the method can promote hydroxyl ions and the like in the sewage and wastewater to lose electrons and generate oxide substances with stronger activity, and the pollutant removal effect is improved; in addition, the electrolytic catalyst is uniformly fixed on the lining diaphragm, so that the catalytic active site of the electrolytic catalyst is effectively increased, and the risk of water quality pollution caused by catalyst loss is avoided.
The cathode 22 is made of stainless steel with uniform roughness on the surface, and one or more metal catalysts (the loading amount of the catalyst on the surface of the cathode is 0.0001-0.05 wt%) are sprayed on the surface of the cathode, so that the generation rate of bubbles on the cathode can be remarkably improved, the contact and adsorption of the bubbles with flocculates are increased, the particle size and distribution of the bubbles are optimized through the concave-convex surface structure, and the air floatation effect of electric flocculation is enhanced.
The preparation method of the hydrophilic-low surface energy hollow fiber membrane 23 includes: hydrophilic nano particles (titanium oxide, silicon oxide and the like) and polysulfone or polyether sulfone are adopted to prepare a hollow fiber mixed matrix membrane through dry-wet spinning, so that the regulation and control of a membrane pore structure are facilitated, the hydrophilicity of the membrane is improved, and the permeation flux of the membrane can be effectively improved; and polyamine (m-phenylenediamine, piperazine, etc.), polybasic acyl chloride (trimesoyl chloride, adipoyl chloride, etc.), chitosan quaternary ammonium salt and zwitterionic polyacrylamide are adopted to generate positively charged hydrophilic-low surface energy hollow fiber membrane through polymerization reaction, specifically, the inner surface of the hollow fiber mixed matrix membrane is coated with polyamine solution containing chitosan quaternary ammonium salt, the concentration of polyamine in the solution is 0.5-2wt%, the concentration of chitosan quaternary ammonium salt is 0.1-1wt%, then the outer surface is coated with polybasic acyl chloride solution with concentration of 0.2-1.5wt%, the reaction is carried out for 0.5-3min, residual solution is removed, and the solution is dried and then immersed into zwitterionic polyacrylamide (formed by hydrolysis and copolymerization of vinylamide and vinyl cationic monomer acrylamide monomer) with concentration of 0.1-2wt% for 10-200s, and the positively charged hydrophilic-low surface energy hollow fiber membrane is generated after the surface solution is removed and dried. The hollow fiber mixed matrix membrane can effectively intercept residual metal ions (Al) in the solution after the electric flocculation reaction through secondary surface modification 3+ 、Fe 2+ 、Fe 3+ ) Meanwhile, the hydrophilic-low surface energy area formed on the membrane layer can weaken the adsorption effect of the membrane on pollutants, and the anti-pollution performance of the hollow fiber membrane is improved.
The water inlet is connected with the sewage and wastewater storage device, the water producing port is connected with the purified water collection device, and the sewage outlet is connected with the flocculate collection device. The operating conditions of the device are that the current density is 10-150A/m 2 The operating pressure is 0.05-1MPa.
The following is an application example of the present invention.
Example 1
In this embodiment, the device for treating sewage and wastewater by electroflocculation includes an electrode device disposed in a cylindrical housing, the electrode device includes a hollow cylindrical anode, a cathode, and a hollow fiber membrane module, the hollow cylindrical anode is sleeved outside the cathode, and a cavity is formed between the hollow cylindrical anode and the cathode, and a hydrophilic-low surface energy hollow fiber membrane module is vertically disposed in the formed cavity. The hollow columnar anode and the cathode are connected with a power supply outside the device. The electric flocculation sewage treatment device also comprises a water inlet, a water producing port and a sewage draining port, wherein the water inlet is positioned on the side wall of the lower end of the shell, is connected with the cavity at the bottom of the electrode device and is used for conveying sewage to be treated into the electrode device; the water producing port is positioned on the side wall of the upper end of the shell, is connected with the inner hole of the membrane bundle of the hollow fiber membrane component at the top of the electrode device and is used for outputting the produced water after being treated by the electrode device; the upper end of the shell is internally provided with a water outlet cavity, one end of the water outlet cavity is communicated with an inner hole of the membrane bundle of the hollow fiber membrane component, and the other end of the water outlet cavity is communicated with the water producing port. The hydrophilic-low surface energy hollow fiber membrane is positioned below the water producing port, and a certain distance is reserved between the bottom of the electrode device and the bottom of the shell. A drain outlet is arranged on the side wall of the lower end of the shell and is also connected with the cavity at the bottom of the electrode device for discharging flocculate generated in the electrode device. Valves are arranged on the water inlet, the water producing port and the sewage outlet.
The hollow columnar anode is aluminum, and the inner surface of the hollow columnar anode is modified by styrene in a hydrophobic manner. The hollow columnar anode is internally lined with a charged diaphragm, namely, one surface of a porous membrane (made of polypropylene and with the aperture of 100 nm) facing the cathode is a negatively charged polyamide membrane layer prepared by reacting p-phenylenediamine, isophthaloyl dichloride and sodium dodecyl sulfonate, wherein in the reaction, the concentration of sodium dodecyl sulfonate in a water phase is 0.5wt%, the concentration of p-phenylenediamine is 1wt%, the concentration of phthaloyl dichloride in an oil phase is 0.8wt%, and the reaction time is 10s.
The side of the porous membrane facing the anode was polyethylene glycol-polyacrylic acid containing 10wt% titanate.
The cathode is made of stainless steel, and the surface of the cathode has uniform roughness, and nickel catalyst is sprayed on the surface.
The hydrophilic-low surface energy hollow fiber membrane is a hollow fiber mixed matrix membrane prepared by dry-wet spinning of hydrophilic titanium oxide nano particles and polysulfone, and is generated by polymerization reaction of m-phenylenediamine, trimesic acid chloride, chitosan quaternary ammonium salt and zwitterionic polyacrylamide. Specifically, a polyamine solution containing chitosan quaternary ammonium salt is coated on the inner surface of a hollow fiber mixed matrix membrane, the concentration of m-phenylenediamine is 2wt%, the concentration of chitosan quaternary ammonium salt is 1wt%, then a trimesoyl chloride solution with the concentration of 1.5wt% is coated on the outer surface, the reaction is carried out for 0.5min, the residual solution is removed, the solution is dried in the air, and then the solution is immersed into a zwitterionic polyacrylamide solution with the concentration of 2wt% for 100s, and the surface solution is removed and then dried, so that the positively charged hydrophilic-low surface energy hollow fiber membrane is formed.
The water inlet is connected with the sewage and wastewater storage device, the water producing port is connected with the purified water collection device, and the sewage outlet is connected with the flocculate collection device. The operating conditions of the device were a current density of 70A/m 2 The operating pressure was 0.1MPa.
The conductivity of the sewage to be treated is 17640 mu S/cm, the silicon compound content is 126mg/L, the hardness content is 272mg/L, and the COD content is 417mg/L. The purified water obtained after 30min of treatment by the apparatus of this example had a silicon compound content of 2.4mg/L, a hardness content of 5.8mg/L, a COD content of 14.3mg/L and a residual metal (iron/aluminum) ion content of 0.039mg/L. The purified water obtained after 360min of treatment by the device of the embodiment has the silicon compound content of 2.5mg/L, the hardness content of 5.7mg/L, the COD content of 16.5mg/L and the residual metal (iron/aluminum) ion content of 0.041mg/L. The device of this embodiment still keeps steadily to the removal effect of pollutant such as silicon compound, hardness, COD in the dirty waste water after 360min operation, and the state of the pollutant in the dirty waste water of high-efficient removal can be kept to the device of this embodiment when long-time operation.
Example 2
In this embodiment, the device for treating sewage and wastewater by electroflocculation includes an electrode device disposed in a cylindrical housing, the electrode device includes a hollow cylindrical anode, a cathode, and a hollow fiber membrane module, the hollow cylindrical anode is sleeved outside the cathode, and a cavity is formed between the hollow cylindrical anode and the cathode, and a hydrophilic-low surface energy hollow fiber membrane module is vertically disposed in the formed cavity. The hollow columnar anode and the cathode are connected with a power supply outside the device. The electric flocculation sewage treatment device also comprises a water inlet, a water producing port and a sewage draining port, wherein the water inlet is positioned on the side wall of the lower end of the shell, is connected with the cavity at the bottom of the electrode device and is used for conveying sewage to be treated into the electrode device; the water producing port is positioned on the side wall of the upper end of the shell, is connected with the inner hole of the membrane bundle of the hollow fiber membrane component at the top of the electrode device and is used for outputting the produced water after being treated by the electrode device; the upper end of the shell is internally provided with a water outlet cavity, one end of the water outlet cavity is communicated with an inner hole of the membrane bundle of the hollow fiber membrane component, and the other end of the water outlet cavity is communicated with the water producing port. The hydrophilic-low surface energy hollow fiber membrane is positioned below the water producing port, and a certain distance is reserved between the bottom of the electrode device and the bottom of the shell. A drain outlet is arranged on the side wall of the lower end of the shell and is also connected with the cavity at the bottom of the electrode device for discharging flocculate generated in the electrode device. Valves are arranged on the water inlet, the water producing port and the sewage outlet.
The hollow columnar anode is iron, and the inner surface is modified by styrene in a hydrophobic way. The hollow columnar anode is internally lined with a charged diaphragm, namely, one surface of a porous membrane (made of polyvinylidene fluoride with the pore diameter of 50 nm) facing the cathode is a negatively charged polyamide membrane layer prepared by reacting p-phenylenediamine, isophthaloyl chloride and sodium dodecyl benzene sulfonate, wherein in the reaction, the concentration of sodium dodecyl sulfonate in a water phase is 0.05wt%, the concentration of p-phenylenediamine is 0.15wt%, the concentration of phthaloyl chloride in an oil phase is 0.1wt%, and the reaction time is 30s.
The side of the porous membrane facing the anode was polyvinylpyrrolidone-polyacrylic acid containing 0.5wt% vanadate.
The cathode is made of stainless steel, and the surface of the cathode has uniform roughness, and cobalt catalyst is sprayed on the surface.
The hydrophilic-low surface energy hollow fiber membrane is a hollow fiber mixed matrix membrane prepared by dry-wet spinning of hydrophilic silica nano particles and polyethersulfone, and is generated by polymerization reaction of m-phenylenediamine, adipoyl chloride, chitosan quaternary ammonium salt and zwitterionic polyacrylamide. Specifically, a polyamine solution containing chitosan quaternary ammonium salt is coated on the inner surface of a hollow fiber mixed matrix membrane, the concentration of m-phenylenediamine is 0.5wt%, the concentration of chitosan quaternary ammonium salt is 0.1wt%, then adipoyl chloride solution with the concentration of 0.2wt% is coated on the outer surface of the hollow fiber mixed matrix membrane, the hollow fiber membrane is reacted for 3min, the residual solution is removed, and the hollow fiber membrane is immersed into a zwitterionic polyacrylamide solution with the concentration of 2wt% after being dried, and the hollow fiber membrane with positively charged hydrophilic-low surface energy is produced after the surface solution is removed and dried.
The water inlet is connected with the sewage and wastewater storage device, the water producing port is connected with the purified water collection device, and the sewage outlet is connected with the flocculate collection device. The operating conditions of the device were a current density of 150A/m 2 The operating pressure was 1MPa.
The conductivity of the sewage to be treated is 17640 mu S/cm, the silicon compound content is 126mg/L, the hardness content is 272mg/L, and the COD content is 417mg/L. The purified water obtained after 30min of treatment by the device of the embodiment had a silicon compound content of 1.6mg/L, a hardness content of 3.5mg/L, a COD content of 12.8mg/L and a residual metal (iron/aluminum) ion content of 0.032mg/L. The purified water obtained after 360 minutes of treatment by the device of the embodiment had a silicon compound content of 1.8mg/L, a hardness content of 3.8mg/L, a COD content of 14.2mg/L and a residual metal (iron/aluminum) ion content of 0.033mg/L. The device of this embodiment still keeps steadily to the removal effect of pollutant such as silicon compound, hardness, COD in the dirty waste water after 360min operation, and the state of the pollutant in the dirty waste water of high-efficient removal can be kept to the device of this embodiment when long-time operation.
Example 3
In this embodiment, the device for treating sewage and wastewater by electroflocculation includes an electrode device disposed in a cylindrical housing, the electrode device includes a hollow cylindrical anode, a cathode, and a hollow fiber membrane module, the hollow cylindrical anode is sleeved outside the cathode, and a cavity is formed between the hollow cylindrical anode and the cathode, and a hydrophilic-low surface energy hollow fiber membrane module is vertically disposed in the formed cavity. The hollow columnar anode and the cathode are connected with a power supply outside the device. The electric flocculation sewage treatment device also comprises a water inlet, a water producing port and a sewage draining port, wherein the water inlet is positioned on the side wall of the lower end of the shell, is connected with the cavity at the bottom of the electrode device and is used for conveying sewage to be treated into the electrode device; the water producing port is positioned on the side wall of the upper end of the shell, is connected with the inner hole of the membrane bundle of the hollow fiber membrane component at the top of the electrode device and is used for outputting the produced water after being treated by the electrode device; the upper end of the shell is internally provided with a water outlet cavity, one end of the water outlet cavity is communicated with an inner hole of the membrane bundle of the hollow fiber membrane component, and the other end of the water outlet cavity is communicated with the water producing port. The hydrophilic-low surface energy hollow fiber membrane is positioned below the water producing port, and a certain distance is reserved between the bottom of the electrode device and the bottom of the shell. A drain outlet is arranged on the side wall of the lower end of the shell and is also connected with the cavity at the bottom of the electrode device for discharging flocculate generated in the electrode device. Valves are arranged on the water inlet, the water producing port and the sewage outlet.
The hollow columnar anode is aluminum, and the inner surface of the hollow columnar anode is modified by styrene in a hydrophobic manner. The hollow columnar anode is internally lined with a charged diaphragm, namely, one surface of a porous membrane (made of polysulfone and with the aperture of 10 nm) facing the cathode is a negatively charged polyamide membrane layer prepared by reacting p-phenylenediamine, isophthaloyl dichloride and sodium hexadecyl sulfonate, wherein in the reaction, the concentration of sodium hexadecyl sulfonate in a water phase is 0.2wt%, the concentration of p-phenylenediamine is 0.5wt%, the concentration of phthaloyl dichloride in an oil phase is 0.4wt%, and the reaction time is 5s.
The side of the porous membrane facing the anode was polyethylenimine-polyacrylic acid containing 5wt% tungstate.
The cathode is made of stainless steel, and the surface of the cathode has uniform roughness, and platinum catalyst is sprayed on the surface.
The hydrophilic-low surface energy hollow fiber membrane is a hollow fiber mixed matrix membrane prepared by dry and wet spinning of hydrophilic titanium oxide nano particles and polysulfone, and is generated by polymerization reaction of piperazine, trimesic chloride, chitosan quaternary ammonium salt and zwitterionic polyacrylamide. Specifically, a polyamine solution containing chitosan quaternary ammonium salt is coated on the inner surface of a hollow fiber mixed matrix membrane, the concentration of piperazine in the solution is 1wt%, the concentration of chitosan quaternary ammonium salt is 0.5wt%, then a trimesoyl chloride solution with the concentration of 1.2wt% is coated on the outer surface of the hollow fiber mixed matrix membrane, the mixture is reacted for 1min, the residual solution is removed, the mixture is dried in the air, and then the mixture is immersed into a zwitterionic polyacrylamide solution with the concentration of 1wt% for 50s, and the surface solution is removed and then dried, so that the positively charged hydrophilic-low surface energy hollow fiber membrane is formed.
The water inlet is connected with the sewage and wastewater storage device, the water producing port is connected with the purified water collection device, and the sewage outlet is connected with the flocculate collection device. The operating conditions of the device were a current density of 10A/m 2 The operating pressure was 0.05MPa.
The conductivity of the sewage to be treated is 17640 mu S/cm, the silicon compound content is 126mg/L, the hardness content is 272mg/L, and the COD content is 417mg/L. The purified water obtained after 30min of treatment by the apparatus of this example had a silicon compound content of 2.9mg/L, a hardness content of 6.5mg/L, a COD content of 15.3mg/L and a residual metal (iron/aluminum) ion content of 0.045mg/L. The purified water obtained after 360 minutes of treatment by the device of the embodiment had a silicon compound content of 3.2mg/L, a hardness content of 6.7mg/L, a COD content of 15.9mg/L and a residual metal (iron/aluminum) ion content of 0.045mg/L. The device of this embodiment still keeps steadily to the removal effect of pollutant such as silicon compound, hardness, COD in the dirty waste water after 360min operation, and the state of the pollutant in the dirty waste water of high-efficient removal can be kept to the device of this embodiment when long-time operation.
Example 4
In this embodiment, the device for treating sewage and wastewater by electroflocculation includes an electrode device disposed in a cylindrical housing, the electrode device includes a hollow cylindrical anode, a cathode, and a hollow fiber membrane module, the hollow cylindrical anode is sleeved outside the cathode, and a cavity is formed between the hollow cylindrical anode and the cathode, and a hydrophilic-low surface energy hollow fiber membrane module is vertically disposed in the formed cavity. The hollow columnar anode and the cathode are connected with a power supply outside the device. The electric flocculation sewage treatment device also comprises a water inlet, a water producing port and a sewage draining port, wherein the water inlet is positioned on the side wall of the lower end of the shell, is connected with the cavity at the bottom of the electrode device and is used for conveying sewage to be treated into the electrode device; the water producing port is positioned on the side wall of the upper end of the shell, is connected with the inner hole of the membrane bundle of the hollow fiber membrane component at the top of the electrode device and is used for outputting the produced water after being treated by the electrode device; the upper end of the shell is internally provided with a water outlet cavity, one end of the water outlet cavity is communicated with an inner hole of the membrane bundle of the hollow fiber membrane component, and the other end of the water outlet cavity is communicated with the water producing port. The hydrophilic-low surface energy hollow fiber membrane is positioned below the water producing port, and a certain distance is reserved between the bottom of the electrode device and the bottom of the shell. A drain outlet is arranged on the side wall of the lower end of the shell and is also connected with the cavity at the bottom of the electrode device for discharging flocculate generated in the electrode device. Valves are arranged on the water inlet, the water producing port and the sewage outlet.
The hollow columnar anode is aluminum, and the inner surface of the hollow columnar anode is modified by styrene in a hydrophobic manner. The hollow columnar anode is internally lined with a charged diaphragm, namely, one surface of a porous membrane (made of polyethersulfone and with the aperture of 100 nm) facing the cathode is a negatively charged polyamide membrane layer prepared by reacting p-phenylenediamine, isophthaloyl dichloride, sodium dodecyl benzene sulfonate and sodium hexadecyl benzene sulfonate, wherein in the reaction, the concentration of the sodium dodecyl sulfonate in a water phase is 0.5wt%, the concentration of the p-phenylenediamine is 1wt%, the concentration of the sodium dodecyl benzene sulfonate and the sodium hexadecyl benzene sulfonate in an oil phase is 0.8wt%, and the reaction time is 60s.
The side of the porous membrane facing the anode was polyethylenimine-polyacrylic acid containing 10wt% tungstate.
The cathode is made of stainless steel, and the surface of the cathode has uniform roughness, and rhodium catalyst is sprayed on the surface.
The hydrophilic-low surface energy hollow fiber membrane is a hollow fiber mixed matrix membrane prepared by dry and wet spinning of hydrophilic titanium oxide nano particles and polysulfone, and is generated by polymerization reaction of piperazine, trimesic chloride, chitosan quaternary ammonium salt and zwitterionic polyacrylamide. Specifically, a polyamine solution containing chitosan quaternary ammonium salt is coated on the inner surface of a hollow fiber mixed matrix membrane, the concentration of piperazine in the solution is 2wt%, the concentration of chitosan quaternary ammonium salt is 1wt%, then a trimesoyl chloride solution with the concentration of 1.5wt% is coated on the outer surface of the hollow fiber mixed matrix membrane, the mixture is reacted for 2min, the residual solution is removed, the mixture is dried in the air, and then the mixture is immersed into a zwitterionic polyacrylamide solution with the concentration of 1.5wt% for 150s, and the surface solution is removed and then dried, so that the positively charged hydrophilic-low surface energy hollow fiber membrane is formed.
The water inlet is connected with the sewage and wastewater storage device, the water producing port is connected with the purified water collection device, and the sewage outlet is connected with the flocculate collection device. The operating conditions of the device are currentDensity of 120A/m 2 The operating pressure was 0.3MPa.
The conductivity of the sewage to be treated is 17640 mu S/cm, the silicon compound content is 126mg/L, the hardness content is 272mg/L, and the COD content is 417mg/L. The purified water obtained after 30min of treatment by the apparatus of this example had a silicon compound content of 1.2mg/L, a hardness content of 3.7mg/L, a COD content of 9.6mg/L and a residual metal (iron/aluminum) ion content of 0.016mg/L. The purified water obtained after 360 minutes of treatment by the device of the embodiment had a silicon compound content of 1.3mg/L, a hardness content of 4.0mg/L, a COD content of 11.5mg/L and a residual metal (iron/aluminum) ion content of 0.017mg/L. The device of this embodiment still keeps steadily to the removal effect of pollutant such as silicon compound, hardness, COD in the dirty waste water after 360min operation, and the state of the pollutant in the dirty waste water of high-efficient removal can be kept to the device of this embodiment when long-time operation.
Example 5
In this embodiment, the device for treating sewage and wastewater by electroflocculation includes an electrode device disposed in a cylindrical housing, the electrode device includes a hollow cylindrical anode, a cathode, and a hollow fiber membrane module, the hollow cylindrical anode is sleeved outside the cathode, and a cavity is formed between the hollow cylindrical anode and the cathode, and a hydrophilic-low surface energy hollow fiber membrane module is vertically disposed in the formed cavity. The hollow columnar anode and the cathode are connected with a power supply outside the device. The electric flocculation sewage treatment device also comprises a water inlet, a water producing port and a sewage draining port, wherein the water inlet is positioned on the side wall of the lower end of the shell, is connected with the cavity at the bottom of the electrode device and is used for conveying sewage to be treated into the electrode device; the water producing port is positioned on the side wall of the upper end of the shell, is connected with the inner hole of the membrane bundle of the hollow fiber membrane component at the top of the electrode device and is used for outputting the produced water after being treated by the electrode device; the upper end of the shell is internally provided with a water outlet cavity, one end of the water outlet cavity is communicated with an inner hole of the membrane bundle of the hollow fiber membrane component, and the other end of the water outlet cavity is communicated with the water producing port. The hydrophilic-low surface energy hollow fiber membrane is positioned below the water producing port, and a certain distance is reserved between the bottom of the electrode device and the bottom of the shell. A drain outlet is arranged on the side wall of the lower end of the shell and is also connected with the cavity at the bottom of the electrode device for discharging flocculate generated in the electrode device. Valves are arranged on the water inlet, the water producing port and the sewage outlet.
The hollow columnar anode is iron, and the inner surface is modified by styrene in a hydrophobic way. The hollow columnar anode is internally lined with a charged diaphragm, namely, one surface of a porous membrane (made of polyimide and with the aperture of 100 nm) facing the cathode is a negatively charged polyamide membrane layer prepared by reacting p-phenylenediamine, isophthaloyl dichloride and sodium hexadecyl sulfonate, wherein in the reaction, the concentration of sodium hexadecyl sulfonate in a water phase is 0.5wt%, the concentration of p-phenylenediamine is 1wt%, the concentration of phthaloyl dichloride in an oil phase is 0.8wt%, and the reaction time is 50s.
The side of the porous membrane facing the anode was polyethylene glycol-polyacrylic acid containing 10wt% titanate.
The cathode is made of stainless steel, the surface of the cathode has uniform roughness, and nickel and palladium catalysts are sprayed on the surface of the cathode.
The hydrophilic-low surface energy hollow fiber membrane is a hollow fiber mixed matrix membrane prepared by dry-wet spinning of hydrophilic titanium oxide nano particles and polysulfone, and is generated by polymerization reaction of piperazine, adipoyl chloride, chitosan quaternary ammonium salt and zwitterionic polyacrylamide. Specifically, a polyamine solution containing chitosan quaternary ammonium salt is coated on the inner surface of a hollow fiber mixed matrix membrane, the concentration of piperazine in the solution is 2wt%, the concentration of chitosan quaternary ammonium salt is 1wt%, then adipoyl chloride solution with the concentration of 1.5wt% is coated on the outer surface of the hollow fiber mixed matrix membrane, the hollow fiber membrane is reacted for 2min, the residual solution is removed, and the hollow fiber membrane is dried and immersed into a zwitterionic polyacrylamide solution with the concentration of 1.5wt% for 150s, and the hollow fiber membrane with positively charged hydrophilic-low surface energy is obtained after the surface solution is removed and dried.
The water inlet is connected with the sewage and wastewater storage device, the water producing port is connected with the purified water collection device, and the sewage outlet is connected with the flocculate collection device. The operating conditions of the device were a current density of 40A/m 2 The operating pressure was 0.5MPa.
The conductivity of the sewage to be treated is 17640 mu S/cm, the silicon compound content is 126mg/L, the hardness content is 272mg/L, and the COD content is 417mg/L. The purified water obtained after 30 minutes of treatment by the apparatus of this example had a silicon compound content of 2.3mg/L, a hardness content of 5.3mg/L, a COD content of 12.6mg/L and a residual metal (iron/aluminum) ion content of 0.024mg/L. The purified water obtained after 360 minutes of treatment by the device of the embodiment had a silicon compound content of 2.5mg/L, a hardness content of 5.9mg/L, a COD content of 14.1mg/L and a residual metal (iron/aluminum) ion content of 0.024mg/L. The device of this embodiment still keeps steadily to the removal effect of pollutant such as silicon compound, hardness, COD in the dirty waste water after 360min operation, and the state of the pollutant in the dirty waste water of high-efficient removal can be kept to the device of this embodiment when long-time operation.
Example 6
In this embodiment, the device for treating sewage and wastewater by electroflocculation includes an electrode device disposed in a cylindrical housing, the electrode device includes a hollow cylindrical anode, a cathode, and a hollow fiber membrane module, the hollow cylindrical anode is sleeved outside the cathode, and a cavity is formed between the hollow cylindrical anode and the cathode, and a hydrophilic-low surface energy hollow fiber membrane module is vertically disposed in the formed cavity. The hollow columnar anode and the cathode are connected with a power supply outside the device. The electric flocculation sewage treatment device also comprises a water inlet, a water producing port and a sewage draining port, wherein the water inlet is positioned on the side wall of the lower end of the shell, is connected with the cavity at the bottom of the electrode device and is used for conveying sewage to be treated into the electrode device; the water producing port is positioned on the side wall of the upper end of the shell, is connected with the inner hole of the membrane bundle of the hollow fiber membrane component at the top of the electrode device and is used for outputting the produced water after being treated by the electrode device; the upper end of the shell is internally provided with a water outlet cavity, one end of the water outlet cavity is communicated with an inner hole of the membrane bundle of the hollow fiber membrane component, and the other end of the water outlet cavity is communicated with the water producing port. The hydrophilic-low surface energy hollow fiber membrane is positioned below the water producing port, and a certain distance is reserved between the bottom of the electrode device and the bottom of the shell. A drain outlet is arranged on the side wall of the lower end of the shell and is also connected with the cavity at the bottom of the electrode device for discharging flocculate generated in the electrode device. Valves are arranged on the water inlet, the water producing port and the sewage outlet.
The hollow columnar anode is aluminum, and the inner surface of the hollow columnar anode is modified by styrene in a hydrophobic manner. The hollow columnar anode is internally lined with a charged diaphragm, namely, one surface of a porous membrane (made of polypropylene and with the aperture of 100 nm) facing the cathode is a negatively charged polyamide membrane layer prepared by reacting p-phenylenediamine, isophthaloyl chloride and sodium hexadecyl benzene sulfonate, wherein in the reaction, the concentration of sodium hexadecyl benzene sulfonate in a water phase is 0.5wt%, the concentration of p-phenylenediamine is 1wt%, the concentration of phthaloyl chloride in an oil phase is 0.8wt%, and the reaction time is 40s.
The side of the porous membrane facing the anode was polyvinylpyrrolidone-polyacrylic acid containing 10wt% of titanate and tungstate.
The cathode is made of stainless steel, and the surface of the cathode has uniform roughness, and palladium catalyst is sprayed on the surface.
The hydrophilic-low surface energy hollow fiber membrane is a hollow fiber mixed matrix membrane prepared by dry-wet spinning of hydrophilic titanium oxide nano particles and polysulfone, and is generated by polymerization reaction of m-phenylenediamine, trimesic acid chloride, chitosan quaternary ammonium salt and zwitterionic polyacrylamide. Specifically, a polyamine solution containing chitosan quaternary ammonium salt is coated on the inner surface of a hollow fiber mixed matrix membrane, the concentration of m-phenylenediamine is 2wt%, the concentration of chitosan quaternary ammonium salt is 1wt%, then a trimesoyl chloride solution with the concentration of 1.5wt% is coated on the outer surface of the hollow fiber mixed matrix membrane, the mixture is reacted for 2min, the residual solution is removed, the mixture is dried in the air, and then the mixture is immersed into a zwitterionic polyacrylamide solution with the concentration of 1.5wt% for 200s, and the surface solution is removed and then dried, so that the positively charged hydrophilic-low surface energy hollow fiber membrane is formed.
The water inlet is connected with the sewage and wastewater storage device, the water producing port is connected with the purified water collection device, and the sewage outlet is connected with the flocculate collection device. The operating conditions of the device were a current density of 100A/m 2 The operating pressure was 0.8MPa.
The conductivity of the sewage to be treated is 17640 mu S/cm, the silicon compound content is 126mg/L, the hardness content is 272mg/L, and the COD content is 417mg/L. The purified water obtained after 30 minutes of treatment by the apparatus of this example had a silicon compound content of 1.9mg/L, a hardness content of 4.5mg/L, a COD content of 11.8mg/L and a residual metal (iron/aluminum) ion content of 0.019mg/L. The purified water obtained after 360 minutes of treatment by the device of the embodiment had a silicon compound content of 2.2mg/L, a hardness content of 4.8mg/L, a COD content of 13.0mg/L and a residual metal (iron/aluminum) ion content of 0.022mg/L. The device of this embodiment still keeps steadily to the removal effect of pollutant such as silicon compound, hardness, COD in the dirty waste water after 360min operation, and the state of the pollutant in the dirty waste water of high-efficient removal can be kept to the device of this embodiment when long-time operation.
Comparative example 1
In this comparative example, the construction of the electroflocculation apparatus was the same as in example 1, except that the apparatus of this comparative example was operated under conditions of a current density of 5A/m 2 The operating pressure was 0.2MPa.
The conductivity of the sewage to be treated is 17640 mu S/cm, the silicon compound content is 126mg/L, the hardness content is 272mg/L, and the COD content is 417mg/L. The purified water obtained after 30min treatment by the device of the comparative example had a silicon compound content of 28.6mg/L, a hardness content of 66.5mg/L, a COD content of 78.6mg/L and a residual metal (iron/aluminum) ion content of 0.056mg/L.
This comparative example demonstrates that the operation of the device under low current density conditions can affect the treatment of the device to waste water, and that the purified water has poor silicon-containing compounds, hardness and COD removal.
Comparative example 2
In this comparative example, the construction of the electroflocculation apparatus was the same as in example 1, except that the apparatus of this comparative example was operated under conditions of a current density of 100A/m 2 The operating pressure was 0.03MPa.
The conductivity of the sewage to be treated is 17640 mu S/cm, the silicon compound content is 126mg/L, the hardness content is 272mg/L, and the COD content is 417mg/L. The purified water obtained after 30min of treatment by the device of the comparative example contains 20.5mg/L of silicon compound, 26.3mg/L of hardness, 65.1mg/L of COD and 0.053mg/L of residual metal (iron/aluminum) ions.
This comparative example demonstrates that too low an operating pressure of the apparatus can affect the treatment of the apparatus to waste water, and that the purified water has poor silicon-containing compound, hardness and COD removal.
Comparative example 3
In this comparative example, the hollow columnar anode aluminum of this comparative example was not hydrophobically modified, and the remainder was the same as in example 1.
The conductivity of the sewage to be treated is 17640 mu S/cm, the silicon compound content is 126mg/L, the hardness content is 272mg/L, and the COD content is 417mg/L. The purified water obtained after 30min of treatment by the apparatus of this example had a silicon compound content of 2.7mg/L, a hardness content of 5.8mg/L, a COD content of 14.5mg/L and a residual metal (iron/aluminum) ion content of 0.043mg/L. The purified water obtained after 360min treatment by the device of the comparative example contains 21.2mg/L of silicon compound, 43.8mg/L of hardness, 52.4mg/L of COD and 0.061mg/L of residual metal (iron/aluminum) ions. The device of this comparative example was remarkably reduced in the removal effect of contaminants such as silicon compounds, hardness and COD in the turbidity of the sewage after 360 minutes of operation, indicating that the device of this comparative example could not ensure a stable state when operated for a long time.
The hollow columnar anode of the comparative example is not subjected to hydrophobic modification, and the anode is easily polluted by impurities in polluted wastewater in the running process of the device, so that a passivation layer is formed on the surface of the electrode, the current efficiency of the device is reduced, the treatment effect is reduced, and the running of the device is unstable.
Comparative example 4
In this comparative example, the hollow cylindrical anode lining separator of this comparative example was sprayed with polyethylene glycol-polyacrylic acid containing titanate only on the anode-facing side thereof, and the remainder was the same as in example 1.
The conductivity of the sewage to be treated is 17640 mu S/cm, the silicon compound content is 126mg/L, the hardness content is 272mg/L, and the COD content is 417mg/L. The purified water obtained after 30min of treatment by the device of the embodiment had a silicon compound content of 4.6mg/L, a hardness content of 8.9mg/L, a COD content of 18.3mg/L and a residual metal (iron/aluminum) ion content of 0.067mg/L. The purified water obtained after 360min treatment by the device of the comparative example contains 23.5mg/L of silicon compound, 38.1mg/L of hardness, 62.6mg/L of COD and 0.074mg/L of residual metal (iron/aluminum) ions. The device of this comparative example was remarkably reduced in the removal effect of contaminants such as silicon compounds, hardness and COD in the turbidity of the sewage after 360 minutes of operation, indicating that the device of this comparative example could not ensure a stable state when operated for a long time.
The hollow columnar anode lining diaphragm of the comparative example is not provided with a negatively charged polyamide membrane layer, and oxygen anions generated in the running process of the device are easy to form oxides with metal at the anode interface, so that the electrode is passivated, the current efficiency of the device is reduced, the treatment effect is reduced, and the running of the device is unstable.
Comparative example 5
In this comparative example, the hollow cylindrical anode-lined separator of this comparative example was provided with a negatively charged polyamide membrane layer prepared by introducing sodium dodecyl sulfate only to the cathode side, and the rest was the same as in example 1.
The conductivity of the sewage to be treated is 17640 mu S/cm, the silicon compound content is 126mg/L, the hardness content is 272mg/L, and the COD content is 417mg/L. The purified water obtained after 30min of treatment by the device of the embodiment had a silicon compound content of 6.8mg/L, a hardness content of 12.8mg/L, a COD content of 20.5mg/L and a residual metal (iron/aluminum) ion content of 0.050mg/L. The purified water obtained after 360min of treatment by the device of the comparative example had a silicon compound content of 27.3mg/L, a hardness content of 39.7mg/L, a COD content of 67.8mg/L and a residual metal (iron/aluminum) ion content of 0.053mg/L. The device of this comparative example was remarkably reduced in the removal effect of contaminants such as silicon compounds, hardness and COD in the turbidity of the sewage after 360 minutes of operation, indicating that the device of this comparative example could not ensure a stable state when operated for a long time.
The hollow cylindrical anode lining diaphragm of this comparative example is not provided with a catalyst-containing copolymer layer, and compared with example 1, the removal effect of silicon-containing compound, hardness and COD in the turbidity of sewage is reduced, and the operation of the device is unstable, and the anode lining diaphragm catalyst-containing copolymer layer of example 1 can activate the electrode electrolytic reaction, promote the generation of active oxidation substances, and improve the removal effect of pollutants.
Comparative example 6
In this comparative example, the cathode of this comparative example was a conventional stainless steel, the surface of which was not treated, and the rest was the same as in example 1.
The conductivity of the sewage to be treated is 17640 mu S/cm, the silicon compound content is 126mg/L, the hardness content is 272mg/L, and the COD content is 417mg/L. The purified water obtained after 30 minutes of treatment by the apparatus of this example had a silicon compound content of 7.5mg/L, a hardness content of 19.3mg/L, a COD content of 25.7mg/L and a residual metal (iron/aluminum) ion content of 0.048mg/L. The purified water obtained after 360min treatment by the device of the comparative example contains 30.6mg/L of silicon compound, 54.4mg/L of hardness, 72.1mg/L of COD and 0.048mg/L of residual metal (iron/aluminum) ions. The device of this comparative example was remarkably reduced in the removal effect of contaminants such as silicon compounds, hardness and COD in the turbidity of the sewage after 360 minutes of operation, indicating that the device of this comparative example could not ensure a stable state when operated for a long time.
Compared with the example 1, the rough structure of the cathode surface and the spraying treatment of the catalyst have the advantages that the removing effect of silicon compounds, hardness and COD in the turbidity of sewage is reduced, the device is unstable in operation, the cathode with uniform roughness on the surface of the example 1 and sprayed with the catalyst can accelerate bubble generation, optimize the particle size and distribution of bubbles, strengthen the air floatation effect and promote the absorption and removal of pollutants.
Comparative example 7
In this comparative example, the hollow fiber membrane of this comparative example was provided with only a charged positive film layer, i.e., p-phenylenediamine, isophthaloyl chloride and chitosan quaternary ammonium salt were used only on the outer surface of the hollow fiber mixed matrix membrane to produce a charged positive film layer by polymerization, and the remainder was the same as in example 1.
The conductivity of the sewage to be treated is 17640 mu S/cm, the silicon compound content is 126mg/L, the hardness content is 272mg/L, and the COD content is 417mg/L. The purified water obtained after 30 minutes of treatment by the apparatus of this example had a silicon compound content of 2.9mg/L, a hardness content of 6.1mg/L, a COD content of 17.0mg/L and a residual metal (iron/aluminum) ion content of 0.042mg/L. The purified water obtained after 360min of treatment by the device of the comparative example had a silicon compound content of 16.9mg/L, a hardness content of 34.9mg/L, a COD content of 57.2mg/L and a residual metal (iron/aluminum) ion content of 0.315mg/L. The device of this comparative example was remarkably reduced in the removal effect of contaminants such as silicon compounds, hardness and COD in the turbidity of the sewage after 360 minutes of operation, indicating that the device of this comparative example could not ensure a stable state when operated for a long time.
By using the hollow fiber membrane of the comparative example, pollutants in the polluted wastewater are easily adsorbed by the hollow fiber membrane in the running process of the device, so that the membrane permeation separation performance is reduced, the pollutant removal effect of the device is reduced, and the running of the device is unstable.
Comparative example 8
In this comparative example, the hollow fiber membrane surface of this comparative example was subjected to only hydrophilic-low surface energy modification, that is, isophthaloyl dichloride and zwitterionic polyacrylamide were used only on the outer surface of the hollow fiber mixed matrix membrane to produce a hydrophilic-low surface energy hollow fiber membrane by interfacial reaction, and the remainder was the same as in example 1.
The conductivity of the sewage to be treated is 17640 mu S/cm, the silicon compound content is 126mg/L, the hardness content is 272mg/L, and the COD content is 417mg/L. The purified water obtained after 30min treatment by the device of the comparative example had a silicon compound content of 2.5mg/L, a hardness content of 22.1mg/L, a COD content of 13.7mg/L and a residual metal (iron/aluminum) ion content of 4.759mg/L.
The hollow fiber membrane of the comparative example can affect the treatment of the device on sewage and wastewater, and residual metal (iron/aluminum) ions in the purified water can not be effectively removed.
It should be understood that the above description of the specific embodiments of the present invention is only for illustrating the technical features of the present invention, and is for enabling those skilled in the art to understand the present invention and implement it accordingly, but the present invention is not limited to the above-described specific embodiments. All changes or modifications made within the scope of the technical proposal of the invention are covered by the protection scope of the invention.

Claims (8)

1. The device for treating the sewage and wastewater by the electric flocculation is characterized by comprising a shell (1), wherein an electrode device (2) is arranged in the shell (1), the electrode device (2) comprises a hollow columnar anode (21), a cathode (22) and a hollow fiber membrane component (23), the hollow columnar anode (21) is sleeved outside the cathode (22), a cavity is formed between the hollow columnar anode (21) and the cathode (22), and the hollow fiber membrane component (23) is arranged in the cavity;
the inner surface of the hollow columnar anode (21) is subjected to hydrophobic modification;
the surface of the cathode (22) is provided with a metal catalyst coating;
the hollow fiber membrane module (23) is: preparing a hollow fiber mixed matrix membrane by taking hydrophilic nano particles and polysulfone or polyether sulfone as raw materials, and generating a positively charged membrane layer on the surface of the hollow fiber mixed matrix membrane by adopting polyamine, polybasic acyl chloride, chitosan quaternary ammonium salt and zwitterionic polyacrylamide through interfacial polymerization reaction;
the hollow columnar anode (21) is internally lined with a charging diaphragm (24);
the preparation method of the charged membrane (24) comprises the following steps: adopting polyamine, polybasic acyl chloride and a fatty acid anionic surfactant to react on the surface of the porous membrane facing the cathode to generate a negatively charged membrane layer; the fatty acid anionic surfactant is at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium hexadecyl sulfonate and sodium hexadecyl benzene sulfonate;
During the reaction, the mass concentration of the polybasic acyl chloride in the oil phase is 0.1-0.8%, the mass concentration of the polybasic amine in the water phase is 0.15-1%, and the mass concentration of the fatty acid anionic surfactant is 0.05-0.5%;
spraying a polyacrylic acid copolymer containing at least one of titanate, tungstate and vanadate on the surface of the porous membrane facing the anode;
the polyacrylic acid copolymer is one of polyethylene glycol-polyacrylic acid, polyvinylpyrrolidone-polyacrylic acid and polyethyleneimine-polyacrylic acid.
2. An apparatus for treating waste water and sewage by electric flocculation according to claim 1, characterized in that said hollow columnar anode (21) is iron or aluminum whose inner surface is hydrophobically modified.
3. An apparatus for treating waste water and sewage by electric flocculation according to claim 1 or 2, wherein the method for hydrophobically modifying the inner surface of the hollow columnar anode (21) comprises: and (3) adopting styrene or polybutadiene to carry out grafting reaction on the inner surface of the hollow columnar anode (21).
4. An apparatus for treating sewage and wastewater by electric flocculation according to claim 1 and wherein said hydrophilic nanoparticles are SiO 2 Or a metal oxide; the polyamine is one or more of piperazine, m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, diaminotoluene and 2, 5-dimethylpiperazine; the polybasic acyl chloride is one or more of trimesoyl chloride, phthaloyl chloride, isophthaloyl chloride, 3', 5' -biphenyl tetra-formyl chloride, terephthaloyl chloride and adipoyl chloride;
In the interfacial polymerization reaction, the mass concentration of the polybasic acyl chloride in the oil phase is 0.2-1.5%, the mass concentration of the polybasic amine in the water phase is 0.5-2%, and the mass concentration of the chitosan quaternary ammonium salt is 0.1-1%.
5. An apparatus for treating waste water by electroflocculation according to claim 1, characterized in that said cathode (22) is stainless steel provided with a metallic catalyst coating on the surface.
6. An electroflocculation treatment apparatus for waste water according to claim 1 or 5, characterized in that the surface of the cathode (22) has a uniform roughness; the metal catalyst is one or more of nickel, cobalt, platinum, rhodium and palladium.
7. An electroflocculation sewage treatment device according to claim 1, further comprising a water inlet (3), a water outlet (4) and a drain outlet (5), wherein the water inlet (3) and the drain outlet (5) are connected with the cavity at the bottom of the electrode device (2), and the water outlet (4) is connected with the inner hole of the membrane bundle of the hollow fiber membrane module (23) at the top of the electrode device (2).
8. The electroflocculation of any one of claims 1-7The use of a device for treating waste water, characterized in that the operating conditions of the device are a current density of 10-150A/m 2 The operating pressure is 0.05-1MPa.
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