CN113003877B - Treatment device and method for refractory organic wastewater - Google Patents

Treatment device and method for refractory organic wastewater Download PDF

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CN113003877B
CN113003877B CN202110260569.1A CN202110260569A CN113003877B CN 113003877 B CN113003877 B CN 113003877B CN 202110260569 A CN202110260569 A CN 202110260569A CN 113003877 B CN113003877 B CN 113003877B
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membrane
water outlet
water
water inlet
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CN113003877A (en
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夏伊静
冯华军
马香娟
叶玲
吕淼
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Zhejiang Gongshang University
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Abstract

The invention relates to the technical field of wastewater treatment, in particular to an electrocatalysis coupling aerobic self-generation dynamic membrane reactor for treating refractory organic wastewater and a treatment method of the refractory organic wastewater. The invention firstly makes aerobic sludge deposited on the outer side of the electrocatalytic membrane component by utilizing water pressure to form an aerobic sludge self-generating dynamic membrane, then makes wastewater enter the electrified electrocatalytic membrane component, biodegradable organic pollutants are degraded under the action of the aerobic sludge, and the formed membrane system plays a role of filtering, and is electrified to the membrane component, thereby not only prolonging the effective filtering period of the membrane, but also further degrading and mineralizing the biological refractory organic pollutants, and sterilizing and disinfecting the filtrate, and making the quality of the treated wastewater better.

Description

Treatment device and method for refractory organic wastewater
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to an electro-catalytic coupling aerobic self-generated dynamic membrane reactor for treating refractory organic wastewater and a treatment method of the refractory organic wastewater.
Background
The dynamic membrane biological method combines a biological treatment technology and a dynamic membrane filtration technology, uses a macroporous cheap support material as a base material to replace a microfiltration ultrafiltration membrane, and utilizes pollutants intercepted in the initial stage and microorganisms adhered in the later stage in the filtration process to form a biological dynamic membrane with the filtration effect of the microfiltration membrane on the membrane base material, thereby achieving the purpose of improving the effluent quality. Compared with the traditional membrane biological method, the dynamic membrane reactor not only greatly reduces the manufacturing cost of the membrane component, but also has the advantages of excellent effluent quality, large flux, strong pollution resistance, low energy consumption and the like, and has wide application prospect. However, the current dynamic membrane biological method has the problems that the membrane is easy to block and toxic and nondegradable pollutants are difficult to remove.
The electrocatalytic oxidation method is a novel sewage treatment technology and can effectively remove organic pollutants which are difficult to degrade in sewage. The technology is a process of degrading organic pollutants and converting the organic pollutants into harmless substances by hydroxyl radicals with extremely strong oxidizing capacity generated by an anode material with electrocatalytic activity under the condition of electrifying. In recent years, in the treatment of organic wastewater containing difficult biodegradation, an electrochemical oxidation method has been a research hotspot because of the advantages of no secondary pollution, simple operation, strong oxidation capability, mild reaction conditions, small occupied area and the like. However, the prior electrocatalytic oxidation method has the problems of large energy consumption, short electrode life and the like.
Chinese patent application CN 109354161A provides an electrochemical coupling dynamic membrane module and a membrane reactor for sewage treatment, the reactor uses an activated carbon fiber felt as an anode, a titanium mesh as a cathode, and a dynamic membrane substrate is arranged outside the activated carbon fiber felt. The reactor is simple in structure, can be used for carrying out filtering separation and sterilization and disinfection integrated treatment on sewage, but cannot effectively remove the trace pollutants which are difficult to degrade in the wastewater. In addition, as macromolecular colloidal substances such as Extracellular Polymeric Substances (EPS) causing membrane pollution are generally electronegative, the dynamic membrane substrate arranged outside the anode activated carbon fiber felt is not beneficial to relieving the membrane pollution compared with the dynamic membrane substrate serving as a cathode in the invention.
Chinese patent application CN104176797A discloses an electrochemical treatment device and method for refractory organic wastewater, and designs a 'zero-polar-distance' SPE electrooxidation sewage treatment electrolytic cell similar to a solid polymer electrolyte fuel cell technology. The device separates an anode chamber from a cathode chamber by using an ion exchange membrane, and compresses a (titanium-based dimensionally stable) anode, the ion exchange membrane and a (nickel) cathode by using an end plate to form a 'zero-polar-distance' SPE (solid phase extraction) electrooxidation sewage treatment electrolytic cell. When the device is in electrolytic operation, the waste water is subjected to electrooxidation at the anode, so that organic matters and ammonia nitrogen in the water are mineralized and degraded; tap water (or waste water) is introduced into the cathode chamber, and the cathode electrolysis hydrogen evolution is recovered.
Disclosure of Invention
The invention aims to couple the dynamic membrane biological method and the electrocatalytic oxidation method, firstly develops an electrochemical membrane component suitable for the combination of the dynamic membrane biological method and the electrocatalytic oxidation method for anhydrous treatment, and then further develops an integrated electrocatalytic coupling aerobic self-generating dynamic membrane wastewater treatment device comprising the electrocatalytic membrane component. The coupling system not only effectively slows down the membrane pollution of the dynamic membrane, but also can synchronously realize the purposes of mud-water separation, organic pollutant degradation, trace amount of biodegradation pollutant mineralization, effluent sterilization and disinfection and the like, and has the advantages of good effluent quality, small occupied area of the reactor, short flow, low energy consumption and the like.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
an electrocatalytic membrane component comprises a membrane frame (15), an outer side mesh pipe (12), a porous coating electrode pipe (13) and an inner side mesh pipe (14);
the lengths of the outer side mesh pipe (12), the porous coating electrode pipe (13) and the inner side mesh pipe (14) are equal, the porous coating electrode pipe (13) is arranged inside the outer side mesh pipe (12), the inner side mesh pipe (14) is arranged inside the porous coating electrode (13), two ends of the outer side mesh pipe (12), the porous coating electrode pipe (13) and the inner side mesh pipe (14) are sealed by a membrane frame (15) to form a cavity I (16), a cavity II (17) and a cavity III (18), wherein a water outlet (19) is formed at one end of the cavity III (18) which is in contact with the membrane frame (15);
the membrane frame (15) is made of an insulating inert material, preferably organic glass or polyvinyl chloride (PVC) and the like.
The invention does not specially limit the material and length of the water outlet (19), and only needs to meet the sealing performance required by the device.
Furthermore, in the electrocatalytic membrane component, the distance between the porous coating electrode tube (13) and the outer side mesh tube (12) is 10-40mm, and the distance between the porous coating electrode tube (13) and the inner side mesh tube (14) is 10-40mm.
Further, the porous coating electrode tube (13) is tubular Ti/TiO 2 -NTs/SnO 2 -an Sb electrode.
Further, the tubular Ti/TiO 2 -NTs/SnO 2 the-Sb electrode comprises a Ti substrate and TiO 2 -NTs intermediate layer and SnO 2 -an Sb outer layer, the Ti matrix being a tubular porous titanium matrix having a porosity of 20% to 50%; tiO 2 2 The NTs intermediate layer is a layer of vertically ordered TiO obtained on the Ti substrate 2 A nanotube; snO 2 The outer layer of Sb is a metal oxide coating with a nanostructure.
Further, the tubular Ti/TiO 2 -NTs/SnO 2 The preparation method of the-Sb electrode is as follows:
(1) Pretreatment of a porous Ti substrate: cutting a titanium substrate according to the size requirement, and mechanically grinding and polishing by using abrasive paper, removing oil from NaOH solution and etching by using oxalic acid solution to obtain a pitted porous Ti substrate;
(2) Preparation of Ti/TiO by electrochemical anode oxidation method 2 -NTs: using the Ti substrate in the step (1) as a working electrode, stainless steel as a counter electrode, a voltage of 20 to 40V, 0.05 to 1.0wt% of NaF as an electrolyte, 1.4 to 2.0wt% of a supporting electrolyte as a solute, adding 10 to 50wt% of an alcohol additive, and a solvent of ultrapure water;
(3) Preparation of SnO by thermal decomposition method 2 -an outer layer of Sb: uniformly coating the Ti/TiO treated in the step (2) with the tin-antimony oxide sol solution 2 Drying the NTs surface, carrying out thermal decomposition treatment at 500-550 ℃ for 10-15 minutes, repeating the steps for 8-15 times, wherein the time of the last thermal decomposition is 60-80 minutes, and naturally cooling to room temperature. The tin-antimony oxide sol solution is prepared from the following components: 5 to 10g of SbCl 3 ，90～110g SnCl 4 ·5H 2 O, 240-260 mL of glycol solution and 180-210 g of citric acid.
Further, the outer side mesh pipe (12) and the inner side mesh pipe (14) are respectively and independently selected from stainless steel mesh pipes, titanium mesh pipes or nickel mesh pipes, and the mesh aperture of the mesh pipes is 100-350 meshes.
The mesh tube can be replaced by a metal mesh tube with high conductivity, strong corrosion resistance and better mechanical strength known by the technical personnel, wherein the outer mesh tube (12) not only serves as a cathode of an electrocatalysis system, but also serves as a support material of an aerobic self-generated dynamic membrane.
When the electrocatalytic membrane module is used, the porous coating electrode tube (13) is connected with the positive electrode of the power supply (4), and the outer side mesh tube (12) and the inner side mesh tube (14) are simultaneously connected with the negative electrode of the power supply (4). The outer side net pipe (12) is also used as a supporting material of aerobic sludge, so that the aerobic sludge can form an aerobic self-generating dynamic membrane on the outer side net pipe (12) of the electro-catalytic membrane component.
A treatment device for refractory organic wastewater comprises a water inlet system, an aerobic sludge reaction tank (10), a power supply (4), an electro-catalytic membrane component, an aeration system and a water outlet system.
The electrocatalytic membrane component is arranged in the aerobic sludge reaction tank (10), the anode of the power supply (4) is connected with the porous coating electrode pipe (13), and the cathode of the power supply (4) is simultaneously connected with the outer side net pipe (12) and the inner side net pipe (14);
the water outlet system comprises a water outlet pipe (5), a water outlet pump (22) and a water outlet groove (6), two ends of the water outlet pipe (5) are respectively connected with the water outlet (19) and the water outlet groove (6), the water outlet pump (22) is arranged between the water outlet (19) and the water outlet groove (6), and the water outlet pipe (5) is in sealing connection with the water outlet (19);
the water inlet system comprises a water inlet tank (1), a water inlet pump (21) and a water inlet pipe (3), one end of the water inlet pipe (3) is connected to the water inlet tank (1), the other end of the water inlet pipe is communicated with the aerobic sludge reaction tank (10), and the water inlet pump (21) is arranged between the water inlet tank (1) and the aerobic sludge reaction tank (10);
the aeration system comprises an air blower (8), an aeration pipe (11) and an aeration head (9), one end of the aeration pipe (11) is introduced into the aerobic sludge reaction tank (10), the aeration pipe (11) introduced into the aerobic sludge reaction tank (10) is provided with the aeration head (9), the aeration head (9) is arranged below the electro-catalytic membrane component, and the other end of the aeration pipe (11) is connected with the air blower (8).
A method for treating refractory organic wastewater using the device, comprising the steps of:
step 1) self-generated dynamic film generation stage: adding aerobic sludge into an aerobic sludge reaction tank (10), adding clear water through a water inlet system to enable the water level to be over the whole electrocatalytic membrane component, simultaneously pumping water outwards through a water outlet system, depositing sludge particles on an outer side net pipe (12) by utilizing the water flow pressure to form an autogenous dynamic membrane, and detecting the turbidity of outlet water;
step 2) wastewater treatment stage: wastewater is added into an aerobic sludge reaction tank (10) through a water inlet system, a power supply (4) is switched on, and the wastewater is discharged through a water outlet system after passing through an electro-catalytic membrane assembly;
further, in step 1), when the effluent turbidity is less than 5NTU, the step 1) is completed.
Further, in the step 2), the hydraulic retention time is 2-6h, and the flux of the self-generated dynamic membrane is 20-200L/(m) 2. h)。
Further, in the step 2), the voltage intensity of the power supply (4) is less than or equal to 4V/cm.
Further, the method further comprises, after step 2), the step of
Step 3): and (3) a reactor dynamic membrane cleaning stage: when the transmembrane pressure (TMP) of the inner side and the outer side of the self-generated dynamic membrane is more than 40KPa, stopping working and cleaning the membrane module.
Furthermore, the cleaning adopts an air back flushing mode, the back flushing pressure is 8-12 kPa, and the back flushing air quantity is 15-30L/(m) 2 S); the back flushing time is 2-5 min; when the flux recovery rate is lower than 90%, taking out and then adopting NaClO chemical cleaning, wherein the concentration of NaClO is 500-3000 mg/L, and the weight percentage of citric acid is 0.4-2.0%.
The invention has the advantages that:
the principle of the wastewater treatment of the invention is that the wastewater enters an aerobic sludge reaction tank (10) through a water inlet system, and biodegradable organic pollutants are degraded and removed under the action of aerobic sludge; under the action of water pressure, separating the mud-water mixture obtained by aerobic treatment by using an autogenous dynamic membrane on a cathode net, retaining aerobic sludge in a reaction zone, and allowing filtrate to enter the interior of a membrane body through the aerobic autogenous dynamic membrane; the wastewater entering the membrane body is degraded, mineralized, sterilized and disinfected by strong oxidizing substances such as hydroxyl radicals, hydrogen peroxide and the like generated in the electrocatalysis process, and then is discharged from the water outlet pipe (5), and the current can further relieve the pollution of the self-generated dynamic membrane and prolong the working time.
The invention operates in a continuous flow mode, not only removes and filters particles, colloid and macromolecular pollutants, but also realizes the removal, sterilization and disinfection of nonbiodegradable pollutants due to strong oxidizing substances such as hydroxyl free radicals, hydrogen peroxide and the like generated in situ in the electrocatalysis process, thereby achieving the high-efficiency coupling of dynamic membrane separation degradation and electrocatalysis oxidation technology; the defect that the microfiltration/ultrafiltration membrane is difficult to remove low-molecular-weight refractory organic pollutants is effectively overcome, no chemical additive is added, and no secondary pollution is generated; the cathode and the anode of the reactor are of cylindrical structures, so that the specific surface area of the electrode is greatly improved, and the active sites on the surface of the electrode are increased; the aeration system reduces the deposition of pollutants on the surface of the membrane by using the principles of water shearing force, air stirring and the like, effectively relieves membrane pollution and reduces the cleaning frequency; the applied voltage is lower, and the water treatment cost is reduced; the applied lower electric field intensity has no negative influence on the activity of microorganisms, and can prolong the service life of the self-generated dynamic membrane and further relieve membrane pollution.
The anode is arranged between the two cathodes, and the cathode at the outermost layer is used as the base material of the self-generated dynamic membrane, so that the membrane pollution period of the self-generated dynamic membrane is prolonged, the cleaning frequency of the membrane catalytic assembly is reduced, and the overall production cost is reduced.
Drawings
FIG. 1: the cross section of the electrocatalytic membrane component is a schematic structural diagram, and an arrow represents the water flow direction.
FIG. 2 is a schematic diagram: the structure of the reaction device is shown schematically;
reference numerals:
1. a water inlet tank; 21. a water inlet pump; 3. a water inlet pipe; 4. a power source; 5. a water outlet pipe; 22. discharging the water pump; 6. a water outlet groove; 7. an electrocatalytic membrane module; 8. a blower; 9. an aeration head; 10. an aerobic sludge reaction tank; 11. a breather pipe;
12. outer side net pipe; 13. a porous coated electrode tube; 14. inner side net pipe; 15. a film frame; 16. a cavity I;17. a cavity II;18. a cavity III;19. water outlet
Detailed Description
Example 1
An electrocatalytic membrane component 7 comprises a membrane frame 15, an outer side mesh tube 12, a porous coating electrode tube 13 and an inner side mesh tube 14;
the outer side mesh pipe 12 is a stainless steel mesh pipe with the aperture of 250 meshes, the inner diameter of 60mm and the length of 100 mm;
the inner side mesh pipe 14 is a stainless steel mesh pipe with the aperture of 250 meshes, the outer diameter of 20mm and the length of 100 mm;
the lengths of the outer mesh tube 12, the porous coating electrode tube 13 and the inner mesh tube 14 are equal, the outer mesh tube 12, the porous coating electrode tube 13 and the inner mesh tube 14 are nested in a concentric circle mode, the porous coating electrode tube 13 is arranged inside the outer mesh tube 12, the inner mesh tube 14 is arranged inside the porous coating electrode tube 13, the distance between the porous coating electrode tube 13 and the outer mesh tube 12 is 10mm, and the distance between the porous coating electrode tube 13 and the inner mesh tube 14 is 10mm.
The two ends of the outer side mesh tube 12, the porous coating electrode tube 13 and the inner side mesh tube 14 are sealed by a membrane frame 15 to form a cavity I16, a cavity II17 and a cavity III18, wherein a water outlet 19 is arranged at one end of the cavity III18, which is in contact with the membrane frame 15;
wherein the porous coating electrode tube 13 is tubular Ti/TiO 2 -NTs/SnO 2 -an Sb electrode.
The tubular Ti/TiO 2 -NTs/SnO 2 In the Sb electrode, a Ti matrix is a tubular porous titanium matrix with the porosity of 20-50 percent; tiO 2 2 The NTs intermediate layer is a layer of vertically ordered TiO obtained on the Ti substrate 2 A nanotube; snO 2 The outer layer of Sb is a metal oxide coating with a nanostructure.
The tubular Ti/TiO 2 -NTs/SnO 2 The preparation method of the-Sb electrode is as follows:
(1) Pretreatment of a porous Ti substrate: sequentially polishing a pure titanium net with the thickness of 0.3mm and the porosity of 30% by using 120-mesh, 600-mesh and 1200-mesh abrasive paper until a titanium substrate presents silvery white metallic luster, and washing by using deionized water; placing the polished and cleaned titanium sheet into a NaOH solution with the mass fraction of 40% to soak for 30min, and washing with deionized water; then etching for 3h in oxalic acid solution (15 wt%) at 80 ℃, washing with a large amount of distilled water to remove residual oxalic acid and titanium oxalate on the surface of the titanium substrate, and obtaining a pretreated titanium substrate;
(2) Preparation of Ti/TiO by electrochemical anode oxidation 2 -NTs: the Ti substrate in the step (1) is made into a cylinder shape to be used as a working electrodeStainless steel mesh tube as counter electrode, voltage 20V, electrolyte 0.08wt% NaF,1.6wt% supporting electrolyte Na 2 SO 4 Adding 30wt% of alcohol additive as solute, and the solvent is ultrapure water;
(3) Preparation of SnO by thermal decomposition method 2 -an outer layer of Sb: uniformly coating the Ti/TiO treated in the step (2) with the tin-antimony oxide sol solution 2 -NTs surface, drying, thermal decomposition at 550 deg.C for 15 min, repeating for 10 times, the final thermal decomposition time is 60 min, and naturally cooling to room temperature. The tin-antimony oxide sol solution is prepared from the following components: 7.53SbCl 3 ，104.16g SnCl 4 ·5H 2 O,251mL of ethylene glycol solution, 192.14g of citric acid;
example 2
A treatment device for refractory organic wastewater comprises a water inlet system, an aerobic sludge reaction tank 10, a power supply 4, an electro-catalytic membrane component 7 of embodiment 1, an aeration system and a water outlet system.
The electrocatalysis membrane component 7 is arranged in the aerobic sludge reaction tank 10, the anode of the power supply 4 is connected with the porous coating electrode tube 13, and the cathode of the power supply 4 is simultaneously connected with the outer side network tube 12 and the inner side network tube 14;
the water outlet system comprises a water outlet pipe 5, a water outlet pump 22 and a water outlet groove 6, two ends of the water outlet pipe 5 are respectively connected with the water outlet 19 and the water outlet groove 6, the water outlet pump 22 is arranged between the water outlet 19 and the water outlet groove, and the water outlet pipe 5 is connected with the water outlet 19 in a sealing manner;
the water inlet system comprises a water inlet tank 1, a water inlet pump 21 and a water inlet pipe 3, one end of the water inlet pipe 3 is connected to the water inlet tank 1, the other end of the water inlet pipe is communicated with the aerobic sludge reaction tank 10, and the water inlet pump 21 is arranged between the water inlet tank 1 and the aerobic sludge reaction tank 10;
the aeration system comprises an air blower 8, a vent pipe 11 and an aeration head 9, wherein one end of the vent pipe 11 is communicated with an aerobic sludge reaction tank 10, the vent pipe 11 communicated with the aerobic sludge reaction tank 10 is provided with the aeration head 9, meanwhile, the aeration head 9 is arranged below the electro-catalytic membrane component 7, and the other end of the vent pipe 11 is connected with the air blower 8.
The specific operation mode of the treatment device for the refractory organic wastewater is
Step 1) self-generated dynamic film generation stage: adding aerobic sludge into an aerobic sludge reaction tank 10, adding clear water through a water inlet system to enable the water level to be over the whole electrocatalytic membrane component 7, simultaneously pumping water outwards by using a water outlet system, controlling the concentration of the aerobic sludge in the aerobic sludge reaction tank 10 to be 10g/L, depositing sludge particles on an outer side net pipe 12 by utilizing water flow pressure to form an autogenous dynamic membrane, and finishing the step 1) when the effluent turbidity is detected to be less than 5 NTU;
step 2) wastewater treatment stage: wastewater is added into an aerobic sludge reaction tank 10 through a water inlet system, a power supply 4 is switched on, and the wastewater is discharged through a water outlet system after passing through an electro-catalytic membrane component 7; the hydraulic retention time is 4h, and the flux of the self-generated dynamic membrane is 30L/(m) 2. h) The voltage intensity of the power supply 4 is 2V/cm.
The electro-catalytic coupling self-generating dynamic membrane reactor of the membrane component is adopted to treat the wastewater,
experimental group parameters were set as: the simulated wastewater contains 471mg/L (about 500mg/L COD) of sucrose and NH 4 Cl 25mg/L、KH 2 PO 4 5mg/L, nitrobenzene 200. Mu.g/L, siO 2 The particle size is 2 μm, the concentration of sludge is controlled at about 10g/L, the voltage intensity is 2V/cm, and the membrane flux is 30L/(m) 2 H), hydraulic retention time 4h. In the form of tubular Ti/TiO 2 -NTs/SnO 2 the-Sb porous coating is an anode, and the inner stainless steel mesh tube and the outer stainless steel mesh tube are cathodes.
Blank control group: the other conditions were the same except that no voltage was applied.
The invention utilizes sucrose and nitrobenzene to simulate organic pollutants and uses SiO 2 Large particle inorganic contaminants were simulated to evaluate the ability of the device of the present invention to remove organic contaminants and prevent clogging of the nascent dynamic membrane.
After the step 1) is finished, the step 2) is continuously operated, when the transmembrane pressure (TMP) of the inner side and the outer side of the self-generated dynamic membrane is more than 40Kpa, the operation is stopped, the self-generated dynamic membrane is cleaned in an air backwashing mode, the backwashing pressure is 8-12 kPa, and the backwashing air quantity is 15-30L/(m & lt/m & gt) 2 S); the back washing time is 2-5 min; when the flux recovery rate is less than 90%And after the reactor is taken out, naClO chemical cleaning is adopted, the concentration of NaClO is 500-3000 mg/L, the citric acid is 0.4-2.0 wt%, the reactor is dried after cleaning is finished, the steps 1), 2) and the cleaning steps are continuously repeated, and the operation is carried out for 20 days, so that the results show that the removal rate of COD (chemical oxygen demand) of the two reactors is higher than 80%, but the removal rate of the nitrobenzene in the reactor with the applied voltage can be stably maintained above 88%, and the removal rate of the nitrobenzene in the blank group can only reach about 10%. In addition, when the transmembrane pressure difference reaches 40kPa, the operation end point is regarded as the operation end point, the dynamic membrane pollution period of the applied voltage is 45h, and the dynamic membrane pollution period of the blank group is 22h, so that the applied electric field can effectively relieve membrane pollution. It can be seen that the sewage treatment device provided by the invention has stronger degradation capability on organic pollutants, and from the aspect of a dynamic membrane pollution period, the sewage treatment device provided by the invention has stronger capability of resisting inorganic pollutant blockage.
Finally, it should be noted that the above-mentioned contents are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, and that the simple modifications or equivalent substitutions of the technical solutions of the present invention by those of ordinary skill in the art can be made without departing from the spirit and scope of the technical solutions of the present invention.

Claims (3)

1. A method for treating refractory organic wastewater by using a treatment device of the refractory organic wastewater, wherein the treatment device comprises a water inlet system, an aerobic sludge reaction tank (10), a power supply (4), an electro-catalytic membrane component, an aeration system and a water outlet system;
the electrocatalysis membrane component is arranged in the aerobic sludge reaction tank (10), the anode of the power supply (4) is connected with the porous coating electrode tube (13), and the cathode of the power supply (4) is simultaneously connected with the outer side mesh tube (12) and the inner side mesh tube (14);
the water outlet system comprises a water outlet pipe (5), a water outlet pump (22) and a water outlet groove (6), two ends of the water outlet pipe (5) are respectively connected with the water outlet (19) and the water outlet groove (6), the water outlet pump (22) is arranged between the water outlet (19) and the water outlet groove (6), and the water outlet pipe (5) is in sealing connection with the water outlet (19);
the water inlet system comprises a water inlet tank (1), a water inlet pump (21) and a water inlet pipe (3), one end of the water inlet pipe (3) is connected to the water inlet tank (1), the other end of the water inlet pipe is introduced into the aerobic sludge reaction tank (10), and the water inlet pump (21) is arranged between the water inlet tank (1) and the aerobic sludge reaction tank (10);
the aeration system comprises an air blower (8), a vent pipe (11) and an aeration head (9), one end of the vent pipe (11) is communicated with the aerobic sludge reaction tank (10), the vent pipe (11) communicated with the aerobic sludge reaction tank (10) is provided with the aeration head (9), the aeration head (9) is arranged below the electro-catalytic membrane component, and the other end of the vent pipe (11) is connected with the air blower (8);
the electrocatalytic membrane component comprises a membrane frame (15), an outer side mesh pipe (12), a porous coating electrode pipe (13) and an inner side mesh pipe (14);
the lengths of the outer side mesh pipe (12), the porous coating electrode pipe (13) and the inner side mesh pipe (14) are equal, the porous coating electrode pipe (13) is arranged inside the outer side mesh pipe (12), the inner side mesh pipe (14) is arranged inside the porous coating electrode pipe (13), two ends of the outer side mesh pipe (12), the porous coating electrode pipe (13) and the inner side mesh pipe (14) are sealed by a membrane frame (15) to form a cavity I (16), a cavity II (17) and a cavity III (18), wherein a water outlet (19) is formed at one end of the cavity III (18) which is in contact with the membrane frame (15);
wherein the outer side mesh pipe (12) and the inner side mesh pipe (14) are used as cathodes, and the porous coating electrode pipe (13) is used as an anode;
the porous coating electrode tube (13) is tubular Ti/TiO 2 -NTs/SnO 2 -an Sb electrode;
the tubular Ti/TiO 2 -NTs/SnO 2 the-Sb electrode comprises a Ti substrate and TiO 2 -NTs intermediate layer and SnO 2 -an Sb outer layer, wherein the Ti matrix is a tubular porous titanium matrix with the porosity of 20-50%; tiO 2 2 The NTs intermediate layer is a layer of vertically ordered TiO obtained on a Ti substrate 2 A nanotube; snO 2 -the Sb outer layer is a metal oxide coating with a nanostructure;
the outer side mesh pipe (12) and the inner side mesh pipe (14) are respectively and independently selected from stainless steel mesh pipes, titanium mesh pipes or nickel mesh pipes, and the mesh aperture of the mesh pipes is 100-350 meshes;
in the electrocatalytic membrane component, the distance between the porous coating electrode tube (13) and the outer side mesh tube (12) is 10-40mm, and the distance between the porous coating electrode tube (13) and the inner side mesh tube (14) is 10-40mm;
the method comprises the following steps:
step 1) self-generated dynamic film generation stage: adding aerobic sludge into an aerobic sludge reaction tank (10), adding clear water through a water inlet system to enable the water level to be over the whole electrocatalytic membrane component, simultaneously pumping water outwards through a water outlet system, depositing sludge particles on an outer side net pipe (12) by utilizing water flow pressure to form an autogenous dynamic membrane, detecting the turbidity of outlet water, and finishing the step 1) when the turbidity of the outlet water is less than 5 NTU;
step 2) wastewater treatment stage: wastewater is added into an aerobic sludge reaction tank (10) through a water inlet system, a power supply (4) is switched on, the wastewater is discharged through a water outlet system after passing through an electro-catalytic membrane component, the hydraulic retention time is 2-6h, and the flux of an authigenic dynamic membrane is 20-200L/(m) 2. h) (ii) a The voltage intensity of the power supply (4) is less than or equal to 4V/cm.
2. The method for treating refractory organic wastewater of claim 1, wherein the tubular Ti/TiO is Ti/TiO 2 -NTs/SnO 2 The preparation method of the-Sb electrode is as follows:
(1) Pretreatment of a porous Ti matrix: etching by using an oxalic acid solution to obtain a pitted porous Ti matrix;
(2) Preparation of Ti/TiO by electrochemical anode oxidation 2 -NTs: taking the Ti substrate in the step (1) as a working electrode, stainless steel as a counter electrode, the voltage is 20-40V, the electrolyte is 0.05-1.0 wt% of NaF, 1.4-2.0 wt% of supporting electrolyte is taken as a solute, 10-50 wt% of alcohol additive is added, and the solvent is ultrapure water;
(3) Preparation of SnO by thermal decomposition method 2 -an outer layer of Sb: uniformly coating the Ti/TiO treated in the step (2) with the tin-antimony oxide sol solution 2 Drying the NTs surface, performing thermal decomposition treatment at 500-550 ℃ for 10-15 minutes, repeating for 8-15 times, performing the last thermal decomposition for 60-80 minutes, and naturally cooling to room temperature;
the tin-antimony oxide sol solution is prepared from the following components: 5 to 10g of SbCl 3 ，90～110g SnCl 4 ·5H 2 O, 240-260 mL of ethylene glycol solution, 180 to 210g of citric acid.
3. The method for treating refractory organic wastewater as defined in claim 1, further comprising the step of, after the step 2), treating refractory organic wastewater
Step 3): and (3) a reactor dynamic membrane cleaning stage: when the transmembrane pressure (TMP) inside and outside the self-generated dynamic membrane is more than 40Kpa, stopping working and cleaning the membrane module;
the cleaning is carried out in an air backwashing mode, the backwashing pressure is 8-12 kPa, and the backwashing air quantity is 15-30L/(m) 2 S); the back washing time is 2-5 min; when the flux recovery rate is lower than 90%, taking out and then adopting NaClO chemical cleaning, wherein the concentration of NaClO is 500-3000 mg/L, and the citric acid is 0.4-2.0 wt%.
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