Constructing a multistage food chain biofilm system enhanced by electrochemistry and its application in pharmaceutical wastewater
12116301 ยท 2024-10-15
Assignee
Inventors
Cpc classification
C02F2201/46115
CHEMISTRY; METALLURGY
C02F9/00
CHEMISTRY; METALLURGY
C02F2103/343
CHEMISTRY; METALLURGY
International classification
Abstract
The present invention belongs to the technical field of environmental engineering and provides a method for constructing a multistage food chain biofilm system enhanced by electrochemistry and an application in pharmaceutical wastewater. A flow-through electrochemical degradation module is constructed based on P/F-TiO.sub.2-n porous membrane electrodes, and a multistage flow-through composite electrochemical-biological submerged fixed film reactor is constructed jointly with the PA-N-rGO fixed fiber carrier and applied to deep purification of high-risk substances in pharmaceutical wastewater. The flow-through electrochemical degradation module can also effectively degrade antibiotics resistance genes and refractory organics in the water, improve the biodegradability of the wastewater and improve the degradation performance and load of shock resistance of the system, so the multistage flow-through composite electrochemical-biological submerged fixed film reactor can realize the high-efficiency low-consumption treatment of pharmaceutical wastewater and effectively reduce the yield of excess activated sludge.
Claims
1. A method for constructing a multistage food chain biofilm system enhanced by electrochemistry, comprising the following steps: step 1: preparing a nylon 66 (PA66) material; step 2: preparing an N-doped reduced graphene oxide (N-rGO) material; step 3: treating the N-rGO material obtained in step 2 by ball milling, taking out the N-rGO material for ultrasonic dispersion with deionized water, conducting suction filtration of the dispersion liquid, taking out black filtrate, and carrying out freeze drying to obtain a few-layer N-rGO nanosheet material; and heating the PA66 material obtained in step 1, adding the few-layer N-rGO nanosheet material in a molten state, conducting stirring in the molten state, forming PA-N-rGO fibers by an extruder, and fixing both ends of the PA-N-rGO fibers on a frame composed of polypropylene pipes by a textile machine to form a plurality of fixed fiber curtains composed of the PA-N-rGO fibers to be used as fixed fiber curtain carriers for carrying microorganisms; step 4: pre-treating porous Ti plates by heating in potassium hydroxide and oxalic acid solutions successively, removing impurities from the surfaces, and forming titanium oxide films in situ on the surfaces of the porous Ti plates; then, conducting repeated dip-coating on the oxidized porous Ti plates in a 0.5-3 mol/L potassium fluoride aqueous solution, and loading potassium fluoride on the surfaces of the Ti plates; and putting the Ti plates into a corundum porcelain boat and then into a tube furnace, placing the porcelain boat with sodium hypophosphite at a distance of 100 mm from the porous Ti plates upwind of the tube furnace, conducting isothermal reactions for 1-2 h at temperatures of 350? C. in a nitrogen atmosphere, then heating up to 450? C. in the nitrogen atmosphere and conducting isothermal reaction for 1-2 h, carrying out natural cooling to room temperature, and finally performing electrochemical reduction treatment of the porous Ti plates, thus obtaining a P/F co-doped titanium suboxide porous membrane electrode material; step 5: constructing flow-through electrochemical degradation modules with anodes made of the obtained P/F co-doped titanium suboxide porous membrane electrode material and cathodes made of 4-30-mesh stainless steel meshes, wherein the cathodes and the anodes are spaced 10-30 mm apart; putting the fixed fiber curtain carriers obtained in step 3 into a microbial reactor, with the fixed fiber curtains spaced 200-500 mm apart, so as to form a biological submerged fixed film reactor; and dividing the biological submerged fixed film reactor into 3-12 cells by the flow-through electrochemical degradation modules to construct a multistage flow-through composite electrochemical-biological submerged fixed film reactor, applying a constant current of 0.5-5 mA/cm.sup.2 for operation, and adding activated sludge to the microbial reactor for culture, which enables fiber surfaces to carry a large number of functional microorganisms in a short time.
2. The method for constructing a multistage food chain biofilm system enhanced by electrochemistry according to claim 1, wherein in step 3, the N-rGO material is treated by dry ball milling at a revolving speed of 3000-5000 rpm for 30-60 min.
3. The method for constructing a multistage food chain biofilm system enhanced by electrochemistry according to claim 1, wherein in step 3, the PA66 material is heated to 230-280? C. and added with the few-layer N-rGO nanosheet material in a molten state at a mass ratio of 7:3-99:1, which are stirred in the molten state for 30 min.
4. The method for constructing a multistage food chain biofilm system enhanced by electrochemistry according to claim 1, wherein in step 3, the length range of the PA-N-rGO fibers is 50-2000 mm.
5. The method for constructing a multistage food chain biofilm system enhanced by electrochemistry according to claim 1, wherein in step 4, the number of times of dip-coating is 3-20.
6. The method for constructing a multistage food chain biofilm system enhanced by electrochemistry according to claim 1, wherein in step 4, a heating rate is 5? C./min.
Description
DESCRIPTION OF DRAWINGS
(1)
(2)
(3)
(4)
(5)
(6) In the figures: 1 water inlet, 2 stainless steel mesh cathode, 3 P/F-TiO.sub.2-n porous anode, 4 PA-N-rGO fixed fiber curtain, 5 water outlet, 6 fixed outer frame, and 7 DC power supply.
DETAILED DESCRIPTION
(7) Specific embodiments of the present invention are further described below in combination with the technical solution.
Embodiment 1
(8) Preparation of N-rGO Material:
(9) Referring to the method in the article Free-Standing 3D Porous N-Doped Graphene Aerogel Supported Platinum Nanocluster for Efficient Hydrogen Production from Ammonia Electrolysis, the specific steps are as follows: graphite powder is pre-oxidized first, 5 g of natural graphite powder, 2.5 g of potassium persulfate and 2.5 g of phosphorus pentoxide are weighed and added into a round-bottom flask, 10 mL of concentrated sulfuric acid is added for stirring action in a 80? C. thermostat water bath for 8 h to form viscous pre-oxidized graphite, and then the graphite is oxidized. In an ice bath, 2.5 g of sodium nitrate and 150 mL of concentrated sulfuric acid are added, and 15 g of potassium permanganate is slowly added (the mass ratio of graphite powder to potassium permanganate is 1:3). During the process, the reaction temperature should not exceed 20? C. After stirring reaction for 1 h, the temperature of the water bath is adjusted to 35? C., the stirring reaction is continued for 2 h, the pre-oxidized graphite is further oxidized by the potassium permanganate, 230 mL of deionized water is added, the temperature of the water bath is increased to 98? C., and then the stirring reaction is continued for 2 h. Finally, the heating in the water bath is stopped, 250 mL of deionized water and 20 mL of hydrogen peroxide solution are added, stirring reaction is conducted for 1 h, and then the reaction is stopped. The brown yellow reaction liquid is poured into the flask, repeatedly washed with 0.1 M hydrochloric acid and tested with a 2 wt % BaCl.sub.2 solution until the SO.sub.4.sup.2- in the solution is clean, and the solution is washed with deionized water until pH is near neutral (pH?6-7). After ultrasonic treatment, uniform and stable GO suspension is obtained.
(10) For the N doping process, after 3 mg mL.sup.?1 GO solution (40 mL) is ultrasonically mixed with melamine of different qualities, the mixtures are added into a 50 mL reactor respectively, sealed and then subjected to hydrothermal synthesis at 180? C. for 12 h, the obtained solid is cleaned with deionized water, dried and calcined in a tube furnace at 550? C. in an argon atmosphere for 4 h, and the obtained black powder is the prepared N-rGO.
Embodiment 2
(11) Preparation of Fixed Fiber Curtain Carrier:
(12) A PA66 material is prepared according to the reference in step 1, the N-rGO solid material in embodiment 1 is put into a ball mill and treated by dry ball milling at a revolving speed of 3000-5000 rpm for 30-60 min, the N-rGO material is taken out for ultrasonic dispersion with deionized water (for 10 min), the dispersion liquid is subjected to suction filtration, black filtrate is taken out, and freeze drying is carried out to obtain a few-layer N-rGO nanosheet material. The PA66 material is heated to 280? C. and added with the few-layer N-rGO nanosheet material in a molten state at a mass ratio of 9:1, which are stirred in the molten state for 30 min, PA-N-rGO1 fibers are formed by an extruder, and the PA-N-rGO1 fibers are fixed on a frame composed of polypropylene pipes by a textile machine to form a fixed fiber curtain carrier for carrying microorganisms.
(13) Reference group: different PA-N-rGO fibers are prepared by the same preparation method at different N-rGO nanosheet addition proportions, the mass ratio of PA66 to N-rGO nanosheets is 7:3, 8:2, 95:5, 99:1 and 10:0 respectively, the fibers are numbered PA-N-rGO3, PA-N-rGO2, PA-N-rGO0.5, PA-N-rGO0.1 and PA-N-rGO0 respectively, and the corresponding fixed fiber curtain carrier is prepared by the textile machine.
Embodiment 3
(14) Physical and Chemical Property Test of PA-N-rGO Fibers:
(15) The specific surface areas of PA-N-rGO3, PA-N-rGO2, PA-N-rGO1, PA-N-rGO0.5, PA-N-rGO0.1 and PA-N-rGO0 are tested by N2 adsorption and desorption experiments, which are 14.1, 19.9, 25.6, 15, 8.6 and 2.7 m.sup.2/g respectively. With the appearance of a large number of two-dimensional lamellar structures on the surfaces of N-RGo-doped PA-N-rGO fibers, the specific surface area is gradually increased, which is conducive to the enrichment of microorganisms on the surface of the materials and the electron transfer between microorganisms. When the addition amount of N-rGO is too high, the specific surface area of the material is decreased, which is because too much N-rGO cannot be completely uniformly dispersed in the system, and aggregates with each other due to ?-? stacking, thus reducing the specific surface area of the material.
(16) The resistances of PA-N-rGO3, PA-N-rGO2, PA-N-rGO1, PA-N-rGO0.5 and PA-N-rGO0.1 are tested by a four-probe method, which are 161, 57, 13, 195 and 940? respectively, and the non-conductivity of PA-N-rGO0 cannot be tested. The electrical conductivity of the N-rGO-doped PA-N-rGO fibers first increases and then decreases, which is also because the excessive N-rGO will aggregate and thus affect the electrical conductivity of the system. An appropriate addition amount of N-rGO can achieve optimal electrical conductivity, so as to promote electron transfer between the carried microorganisms.
(17) The tensile strengths of PA-N-rGO3, PA-N-rGO2, PA-N-rGO1, PA-N-rGO0.5, PA-N-rGO0.1 and PA-N-rGO0 are tested through mechanical properties, which are 86, 111, 231, 199, 134 and 75 Mpa respectively. With the increase of the N-rGO doping amount, the tensile strength of the PA-N-rGO fibers first increases and then decreases, which indicates that the doping of N-rGO can significantly improve the mechanical strength of the fiber material. However, the excessive N-rGO will agglomerate in the system and thus cannot be uniformly distributed in the system, which will seriously affect the mechanical properties of the material.
Embodiment 4
(18) Preparation of P/F-TiO.sub.2-n Porous Membrane Electrode:
(19) Porous Ti plates (200?200 mm, with an average pore size of 80 ?m and porosity of 30%) are pre-treated by heating in potassium hydroxide and oxalic acid solutions successively, impurities are removed from the surfaces, and titanium oxide films are formed in situ on the surfaces of the porous Ti plates by an electrochemical etching method in the article Removal of aqueous triclosan using TiO.sub.2 nanotube arrays reactive membrane by sequential adsorption and electrochemical degradation; The specific method is as follows: an electrochemical etching solution (the mass fraction of glycol is 94.7%, the mass fraction of ultrapure water is 5%, and the mass fraction of ammonium fluoride is 0.3%) is prepared, the pre-treated porous Ti plates are used as anodes and placed in the middle of an electrochemical reactor, two pure Ti plates are used as cathodes and placed on both sides of the porous Ti plates, the electrodes are spaced 40 mm apart and operate at a constant voltage of 40 V, the etching time is 8 h, after the reaction, the porous Ti plates are removed, rinsed with deionized water, dried at ambient temperature and calcined in a muffle furnace at 450? C. for 2 h, the heating rate is 5? C./min, and TiO.sub.2-n porous membrane electrodes are obtained by natural cooling.
(20) Then, the TiO.sub.2-n porous membrane electrodes are put into a 1 mol/L potassium fluoride aqueous solution for repeated dip-coating (for 10 times), and a fluorinated precursor material is loaded on the electrode surfaces. The TiO.sub.2-n porous membrane electrodes are put into a corundum porcelain boat and then into a tube furnace, the porcelain boat with sodium hypophosphite (2 g) is placed at a distance of 100 mm from the TiO.sub.2-n porous membrane electrodes upwind of the tube furnace, gradient heating is carried out in a nitrogen atmosphere at a heating rate of 5? C./min, isothermal reactions are conducted for 1 h respectively at temperatures of 350? C. and 450? C., natural cooling is carried out to room temperature, and finally, electrochemical reduction treatment is performed on the TiO.sub.2-n porous membrane electrodes, thus obtaining the P/F co-doped titanium suboxide (P2/F1-TiO.sub.2-n) porous membrane electrode material.
(21) Reference group: the concentration of the potassium fluoride aqueous solution is fixed to 1 mol/L by the same preparation method, the usage amount of sodium hypophosphite is 0.5, 1, 3 and 5 g respectively, and the porous membrane electrodes are numbered P0.5/F1-TiO.sub.2-n, P1/F1-TiO.sub.2-n, P3/F1-TiO.sub.2-n and P5/F1-TiO.sub.2-n respectively. The usage amount of sodium hypophosphite is fixed to 2 g, the concentration of the potassium fluoride aqueous solution is 0.5, 2 and 3 mol/L respectively, and the porous membrane electrodes are numbered P2/F0.5-TiO.sub.2-n, P2/F2-TiO.sub.2-n and P2/F3-TiO.sub.2-n respectively.
(22) Performance Test of P/F-TiO.sub.2-n Porous Membrane Electrode:
(23) Tests of water contact angles: TiO.sub.2-n, P2/F0.5-TiO.sub.2-n, P2/F1-TiO.sub.2-n, P2/F2-TiO.sub.2-n and P2/F3-TiO.sub.2-n series materials are tested, and the results show that the water contact angles of the materials are gradually increased (47?, 93?, 109?, 140? and) 162? with the increase of the concentration of the potassium fluoride aqueous solution, and the hydrophobicity is significantly enhanced with the increase of the F doping amount. The water contact angles of P0.5/F1-TiO.sub.2-n, P1/F1-TiO.sub.2-n, P2/F1-TiO.sub.2-n, P3/F1-TiO.sub.2-n and P5/F1-TiO.sub.2-n series materials are 115?, 112?, 109?, 101? and 99? respectively, and the P doping amount has no obvious influence on the hydrophobicity of the materials.
(24) The resistances of TiO.sub.2-n, P2/F0.5-TiO.sub.2-n, P2/F1-TiO.sub.2-n, P2/F2-TiO.sub.2-n and P2/F3-TiO.sub.2-n are tested by a four-probe method, which are 21, 2.4, 1.7, 2.1 and 1.9? respectively. The influence of the F doping amount on the electrical conductivity is not obvious. The resistances of P0.5/F1-TiO.sub.2-n, P1/F1-TiO.sub.2-n, P2/F1-TiO.sub.2-n, P3/F1-TiO.sub.2-n and P5/F1-TiO.sub.2-n series materials are 6.4, 4.5, 1.7, 1.1 and 0.8? respectively, and with the increase of the P doping amount, the electrical conductivity of the materials is also enhanced, indicating that P doping can effectively change the electronic structure of the system and regulate the localized electron configuration at the active reaction site, and new electron migration channels are constructed, which is conducive to improving the catalytic stability and catalytic activity of the active site.
(25) Electrocatalytic Degradation Performance
(26) With a mixed aqueous solution of an antibiotic (10 mg/L ciprofloxacin), an anticancer drug (10 mg/L capecitabine) and a non-steroidal anti-inflammatory drug (10 mg/L ibuprofen) as simulated pharmaceutical wastewater, the P2/F0.5-TiO.sub.2-n, P2/F2-TiO.sub.2-n, P1/F1-TiO.sub.2-n, P2/F1-TiO.sub.2-n, P3/F1-TiO.sub.2-n and TiO.sub.2-n (reference group) porous membrane electrodes prepared in embodiment 5 as anodes and 4-mesh stainless steel meshes as cathodes and with the electrode spacing of 15 mm, flow-through electrochemical degradation modules are constructed respectively to treat the above simulated pharmaceutical wastewater and operate at a constant current (3 mA/cm.sup.2), the wastewater is operated in a flow-through mode, the reaction time is 60 min, the reaction liquid is extracted every 10 min, the extracted reaction liquid is filtered with a 0.22-?m filter membrane, then 1 mL is extracted, and the degradation rate is tested by a high performance liquid chromatograph.
(27) The results of high performance liquid phase tests show that the degradation rates of the above three typical drugs on TiO.sub.2-n anodes are only 55%, 28% and 22% after reaction for 60 min, while the degradation rates of the P/F-TiO.sub.2-n series porous membrane electrodes are all higher than that of TiO.sub.2-n (reference group). P2/F1-TiO.sub.2-n has appropriate hydrophobicity and active reaction sites, which can effectively react with hydrophilic and hydrophobic drugs in the water, so that the degradation rates of three target pollutants are all higher than 99% after the mixed wastewater reacts for 40 min. In contrast, the F doping amount that is too high (P2/F2-TiO.sub.2-n) or too low (P2/F0.5-TiO.sub.2-n) can only effectively degrade the hydrophobic drug (the degradation rate of capecitabine and ibuprofen reaches 99% after reaction for 40 min) or hydrophilic drug (the degradation rate of ciprofloxacin reaches 99% after reaction for 40 min), and cannot effectively degrade the two target pollutants at the same time. In addition, when the P doping amount is too low (P1/F1-TiO.sub.2-n), the membrane electrode material has low degradation performance for the target pollutants due to the lack of sufficient active reaction sites on the surface (the degradation rates of the three target pollutants only reach 75% after reaction for 60 min); and when the P doping amount is too high (P3/F1-TiO.sub.2-n), excessive P destroys the lattice structure of TiO.sub.2-n, and the content of the active site Ti.sup.3+ is much lower than that of other materials (P2/F0.5-TiO.sub.2-n, P2/F2-TiO.sub.2-n, P1/F1-TiO.sub.2-n and P2/F1-TiO.sub.2-n) in the series, causing that the degradation rates of the three target pollutants are only about 60% after reaction for 60 min. Therefore, only with appropriate F/P doping amounts and doping methods, the hydrophilicity of the electrode surfaces can be effectively regulated, and effective electron migration channels and active reaction sites can be constructed, which maintains the catalytic activity and improves the catalytic stability at the same time.
Embodiment 5
(28) Comparison Test of Microbial Load:
(29) With PA-N-rGO3, PA-N-rGO2, PA-N-rGO1, PA-N-rGO0.5, PA-N-rGO0.1 and PA-N-rGO0 (reference group) fixed fiber curtains as microbial carriers, a multistage flow-through composite electrochemical-biological submerged fixed film reactor is constructed (the biological submerged fixed film reactor is divided into three cells by a two-stage flow-through electrochemical degradation module), and the anodes used for the flow-through electrochemical degradation module are made of P2/F1-TiO.sub.2-n with optimal testing performance in embodiment 5. A constant current (3 mA/cm.sup.2) is applied for operation, activated sludge is added for culture, and the surface of the fiber carrier can carry a large number of microorganisms in five days. In the case of the same operation conditions and culture time, the microbial load on the fixed fiber curtain carrier containing N-rGO is higher than that on the reference group without N-rGO, wherein the microbial load on the PA-N-rGO1 fiber curtain carrier with the largest specific surface area and the best electrical conductivity is the highest in this series of materials and is 3.5 times that of the reference group (PA-N-rGO0), and the abundance of acid-producing microorganisms in floras is increased by 1.5 times compared with the control group. In addition, the microbial load of the PA-N-rGO1 fiber curtain carrier is more than 5.7 times that of the traditional packings (polypropylene stereo elastic packing and polyethylene porous suspension ball packing).
(30) The microbial load, effluent COD and ammonia nitrogen performance of the multistage flow-through composite electrochemical-biological submerged fixed film reactor constructed from PA-N-rGO1 and P2/F1-TiO.sub.2-n are compared under power-on and power-off conditions, and in the case that the other operation conditions are the same as those of the above biological submerged fixed film reactor, the microbial load, effluent COD and ammonia nitrogen content of the fiber carrier under power-on conditions are 1.4 times, ? and ? of those under power-off conditions respectively.
Embodiment 6
(31) Degradation Test of Actual Pharmaceutical Wastewater Test:
(32) The actual pharmaceutical wastewater is taken as the target water body, the influent quality is COD 3000 mg/l, BOD 600-1000 mg/l, TN 200-300 mg/l and NH.sub.3-N 150-250 mg/l, and the multistage flow-through composite electrochemical-biological submerged fixed film reactor constructed in embodiment 6 is used to operate at a constant current (3 mA/cm.sup.2). After stable operation, effluent water is taken out to test the water quality, and the test results show that COD?50 mg/l, BOD?5 mg/l and TN?10 mg/l. The traditional anaerobic-aerobic-MBR process is selected as the reference group to treat the above actual pharmaceutical wastewater. After stable operation, effluent water is taken out to test the water quality, and the test results show that COD 150-200 mg/l, BOD?10 mg/l and TN is about 60 mg/l. The comparison results show that the treatment capacity of the multistage flow-through composite electrochemical-biological submerged fixed film reactor of the present patent for the actual pharmaceutical wastewater is much better than that of the traditional microbial treatment process. Moreover, in the case that the operation time is the same, the excess activated sludge produced by the multistage flow-through composite electrochemical-biological submerged fixed film reactor is about 1/10 of that of the traditional microbial treatment process, indicating that the multistage flow-through composite electrochemical-biological submerged fixed film reactor constructed by the present patent provides a suitable growing environment for protozoa, metazoa and aquatic animals through the special carrier packing, the specific distribution pattern and the strengthening effect of the electrochemical degradation module to form a stable food chain system, which can make the excessive zoogloea (activated sludge) produced in the system gradually convert into CO.sub.2 and H.sub.2O through the multistage predation process by using the metabolism of different organisms, thereby improving the carbon conversion rate (from organic C to CO.sub.2) and the sludge reduction effect. The whole process achieves the balance transfer of C sources with the conversion of energy and finally maintains the conservation of matter.
Embodiment 7
(33) Degradation Test of Actual Chemical Wastewater Test:
(34) The actual chemical wastewater is taken as the target water body, the influent quality is COD 3000 mg/l, BOD 1000-1200 mg/l and formaldehyde (CH.sub.2O) 300 mg/l, and the multistage flow-through composite electrochemical-biological submerged fixed film reactor constructed in embodiment 6 is used to operate at a constant current (3 mA/cm.sup.2). After stable operation, effluent water is taken out to test the water quality, and the test results show that COD?50 mg/l, BOD?5 mg/l and CH.sub.2O?0.5 mg/l. The traditional UASB-MBBR process is selected as the reference group to treat the above actual chemical wastewater. After stable operation, effluent water is taken out to test the water quality, and the test results show that COD?150 mg/l, BOD?20 mg/l and CH.sub.2O?15 mg/l. Since the actual chemical wastewater contains more toxic CH.sub.2O, the microorganisms are poisoned by CH.sub.2O and thus has low load of shock resistance, which leads to unstable operation of the traditional process. The multistage flow-through composite electrochemical-biological submerged fixed film reactor constructed by the present patent has simple operation conditions of the process, the microbial load of the surface of the fiber carrier is much higher than that of the traditional microbial carrier, the electrochemical degradation module can also carry out electrooxidation step by step, strengthen the degradation and detoxification of toxic organics and improve the biodegradability of the wastewater so that the system has high resistance to CH.sub.2O shock and toxicity and operates stably, the yield of excess activated sludge is more than 90% less than that of the traditional microbial treatment process, the effluent quality is also improved, and the discharge quality of the effluent water meets the first class A discharge standard in Discharge Standard of Pollutants for Municipal Wastewater Treatment Plant (GB/T18918-2002), which also indicates that the multistage flow-through composite electrochemical-biological submerged fixed film reactor can be suitable for treatment of chemical wastewater with high biotoxicity.
Embodiment 8
(35) Degradation Test of Actual Municipal Wastewater Test:
(36) The actual municipal wastewater is taken as the target water body, the influent quality is COD 400 mg/l and NH.sub.3-N 35 mg/l, and the multistage flow-through composite electrochemical-biological submerged fixed film reactor constructed in embodiment 6 is used to operate at a constant current (3 mA/cm.sup.2). After stable operation, effluent water is taken out to test the water quality, and the test results show that COD?30 mg/l and NH.sub.3-N?5 mg/l. The traditional MBR process is selected as the reference group to treat the above actual chemical wastewater. After stable operation, effluent water is taken out to test the water quality, and the test results show that COD?50 mg/l and NH.sub.3-N?15 mg/l. The yield of excess activated sludge of the multistage flow-through composite electrochemical-biological submerged fixed film reactor is only 5% of that of the traditional MBR process, which indicates that the system is also suitable for treatment of municipal wastewater with low COD.