Sewage pollutant treatment device

Abstract

The utility model provides a sewage pollutant treatment device. The sewage pollutant treatment device comprises an anode chamber, a cathode chamber, a cation exchange membrane, an aeration structure and a data acquisition system, the anode chamber contains electrogenesis bacteria liquid containing electrogenesis bacteria; an anode carbon rod is inserted into the anode chamber and is filled with an anode graphite carbon felt; a cathode carbon rod is inserted into the cathode chamber, and a cathode graphite carbon felt is arranged on the cathode carbon rod; the cation exchange membrane is arranged between the anode chamber and the cathode chamber, and the cation exchange membrane is a proton exchange membrane; the conventional pollutants in the sewage are decomposed by utilizing electrogenesis bacteria in an anode solution in the anode chamber, chemical energy is converted into electric energy, and electrons and protons are generated; electrons reach the cathode through an external circuit, and protons are transmitted to the cathode chamber through the cation exchange membrane; the aeration structure is communicated with the cathode chamber, oxygen dissolved in the cathode chamber is combined with electrons and protons to generate H2O2, then the H2O2 and Fe < 2 + > are subjected to a Fenton reaction to generate hydroxyl radical.OH, and the hydroxyl radical.OH mineralizes novel pollutants in a cathode solution.

Description

TECHNICAL FIELD

[0001] The utility model belongs to sewage treatment technical field especially relates to a sewage pollutant treatment device. BACKGROUND

[0002] The conventional pollutants in the sewage of the sewage treatment plant are COD, ammonia nitrogen and total phosphorus, and the emerging contaminants (ECs) are different from the conventional pollutants, refer to the pollutants newly discovered or concerned, which have risks to the ecological environment or human health and have not been included in the management or the existing management measures are insufficient to effectively prevent and control the risks.

[0003] Most of the traditional sewage treatment processes are based on activated sludge method, and the pollutants are removed by external energy supply, which increases the emerging contaminants such as dimethyl phthalate during the treatment.

[0004] The current sewage treatment device can only treat the conventional pollutants, and cannot treat the emerging contaminants. The emerging contaminants are different from the conventional pollutants, have certain persistence and accumulation, have chemical stability in the water environment, and the traditional sewage treatment technology is difficult to completely degrade them.

[0005] Among the technologies for degrading emerging contaminants, the electro-Fenton technology has been widely concerned due to its rapid reaction, simple operation and complete degradation, but it has the disadvantages of large power consumption and high cost.

[0006] Therefore, it is necessary to provide a sewage pollutant treatment device and method. UTILITY MODEL CONTENT

[0007] In view of the deficiencies in the prior art, the purpose of the utility model is to provide a sewage pollutant treatment device and method, which can treat conventional pollutants and emerging contaminants at the same time, so as to reduce power consumption and production cost.

[0008] To achieve this purpose, the utility model adopts the following technical solutions:

[0009] A sewage pollutant treatment device, comprising an anode chamber, a cathode chamber, a cation exchange membrane, an aeration structure and a data acquisition system;

[0010] The anode chamber is communicated with the first peristaltic pump outside, and the first peristaltic pump delivers the sewage to the anode chamber;

[0011] The anode chamber contains an electrogenic bacteria liquid of electrogenic bacteria;

[0012] The anode carbon rod is inserted into the anode chamber and filled with anode graphite carbon felt, and one end of the anode carbon rod is connected with an external circuit;

[0013] The cathode chamber is inserted with a cathode carbon rod, the cathode carbon rod is provided with a cathode graphite carbon felt, and one end of the cathode carbon rod is connected to an external circuit, and the anode carbon rod and the cathode carbon rod are connected through a resistor;

[0014] The cation exchange membrane is arranged between the anode chamber and the cathode chamber, and the cation exchange membrane is a proton exchange membrane;

[0015] The water outlet of the anode chamber is communicated with the water inlet of the cathode chamber through a pipeline, and a second peristaltic pump is installed on the pipeline;

[0016] In the anode solution in the anode chamber, the electrogenic bacteria decompose conventional pollutants in the sewage, convert chemical energy into electrical energy, and generate electrons and protons;

[0017] The electrons reach the cathode through an external circuit, and the protons are transmitted to the cathode chamber through a cation exchange membrane;

[0018] An aeration structure is communicated with the cathode chamber, and dissolved oxygen in the cathode chamber combines with electrons and protons to generate H2O2, and then H2O2 combines with Fe 2+ Fenton reaction occurs to generate hydroxyl radicals ·OH, and the hydroxyl radicals ·OH mineralize new pollutants in the cathode solution;

[0019] The anode carbon rod and the cathode carbon rod are connected to a data acquisition system.

[0020] Preferably, the chemical reaction formula of the electrogenic bacteria in the anode chamber is: COD + 6H2O → 6CO2 + 24H + + 24e - 1);

[0021] The new pollutants are decomposed into intermediate products in the cathode chamber, and further decomposed into small molecular inorganic substances;

[0022] Fe 2+ is oxidized to Fe 3+ , and the chemical reaction formula in the cathode chamber is: O2 + 2H + + 2e - → H2O2);

[0023] H2O2 + Fe 2+ → Fe 3+ + ·OH + OH - (1-2)

[0024] New pollutants + ·OH → intermediate products (1-3)

[0025] Intermediate products + ·OH → CO2 + H2O + small molecular inorganic substances (1-4).

[0026] Preferably, the cathode graphite carbon felt supports the catalytic material.

[0027] Preferably, the cathode graphite carbon felt is fixed to the cathode carbon rod with titanium wire.

[0028] Preferably, the anode graphite carbon felt filling the anode chamber is 2 / 3 of the volume of the anode chamber.

[0029] Preferably, before the anode graphite carbon felt is filled into the anode chamber, it needs to be boiled with 1 mol / L NaOH and 1 mol / L HCl for 20 minutes respectively, rinsed with ultrapure water until neutral, and then soaked in ultrapure water for later use.

[0030] Preferably, the cathode graphite carbon felt is soaked in acetone for 24 hours before being filled into the cathode chamber, then rinsed several times with ultrapure water and fired in a muffle furnace at 450°C for 30 minutes.

[0031] Preferably, the cation exchange membrane is boiled for 1 hour each with 30% H2O2 and 0.5 mol / L H2SO4, and then rinsed with ultrapure water until neutral.

[0032] Preferably, the diameters of the anode carbon rod and the cathode carbon rod are in the range of 5cm-10cm.

[0033] Preferably, the lengths of the anode carbon rod and the cathode carbon rod are in the range of 10cm-25cm.

[0034] Compared with the prior art, the present invention has the following beneficial effects:

[0035] The wastewater pollutant treatment device of this invention has a simple operation process and readily available reactions. Because electrogenic bacteria are added to the anode chamber, these bacteria generate a circuit, resulting in stronger oxidation, a more thorough reaction, and better treatment effects.

[0036] Electrogenic bacteria in the anode chamber use organic pollutants in wastewater as nutrients to degrade organic pollutants (conventional pollutants) and generate electricity at the same time. The current is used for the electro-Fenton technology at the cathode to produce hydroxyl radicals (·OH), thereby mineralizing recalcitrant pollutants, i.e., new pollutants.

[0037] Electro-Fenton technology can effectively and continuously degrade organic matter in wastewater over a long period of time, and reduce Fe in the solution. 2+ H2O2 is continuously generated at a certain rate, resulting in more complete degradation of new pollutants;

[0038] Fe 2+The cathode can be regenerated and recycled, no pollution is caused by Fe(OH)3 sludge, the production of iron sludge is reduced, there is almost no secondary pollution, and subsequent treatment is simple.

[0039] Therefore, the utility model discloses utilize the electricity -generating bacteria in anode chamber to degrade conventional pollutants in sewage and generate electricity, and utilize the cathode electro -fenton technology to mineralize novel pollutants in sewage, can realize the degradation of conventional pollutants and novel pollutants in sewage, reduce the risk of pollutants entering the environment, have remarkable economic benefit and environmental benefit. BRIEF DESCRIPTION OF DRAWINGS

[0040] Figure 1 It is the structural schematic diagram of sewage pollutant treatment device in the utility model;

[0041] Figure 1-1 It is DMP standard curve in the utility model;

[0042] Figure 1-2 It is the voltage change diagram with time in the utility model;

[0043] Figure 1-3 (a) is the current and power curve diagram in the utility model;

[0044] Figure 1-3 (b) is the current and output voltage curve diagram in the utility model;

[0045] Figure 1-4 (a) is the COD degradation efficiency curve diagram in the utility model;

[0046] Figure 1-4 (b) is the DMP degradation efficiency change curve diagram in the utility model.

[0047] Wherein, 1, anode chamber;2, cathode chamber;3, cation exchange membrane;4, anode graphite carbon felt;5, cathode graphite carbon felt;6, electricity -generating bacteria;7, water inlet;8, water outlet;10, cathode carbon rod;11, reference electrode;12, anode carbon rod;13, resistance;14, external circuit;15, first peristaltic pump;16, water pipe;17, municipal sewage;18, aeration head;19, aeration pipe;20, flowmeter;21, air pump;22, data acquisition system;23, computer;24, second peristaltic pump. DETAILED DESCRIPTION

[0048] In order to make the purpose, technical scheme and advantages of the embodiments of the present application clearer, the technical scheme of the embodiments of the present application will be described clearly and completely below in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments are some but not all of the embodiments of the present application. The components of the embodiments of the present application described and shown in the drawings herein can be arranged and designed in various different configurations.

[0049] Therefore, the following detailed description of the embodiments of the present application provided in the drawings is not intended to limit the scope of the claimed present application, but only represents selected embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative labor fall within the scope of protection of the present application.

[0050] It should be noted that: similar reference numbers and letters represent similar items in the following drawings, therefore, once an item is defined in one drawing, it does not need to be further defined and explained in subsequent drawings.

[0051] In the description of the present application, it should be noted that the terms "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer" and the like indicate the orientation or positional relationship based on the orientation or positional relationship shown in the drawings, or the orientation or positional relationship commonly placed when the product of the present application is used, and are only for the convenience of describing the present application and simplifying the description, and therefore cannot be understood as indicating or implying that the indicated device or element must have a particular orientation, be constructed and operated in a particular orientation, and therefore cannot be understood as limiting the present application. In addition, the terms "first", "second", "third" and the like are only used for differentiation in description, and cannot be understood as indicating or implying relative importance. In the description of the present application, unless otherwise specified, the meaning of "a plurality of" is two or more.

[0052] In the description of the present application, it should also be noted that, unless otherwise specified and limited, the terms "provided", "connected" should be understood broadly, for example, it can be fixedly connected, or detachably connected, or integrally connected; it can be mechanically connected, or electrically connected. For those of ordinary skill in the art, the specific meaning of the above terms in the present application can be understood according to the specific circumstances.

[0053] In this invention, unless otherwise explicitly specified and limited, "above" or "below" the second feature can include direct contact between the first and second features, or contact between the first and second features through another feature between them. Furthermore, "above," "over," and "on top" of the second feature includes the first feature directly above or diagonally above the second feature, or simply indicates that the first feature is at a higher horizontal level than the second feature. "Below," "below," and "under" the second feature includes the first feature directly below or diagonally below the second feature, or simply indicates that the first feature is at a lower horizontal level than the second feature.

[0054] The embodiments of this utility model are described in detail below. Examples of the embodiments are shown in the accompanying drawings, wherein the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions throughout. The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain this utility model, and should not be construed as limiting this utility model.

[0055] like Figure 1 As shown, this embodiment provides a wastewater pollutant treatment device, including an anode chamber 1, a cathode chamber 2, a cation exchange membrane 3, an aeration structure, and a data acquisition system 22.

[0056] The anode chamber 1 is connected to the outside of the first peristaltic pump 15, which transports sewage to the anode chamber 1.

[0057] The anode chamber 1 contains a solution of electrogenic bacteria 6;

[0058] An anode carbon rod 12 is inserted into the anode chamber 1 and filled with anode graphite carbon felt 4 as the anode electrode. The anode carbon rod 12 is connected to one end of the external circuit 14.

[0059] A cathode carbon rod 10 is inserted into the cathode chamber 2, and a cathode graphite carbon felt 5 is mounted on the cathode carbon rod 10 as the cathode electrode. The cathode carbon rod 10 is connected to one end of the external circuit 14, and the anode carbon rod 12 and the cathode carbon rod 10 are connected through a resistor 13. Specifically, the cathode graphite carbon felt 5 is fixed to the cathode carbon rod 10 with titanium wire. The cathode chamber 2 is filled with cobalt-doped porous carbon material (Co@NSC), which serves as a catalyst for degrading novel pollutants within the cathode chamber 2.

[0060] A cation exchange membrane 3 is disposed between the anode chamber 1 and the cathode chamber 2. The cation exchange membrane 3 is a proton exchange membrane.

[0061] The outlet 8 of the anode chamber 1 is connected to the inlet 7 of the cathode chamber 2 via a pipe;

[0062] A second peristaltic pump 24 is installed on the pipeline, and the sewage treated in the anode chamber 1 is transported to the cathode chamber 2 via the second peristaltic pump 24;

[0063] The chemical energy is converted into electrical energy by the electrogenic bacteria 6 in the anode solution in the anode chamber 1, producing electrons and protons. Specifically, the chemical reaction of the electrogenic bacteria 6 in the anode chamber 1 is: COD + 6H2O→ 6CO2+ 24H + + 24e - 1).

[0064] The electrons pass through the external circuit 14 to the cathode, and the protons pass through the cation exchange membrane 3 to the cathode chamber 2.

[0065] The cathode chamber 2 is aerated, and the dissolved oxygen in the cathode chamber 2 combines with the electrons and protons to generate H2O2, which then combines with Fe 2+ The Fenton reaction occurs to produce strong oxidizing hydroxyl radicals ·OH (as shown in reaction formula (2)), which mineralize the new pollutants in the cathode solution, decompose the new pollutants into intermediate products, and further decompose into small molecular inorganic substances. Fe 2+ is oxidized to Fe 3+ at the same time, as shown in reaction formulas (1-2, 1-3, 1-4). After that, Fe 3+ can be reduced to Fe 2+ again, and continue to be utilized, improving the utilization rate of the catalyst.

[0066] The chemical reaction in the cathode chamber is: O2+ 2H + + 2e - → H2O2

[0067] H2O2+ Fe 2+ → Fe 3+ + ·OH + OH - (1-2)

[0068] New pollutants + ·OH→ intermediate products (1-3)

[0069] Intermediate products + ·OH→ CO2+ H2O+ small molecular inorganic substances (1-4).

[0070] The operation process of the sewage pollutant treatment device in this embodiment is simple, and the reaction is easy to obtain. Because the electrogenic bacteria 6 is added in the anode chamber 1, the electrogenic bacteria 6 generates an electric circuit, which is more oxidizing and more thorough, and the treatment effect is better.

[0071] The electrogenic bacteria 6 in the anode chamber 1 utilizes the organic pollutants in the sewage as nutrients, degrades the organic pollutants (conventional pollutants) while generating electricity, obtains electric current, and is used for the electro-Fenton technology of the cathode to generate hydroxyl radicals ·OH, thereby mineralizing the refractory pollutants, i.e. new pollutants.

[0072] The electro-Fenton technology can effectively degrade the organic matters in the wastewater for a long time, and Fe 2+ and H2O2 in the solution are continuously generated at a certain rate, and the degradation of the new pollutants is more complete.

[0073] Fe 2+ The Fe(OH)3 sludge is not formed, the production of the iron sludge is reduced, the secondary pollution is almost not caused, and the subsequent treatment is simple.

[0074] Therefore, the utility model discloses a degradation of conventional pollutants and new pollutants in wastewater by the anode chamber 1 and the cathode electro-Fenton technology, which can reduce the risk of pollutants entering the environment and has remarkable economic and environmental benefits.

[0075] Specifically, the power generation bacteria 6 added in the anode chamber 1 are special anaerobic microorganisms, such as Geobacteraceae and rhodoferrax ferrireducens, which can relatively continuously and stably generate current by oxidizing organic matters without adding an electron transfer medium.

[0076] The anaerobic microorganisms are obtained by adding the electrochemically active bacterial suspension in the MFC running for a predetermined time (for example, half a year) into the anode chamber 1 during the starting process of the ALMCC system. The anode chamber 1 contains a nutrient solution, and the nutrient solution and the bacterial suspension are put into the anode chamber 1 at a certain ratio to create a suitable anaerobic environment for the power generation bacteria 6 to survive. The nutrient substance is continuously passed through nitrogen for at least 20 min before being moved into the anode chamber 1. The electrochemically active bacteria in the anode liquid are trained for a period of time, can adapt to the device, and serve as the power generation bacteria 6 of the device. During the training stage of the power generation bacteria 6, the anode liquid in the anode chamber 1 is regularly replaced to provide a training environment for the power generation bacteria 6.

[0077] Preferably, the reference electrode 11 is inserted into the anode chamber 1, and the reference electrode 11 is a calomel electrode. The reference electrode 11 is connected to the data acquisition system 22. The reference electrode 11 is used as a reference electrode when measuring the potentials of various electrodes.

[0078] Preferably, the anode graphite carbon felt 4 filled in the anode chamber 1 accounts for 2 / 3 of the volume of the anode chamber 1. Before being filled in the anode chamber 1, the anode graphite carbon felt 4 is boiled in 1 mol / L NaOH and 1 mol / L HCl for 20 min respectively, washed with ultrapure water until neutral, and soaked in ultrapure water for standby.

[0079] Preferably, the cathode graphite carbon felt 5 is soaked in acetone for 24 hours before being filled into the cathode chamber 2, and then is cleaned several times with ultrapure water and is baked in a muffle furnace at 450°C for 30 minutes.

[0080] In particular, the volume of the anode graphite carbon felt 4 in the embodiment is 1×1×0.5cm 3 5×15×0.5cm 3 The volume of the cathode graphite carbon felt 5 is 5×10.5×0.2cm 3 5×15×0.5cm 3 Further in particular, the volume of the anode graphite carbon felt 4 in the embodiment is 5×15×0.5cm 3 The volume of the cathode graphite carbon felt 5 is 5×15×0.5cm 3 Alternatively, the volume of the anode graphite carbon felt 4 is 1×1×0.5cm 3 The cathode graphite carbon felt 5 is cut into 5×10.5×0.2cm 3 .

[0081] Preferably, the cation exchange membrane 3 is boiled in 30% H2O2 and 0.5mol / L H2SO4 respectively for 1 hour, and then is washed with ultrapure water until neutral.

[0082] Preferably, the diameter of the anode carbon rod 12 and the cathode carbon rod 10 ranges from 5cm to 10cm. Further preferably, the diameter of the anode carbon rod 12 and the cathode carbon rod 10 is 5cm, 8cm or 10cm.

[0083] Preferably, the length of the anode carbon rod 12 and the cathode carbon rod 10 ranges from 10cm to 25cm. Further preferably, the length of the anode carbon rod 12 and the cathode carbon rod 10 is 10cm, 20cm or 25cm.

[0084] Preferably, the aeration structure includes an aeration pipe 19 and an air pump 21, the cathode chamber 2 is connected to the air pump 21 through the aeration pipe 19, and a flow meter 20 and the air pump 21 are installed on the aeration pipe 19. Oxygen is provided to the cathode chamber 2 by the air pump 21, and the flow meter 20 on the aeration pipe 19 is used to detect the gas flow through the aeration pipe 19. In particular, one end of the aeration pipe 19 is connected to the air pump 21, and the other end is connected to an aeration head 18, which is connected to the cathode chamber 2 and is convenient to disassemble.

[0085] Preferably, the pipeline connecting the water outlet 8 of the anode chamber 1 to the water inlet 70 of the cathode chamber 2 is a water pipe 16, and a second peristaltic pump 24 is installed on the water pipe 16.

[0086] Preferably, the anode electrode and the cathode electrode are both connected to the data acquisition system 22, and the device is operated, and the voltage is continuously collected by the data acquisition system 22. Specifically, the anode electrode is connected to one end of the data acquisition system 22, and the cathode electrode is connected to the other end of the data acquisition system 22, and the anode electrode, the data acquisition system 22 and the cathode electrode form a closed loop.

[0087] Preferably, the sewage pollutant treatment device further comprises a computer 23, and the computer is connected to the data acquisition system 22 through an external circuit.

[0088] The sewage pollutant treatment device in this embodiment is started with PBS buffer solution in the cathode chamber 2, and air is continuously supplied to the cathode chamber 2 by the air pump 21. The MFC is started and operated at room temperature, and the voltage is monitored and collected in real time by the data acquisition system 22. When the voltage is collected, the anode nutrient solution needs to be replaced, and the voltage is stable after the nutrient solution is replaced, which means that the MFC is successfully started.

[0089] The volume of the anode graphite carbon felt 4 in this embodiment is 1×1×0.5cm 3 , and the cathode graphite carbon felt 5 is cut into 5×10.5×0.2cm 3 . The diameter of the anode carbon rod 12 and the cathode carbon rod 10 is 5cm, and the length of the anode carbon rod 12 and the cathode carbon rod 10 is 25cm. The capacity of the cathode chamber 2 and the anode chamber 1 is 500mL.

[0090] The anode anaerobic condition is ORP below-200mV, and the cathode aerobic condition is dissolved oxygen content of 2-3mg / L. The pH of the cathode solution is 3.

[0091] The experimental temperature is at room temperature, and the light intensity ranges from 180μ·mol / (m 2 ·s) to 200μ·mol / (m 2 ·s).

[0092] A 500mL double single-groove biological glass reactor is used as a microbial fuel cell, and the device is built according to the design. The anode chamber 1 and the cathode chamber 2 are separated by a cation exchange membrane 3, the anode is filled with an anode graphite carbon felt with a volume of 1×1×0.5cm 3 , and a 25cm long anode carbon rod 12 is inserted as an anode electrode. The cathode is a cathode graphite carbon felt with a thickness of 0.2cm and an area of 5×10.5cm 2 , which is tied with titanium wire on a 25cm long cathode carbon rod 10 as a cathode electrode, and the anode carbon rod 12 and the cathode carbon rod 10 are connected by a resistor 13.

[0093] The pretreatment of carbon felt and cation exchange membrane 3 includes the following:

[0094] Anode carbon felt pretreatment: cut the graphite carbon felt into 1x1x0.5cm 3 , respectively, and washed with ultrapure water until neutral, and soaked in ultrapure water for standby.

[0095] Cathode carbon felt pretreatment: cut the graphite carbon felt into 5x10.5x0.2cm3 size, soak in acetone for 24h, and then wash with ultrapure water several times, and then burn in a muffle furnace at 450℃ for 30min.

[0096] Cation exchange membrane 3 pretreatment: boil with 30% H2O2 and 0.5mol / L H2SO4 for 1h, respectively, and washed with ultrapure water until neutral, and soaked in ultrapure water for standby.

[0097] Preparation of Co@NSC catalytic material

[0098] The Co@NSC catalytic material can be prepared by conventional means, and the focus of the technical solution is not here, which will not be described here.

[0099] MFC start-up

[0100] The nutrient solution and bacterial suspension are placed in the anode chamber 1 in proportion, and in order to create an anaerobic environment suitable for the survival of the electricity-producing bacteria 6, the nutrient substance is continuously purged with nitrogen for at least 20min before being moved into the anode chamber 1. At the start-up, the cathode chamber 2 contains PBS buffer solution, and is continuously aerated by air pump 21. The MFC is started and operated at room temperature, and the voltage is monitored and collected in real time. When the collected voltage decreases, the anode nutrient solution needs to be replaced, and until the voltage can be stabilized after replacing the nutrient solution, the MFC is successfully started.

[0101] Electro-Fenton degradation electrode preparation includes:

[0102] Loading of catalytic material: first weigh 5mg of material, add 1mL of ethanol, and 20μL of Nafion (5wt%) binder, and ultrasonic for 30min to form a uniform suspension. Use a pipette to evenly drop the suspension onto the pretreated carbon cloth electrode, and move 100μL at a time. After each drop, move the carbon cloth to a 60℃ oven, dry, and then proceed to the next drop until the prepared suspension is completely removed. After loading, the carbon cloth is placed in a 60℃ oven for 1h and then taken out for standby. The final loading on the carbon cloth is 0.625mg / cm 2 .

[0103] In the experiment, the sampling time interval is 8h, and sampling is carried out in the anode chamber 1 and the cathode chamber 2, respectively, and the voltage is collected by the data acquisition system 22.

[0104] The experimental device is as follows Figure 1The cathode material of the successfully started microbial fuel cell is replaced with Co@NSC catalytic material modified graphite carbon felt, and the cathode solution is 0.05 mol / L Na2SO4 solution with pH of 3, Fe 2+ The concentration of DMP is 1 mmol / L, and the initial concentration of DMP is 10 mg / L, to form a bio-electric Fenton system.

[0105] Routine pollutant determination:

[0106] According to the corresponding national standard, the COD in the water sample is determined.

[0107] DMP determination: DMP is determined by high performance liquid chromatography. To reduce solution error, 0.05 mol / L Na2SO4 solution is prepared to obtain DMP solutions with concentrations of 0.1 mg / L, 0.5 mg / L, 1 mg / L, 2 mg / L, 5 mg / L and 10 mg / L, and a DMP standard curve is obtained as shown in Figure 1-1 .

[0108] Multiple experimental cycles are carried out, and the voltage is monitored and determined in real time, as shown in Figure 1-2 is a voltage-time change graph, and the maximum output voltage of the sewage pollutant treatment device (the external resistance 13 is 1000 Ω) is 388.3 mV; as shown in Figure 1-3 (a), the maximum power density in the power curve is 434.8 W·m -3 . As shown in Figure 1-3 (b), the polarization curve of the battery is an important means to characterize the performance of the battery, and the existence of various polarization phenomena makes the actual voltage of the battery much lower than the theoretical voltage. This phenomenon of electrode potential deviating from the equilibrium potential is called polarization. Overpotential is caused by the resistance encountered by electrons in the transmission process, and is therefore closely related to the internal resistance of the battery. The internal resistance of the battery can be quantitatively obtained through the polarization curve, and the slope of the polarization curve is the internal resistance of the battery. As shown in Figure 1-3 (b), the modification of the supported catalytic material reduces the internal resistance of the fuel cell, and at the same time, the lower internal resistance has a higher power density, so it can be inferred that the battery with the supported catalytic material modified cathode has a higher power density.

[0109] In one experimental cycle, the COD and DMP concentrations in the water samples taken at different time points are determined, and the COD degradation efficiency curve is obtained as shown in Figure 1-4 (a), Figure 1-4 (b) is a DMP degradation efficiency change curve. As shown in Figure 1-3 It is found that the COD and DMP degradation efficiencies in one experimental cycle are 92.34% and 95.92%, respectively.

[0110] Obviously, the above embodiments of the present application are merely examples for clearly illustrating the present application, and are not intended to limit the implementation modes of the present application. For those skilled in the art, other different forms of changes or variations can be made on the basis of the above description. Here, it is not necessary and also impossible to exhaust all the implementation modes. Any modification, equivalent replacement and improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application claims.

Claims

1. A sewage contaminant treatment apparatus, characterised in that, It comprises an anode chamber (1), a cathode chamber (2), a cation exchange membrane (3), an aeration structure and a data acquisition system (22); The anode chamber (1) is connected with the outside first peristaltic pump (15), which transports sewage to the anode chamber (1); The anode chamber (1) contains an electrogenic bacteria solution of electrogenic bacteria (6); The anode chamber (1) is inserted with an anode carbon rod (12) and filled with an anode graphite carbon felt (4), and one end of the anode carbon rod (12) is connected with an external circuit (14); The cathode chamber (2) is inserted with a cathode carbon rod (10) provided with a cathode graphite carbon felt (5), and one end of the cathode carbon rod (10) is connected with the external circuit (14), and the anode carbon rod (12) and the cathode carbon rod (10) are connected through a resistor (13); The cation exchange membrane (3) is arranged between the anode chamber (1) and the cathode chamber (2), and the cation exchange membrane (3) is a proton exchange membrane; The water outlet (8) of the anode chamber (1) is connected with the water inlet (7) of the cathode chamber (2) through a pipeline, and the pipeline is provided with a second peristaltic pump (24); The anode chamber (1) utilizes the electrogenic bacteria (6) to decompose conventional pollutants in the sewage in the anode solution, converts chemical energy into electrical energy, generates electrons and protons, and generates electrons and protons; The electrons reach the cathode through the external circuit (14), and the protons are transmitted to the cathode chamber (2) through the cation exchange membrane (3); An aeration structure is connected to the cathode chamber (2), and dissolved oxygen in the cathode chamber (2) combines with electrons and protons to generate H2O2, which then combines with Fe 2+ The Fenton reaction occurs to generate hydroxyl radicals ·OH, which mineralize novel pollutants in the cathode solution; The anode carbon rod (12) and the cathode carbon rod (10) are connected with the data acquisition system (22).

2. The device of claim 1, wherein, The chemical reaction formula of the electricity-producing bacteria (6) in the anode chamber (1) is: COD + 6H2O→ 6CO2+ 24H + + 24e - 1; The new pollutants are decomposed into intermediate products in the cathode chamber (2), and further decomposed into small molecular inorganic substances; Fe 2+ is simultaneously oxidized to Fe 3+ , the chemical reaction in the cathode chamber is: + + 2e - → H2O2 H2O2 + Fe 2+ → Fe 3+ + ·OH + OH - (1-2) New pollutants +·OH→ intermediate products (1-3) Intermediate products +·OH→ CO2+H2O+small molecular inorganic substances (1-4).

3. The device of claim 2, wherein, The cathode graphite carbon felt (5) is loaded with a catalytic material.

4. The device of claim 3, wherein, The cathode graphite carbon felt (5) is fixed on the cathode carbon rod (10) by titanium wire.

5. The device of claim 4, wherein, The anode graphite carbon felt (4) filled in the anode chamber (1) accounts for 2 / 3 of the volume of the anode chamber (1).

6. The device of claim 5, wherein, Before being filled in the anode chamber (1), the anode graphite carbon felt (4) needs to be boiled in 1 mol / L NaOH and 1 mol / L HCl for 20 min respectively, washed with ultrapure water until neutral, and soaked in ultrapure water for standby.

7. The device of claim 6, wherein, Before being filled in the cathode chamber (2), the cathode graphite carbon felt (5) needs to be soaked in acetone for 24 h, washed several times with ultrapure water after taking out, and baked at 450℃ for 30 min in a muffle furnace.

8. The device of claim 7, wherein, The cation exchange membrane (3) needs to be boiled in 30% H2O2 and 0.5 mol / L H2SO4 for 1 h respectively, and then washed with ultrapure water until neutral.

9. The device of claim 8, wherein, The diameter of the anode carbon rod (12) and the cathode carbon rod (10) ranges from 5 cm to 10 cm.

10. The device of claim 9, wherein, The length of the anode carbon rod (12) and the cathode carbon rod (10) ranges from 10 cm to 25 cm.

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