CN111410370A - Self-supporting electrocatalytic oxidation-microbial fuel cell coupling system and application thereof - Google Patents
Self-supporting electrocatalytic oxidation-microbial fuel cell coupling system and application thereof Download PDFInfo
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Abstract
The invention provides a self-supporting electrocatalytic oxidation-microbial fuel cell coupling system and application thereof, and relates to the field of electrochemical water treatment. The electrocatalytic oxidation degradation module in the self-supporting electrocatalytic oxidation-microbial fuel cell coupling system provided by the invention can improve the biodegradability of the wastewater, namely, the structural damage (decoloration process) and toxicity reduction of macromolecular organic matters in the wastewater are completed, and the subsequent treatment of a microbial fuel cell module is facilitated. The microbial fuel cell module can remove COD in the wastewater to make the wastewater reach the standard and discharge the wastewater. In addition, the microbial fuel cell battery module can also stably generate electricity, and the electricity is supplied to the electrocatalytic oxidation degradation module through the electric energy storage-regulation module, so that self-sustaining is realized. The coupling system provided by the invention can well remove the color and COD of the dye wastewater.
Description
Technical Field
The invention relates to the field of electrochemical water treatment, in particular to a self-supporting electrocatalytic oxidation-microbial fuel cell coupling system and application thereof.
Background
At present, printing and dyeing and related industries become a large household for discharging industrial wastewater in China, and according to statistics, the wastewater discharge amount of the national printing and dyeing and related industries is about 3 × 106～4×106m3And d. The dye wastewater has the characteristics of high COD value, high chromaticity, high salt content, high toxicity, easy carcinogenesis and difficult biodegradation, so the dye wastewater becomes a difficult point for industrial wastewater treatment. The dye can be classified according to chemical structure (mainly according to the structure of a conjugated system contained in the dye) and can be divided into: azo dyes, phthalocyanine dyes, anthraquinone dyes, cyanine dyes, indigoid dyes, arylmethane dyes, nitro dyes, nitroso dyes, and the like, and among these, azo dyes are most widely used.
The dye wastewater is characterized in that: (1) high COD concentration, low BOD/COD value and poor biodegradability. The COD concentration of water is high due to the lost dye in the dye production process, the biodegradation capability is very low due to the self type and structural complexity of the dye, and the conventional biological treatment technology is difficult to treat. (2) Large color and complex composition. The dyes and intermediates produced by dye plants are of various varieties, have large variation of pH value, develop towards photolysis resistance, oxidation resistance and biological oxidation resistance, and are difficult to find a uniform method, thereby causing the technical difficulty of treatment.
The biggest treatment difficulty of dye wastewater is the removal of wastewater chromaticity and the treatment of the difficultly biodegradable organic matters in water. The treatment mechanism is roughly divided into two types: (1) enrichment of the chromogenic substance: the waste water can be treated by adopting the adsorbent, so that the chromogenic substances in the water are enriched, the waste water is decolorized, and then the waste adsorbent is subjected to advanced treatment; (2) direct destruction of the chromonic material: the wastewater is directly subjected to physical and chemical or biological treatment, so that chromophoric groups of dye organic matters in the wastewater are destroyed, and the color of the wastewater is removed.
The main treatment methods reported in the current research include chemical methods, physical methods and biological methods. (1) The common physical methods mainly include filtration, precipitation, air flotation, extraction, membrane separation, etc. In the pretreatment process of the wastewater, a physical method is mostly adopted, and pollutants are enriched or some solid pollutants in the water are separated, but some organic pollutants with high solubility in the water are difficult to remove. In addition, the physical methods mostly perform pollutant transfer rather than degradation elimination. (2) The chemical method is mainly characterized in that some chemical substances are added into the polluted water body, and the purpose of purifying the water body is achieved by the reaction of the chemical substances and the water body pollutants. Common chemical methods are neutralization, flocculation, oxidation, reduction, and the like. Although the method can achieve a good water treatment effect, the cost is high, secondary pollution is caused to water due to addition of chemical substances, and the method does not accord with the current green and clean principle. (3) The biological method mainly depends on the metabolism of microorganisms to remove organic pollutants in the wastewater. Common biological methods mainly comprise an aerobic activated sludge method, an anaerobic sludge method, a biological membrane, biological enzymes and combination of various biological methods. Biological methods have been studied for the longest time and have been widely used in the field of domestic sewage because of their low cost and good treatment effect on biodegradable sewage. However, the method has the disadvantages of long time consumption, large occupied area and poor treatment effect on some high-toxicity wastewater which is difficult to biodegrade.
Therefore, electrocatalytic oxidation technology and microbial fuel cell technology are attracting attention because of their particular advantages. The electrocatalytic oxidation technology for organic matters refers to a method for achieving the effect of degrading pollutants by utilizing the organic matters to carry out direct electron gain-loss reaction on the surface of an electrode or utilizing various active free radical substances (represented by HO & free radicals) generated in the electrochemical process to oxidize and remove the organic matters. The electrocatalytic oxidation water treatment technology is a green water treatment technology, does not need chemical agents to be added, does not generate sludge, is simple in equipment and operation, mild in reaction process, can be flexibly matched with other technologies, can realize on-site treatment, and is suitable for the sewage treatment process with small sewage discharge scale. However, electrocatalytic oxidation techniques also present some major problems in engineering applications: 1) the catalytic efficiency is low; 2) the mass transfer effect is poor; 3) the energy consumption is high. In view of these characteristics, electrocatalytic oxidation technology is widely used in pretreatment processes for nonbiodegradable organic wastewater to improve the biodegradability of wastewater.
Microbial fuelThe fuel cell (MFC) is a promising energy recovery technology, and its working principle is that organic matters are catalytically degraded by anode microorganisms, and chemical energy can be converted into electric energy in the degradation process, so that it is a clean energy technology. The application direction of the method mainly comprises the fields of bioremediation, biosensors, wastewater treatment, nanoelectronics and biomedicine. Among them, wastewater treatment is recognized as the most promising field of application for microbial fuel cells. Among the main treatment processes in sewage plants, activated sludge processes and biofilters are the most common core technologies for sewage treatment. The advantages of microbial fuel cells over these traditional bioprocessing technologies are: (1) MFC technology can produce electric energy while processing the waste water; (2) the MFC technology greatly reduces the generation of excess sludge; (3) the use of MFC technology avoids the release of malodours into the environment. In addition, the economic benefits of MFC technology are also superior to typical activated sludge processes. Taking domestic sewage as an example, the electric energy of 0.65 kW.h/m can be obtained by adopting MFC to treat the domestic sewage3. The wastewater treatment by the typical activated sludge method needs 0.2-0.4 kwh/m3The electric energy of (1). Despite the outstanding advantages, the characteristics of the dye wastewater still make the MFC system face the characteristics of microbial acclimation, long start-up time, poor treatment effect and the like when the MFC system is treated.
Disclosure of Invention
In view of the above, the present invention provides a self-supporting electrocatalytic oxidation-microbial fuel cell coupling system and applications thereof. The coupling system provided by the invention couples the electrocatalytic oxidation technology with the microbial fuel cell technology, fully exerts the advantages of the electrocatalytic oxidation technology and the microbial fuel cell technology, avoids the disadvantages of the electrocatalytic oxidation technology and the microbial fuel cell technology, and completes high-efficiency and low-energy-consumption treatment on the dye type wastewater difficult to biodegrade.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a self-supporting electrocatalytic oxidation-microbial fuel cell coupling system, which comprises a pretreatment module, an electrocatalytic oxidation degradation module and a microbial fuel cell module which are sequentially communicated; the microbial fuel cell stack module comprises a plurality of microbial fuel cells, and the electrocatalytic oxidative degradation module is communicated with the plurality of microbial fuel cells in parallel;
the microbial fuel cell module is also sequentially connected with the electric energy storage-regulation module and the electrocatalytic oxidation degradation module; the electrocatalytic oxidative degradation module is also communicated with a direct current power supply.
Preferably, the electrocatalytic oxidative degradation module is a 2-dimensional electrocatalytic oxidative degradation system or a 2.5-dimensional electrocatalytic oxidative degradation system.
Preferably, the anode of the 2.5-dimensional electrocatalytic oxidative degradation system consists of a titanium matrix sleeve, an active layer deposited on the titanium matrix sleeve, a magnetic substance attached to the active layer and a magnet filled inside the titanium matrix sleeve; the magnetic substance is magnetic particles wrapped by a functional layer.
Preferably, the functional layer is made of Sb-SnO2、Pb3O4、PbO2Or TiOX。
Preferably, the active layer is made of PbO2、Sb-SnO2Ir/Ru oxide or titanium suboxide.
Preferably, the microbial fuel cell is a single-chamber type air cathode microbial fuel cell.
Preferably, the anode of the single-chamber air cathode microbial fuel cell is a carbon felt electrode.
Preferably, the air cathode of the single-chamber air cathode microbial fuel cell comprises a support layer and a diffusion layer and a catalytic layer which are sequentially attached on the support layer;
the support layer is obtained by brushing carbon fiber cloth on a mixture of carbon black and 40% concentration PTFE emulsion;
the diffusion layer is obtained by coating 60% PTFE emulsion on the support layer, air-drying and sintering at high temperature;
the catalytic layer is Pt/C.
Preferably, the electric energy storage and regulation module comprises two charging modules and a control module.
The invention also provides the application of the self-supporting electrocatalytic oxidation-microbial fuel cell coupling system in the technical scheme in treating dye wastewater difficult to biodegrade.
The invention provides a self-supporting electrocatalytic oxidation-microbial fuel cell coupling system, which comprises a pretreatment module, an electrocatalytic oxidation degradation module and a microbial fuel cell module which are sequentially communicated; the microbial fuel cell stack module comprises a plurality of microbial fuel cells, and the electrocatalytic oxidative degradation module is communicated with the plurality of microbial fuel cells in parallel; the microbial fuel cell module is also sequentially connected with the electric energy storage-regulation module and the electrocatalytic oxidation degradation module; the electrocatalytic oxidative degradation module is also communicated with a direct current power supply. The electrocatalytic oxidation degradation module in the coupling system provided by the invention can improve the biodegradability of dye wastewater, namely, the structural damage (decoloration process) and toxicity reduction of macromolecular organic matters in the wastewater are completed, and the subsequent treatment of a microbial fuel cell Module (MFC) is facilitated. The microbial fuel cell module can remove COD in the wastewater to make the wastewater reach the standard and discharge the wastewater. In addition, the microbial fuel cell battery module can also stably generate electricity, and the electricity is supplied to the electrocatalytic oxidation degradation module through the electric energy storage-regulation module, so that self-sustaining is realized. The coupling system provided by the invention can well remove the color and COD in the dye wastewater. The data of the examples show that: the invention can reach 100% decolorization rate and over 80% COD removal rate for different kinds of dye wastewater.
Drawings
FIG. 1 is a schematic diagram of a 2.5-dimensional electrocatalytic oxidative degradation system for use in the present invention;
FIG. 2 is a schematic view of a self-supporting electrocatalytic oxidation-microbial fuel cell coupling system provided by the present invention.
Detailed Description
The invention provides a self-supporting electrocatalytic oxidation-microbial fuel cell coupling system, which comprises a pretreatment module, an electrocatalytic oxidation degradation module and a microbial fuel cell module which are sequentially communicated; the microbial fuel cell stack module comprises a plurality of microbial fuel cells, and the electrocatalytic oxidative degradation module is communicated with the plurality of microbial fuel cells in parallel;
the microbial fuel cell module is also sequentially connected with the electric energy storage-regulation module and the electrocatalytic oxidation degradation module; the electrocatalytic oxidative degradation module is also communicated with a direct current power supply.
In the invention, the self-supporting electrocatalytic oxidation-microbial fuel cell coupling system comprises a water circuit and an electric circuit on the connection.
In the invention, the waterway comprises a pretreatment module, an electrocatalytic oxidation degradation module and a microbial fuel cell module which are sequentially connected. The water circuit of the self-supporting electrocatalytic oxidation-microbial fuel cell coupling system is specifically described as follows:
the invention provides a waterway of a self-supporting electrocatalytic oxidation-microbial fuel cell coupling system, which comprises a pretreatment module. In the present invention, the purpose of the pretreatment module is to remove solid impurities in wastewater. The specific device of the pretreatment system is not limited in the invention, as long as the solid impurities in the wastewater can be removed, and the device is specifically a filter screen.
The waterway of the self-supporting electrocatalytic oxidation-microbial fuel cell coupling system provided by the invention comprises an electrocatalytic oxidation degradation module. In the present invention, the electrocatalytic oxidative degradation module is preferably a 2-dimensional electrocatalytic oxidative degradation system or a 2.5-dimensional electrocatalytic oxidative degradation system, and is more preferably a 2.5-dimensional electrocatalytic oxidative degradation system. In the present invention, the 2.5-dimensional electrocatalytic oxidative degradation system preferably includes an anode, a cathode, an electrolytic cell, and an electrolyte.
In the present invention, the anode of the 2.5-dimensional electrocatalytic oxidative degradation system preferably consists of a titanium-based casing, an active layer deposited on the titanium-based casing, a magnetic substance attached to the active layer, and a magnet filled inside the titanium-based casing; the magnetic substance is magnetic particles wrapped by the functional layer; the magnetic substance is adsorbed on the titanium substrate sleeve by magnetic force. In the present invention, the magnetic particles are preferably Fe3O4Particles; the particle size of the magnetic particles is preferably 50-300 meshes; the material of the functional layer is preferably Sb-SnO2、Pb3O4、PbO2Or TiOX. In the present invention, the material of the active layer is preferably PbO2、Sb-SnO2Ir/Ru oxide or titanium suboxide.
In the present invention, the cathode of the 2.5-dimensional electrocatalytic oxidative degradation system is preferably a copper sheet.
In the present invention, the material of the electrolytic cell of the 2.5 d electrocatalytic oxidative degradation system is preferably acrylic material.
FIG. 1 is a schematic view of a 2.5-dimensional electrocatalytic oxidative degradation system used in the present invention, wherein a partially enlarged view of an anode shows that an active layer is deposited on a titanium substrate sleeve, and a magnetic substance is attached to the active layer, wherein the magnetic substance is magnetic particles wrapped by a functional layer; the titanium substrate sleeve is filled with a magnet.
In the invention, the electrocatalytic oxidation degradation module can improve the biodegradability of the dye wastewater, namely, the structural damage (decolorization process) and toxicity reduction of macromolecular organic matters in the dye wastewater are completed, and the removal of the wastewater COD belongs to a secondary function, so that the electrocatalytic module can operate under a weak current parameter condition (low power consumption), and the operation power consumption of the electrocatalytic oxidation degradation module can be matched with the electricity generation capacity of the microbial fuel cell module. Specifically, the outer surface of the 2.5-dimensional electrocatalytic oxidation degradation system is not in a traditional flat shape, but has more active particles, so that more electrochemical active sites can be generated, better catalytic degradation effect on organic matters is achieved, and the organic matters are converted into more organic matters with small molecular weight and small toxicity, so that the biological toxicity of the electrolyzed water sample is reduced, and the treatment of a subsequent MFC system is facilitated.
The waterway of the self-supporting electrocatalytic oxidation-microbial fuel cell coupling system provided by the invention comprises a microbial fuel cell module; the microbial fuel cell stack module comprises a plurality of microbial fuel cells; the electrocatalytic oxidative degradation module is in parallel communication with a plurality of Microbial Fuel Cells (MFCs).
In the present invention, the microbial fuel cell is preferably a single-chamber type air cathode microbial fuel cell.
In the present invention, the anode of the single-chamber air cathode microbial fuel cell is preferably a carbon felt electrode; before use, the carbon felt electrode is preferably subjected to soaking cleaning and high-temperature heat treatment; the reagent for soaking and cleaning is preferably NaOH solution; the temperature of the high-temperature heat treatment is preferably 100-450 ℃, and the time is preferably 1-30 min. In the present invention, the air cathode of the single-chamber type air cathode microbial fuel cell preferably comprises a support layer and a diffusion layer and a catalytic layer sequentially attached to the support layer. In the present invention, the support layer is preferably obtained by brushing carbon fiber cloth with a mixture of carbon black and PTFE emulsion; the mass concentration of the PTFE emulsion is preferably 40%; the mass ratio of the carbon black to the PTFE emulsion with the mass concentration of 40% is preferably 1: 1.
In the invention, the diffusion layer is preferably obtained by coating PTFE emulsion on the support layer, air-drying and sintering at high temperature; the mass concentration of the PTFE emulsion is preferably 60%; the high-temperature sintering temperature is preferably 100-450 ℃, and the time is preferably 1-30 min.
In the present invention, the catalytic layer is preferably Pt/C.
In the invention, when the Microbial Fuel Cell (MFC) in the microbial fuel cell group module is used, particularly the starting process is preferably divided into three stages, the first stage preferably adopts artificial synthetic wastewater as a substrate to accelerate the domestication of microorganisms, and the next stage can be entered after the output voltage of the microbial fuel cell group module is stabilized, wherein the artificial synthetic wastewater comprises the components of 250 mg/L glucose and NaHCO3100mg/L、(NH4)2SO432mg/L、KH2PO46mg/L、FeCl3·6H2O1.5mg/L、MgSO4·7H2O2 mg/L and MnCl2·4H2O 1.5mg/L。
The substrate in the second stage is preferably mixed water distribution of the artificial synthetic wastewater and the effluent of the electrocatalytic oxidative degradation module (the proportion of the effluent of the electrocatalytic oxidative degradation module can be gradually increased until the volume ratio of the artificial synthetic wastewater to the effluent of the electrocatalytic oxidative degradation module is 1: 1) to selectively domesticate the electrogenic microorganisms. At this stage, the output voltage of the microbial fuel cell stack module rapidly dropped after substrate replacement, indicating that a sudden change in metabolic environment and load impact would limit the value-added metabolism of some of the electricity-producing microorganisms. In the present invention, the composition of the synthetic wastewater is preferably the same as that of the synthetic wastewater prepared in the first stage, and thus, the details thereof are not repeated. Along with the advancing of the operation, after the electricity-generating microorganisms gradually adapt to a new metabolic environment, the output voltage of the microbial fuel cell stack module gradually rises and is stable, and the next stage can be started after the output voltage is stable.
Preferably, the substrate in the third stage is completely discharged from the module by adopting electrocatalytic oxidation degradation to further acclimate the metabolic activity of the electrogenesis microorganisms, the output voltage of the microbial fuel cell module is firstly reduced and then increased, and finally is stabilized at 0.60 +/-0.05 mV, which indicates that the electrogenesis microorganisms are adapted to the characteristics of actual wastewater.
According to the invention, the microbial fuel cell module can remove the COD of the dye wastewater, so that the dye wastewater can reach the discharge standard, and meanwhile, the electricity can be stably generated. Meanwhile, the single-chamber air cathode microbial fuel cell used by the self-supporting electrocatalytic oxidation-microbial fuel cell coupling system has low cost, pollution-free air is used as a cathode chamber to directly replace the cathode chamber in the double-chamber air cathode microbial fuel cell, cathode materials are directly exposed in the air, and only the anode chamber is left, so that the system structure is simplified, the running cost of the cell is reduced, and in addition, the output power of the self-supporting electrocatalytic oxidation-microbial fuel cell coupling system is higher than that of most double-chamber air cathode microbial fuel cells.
In the invention, the circuit comprises the microbial fuel cell module and is also sequentially connected with the electric energy storage-regulation module and the electrocatalytic oxidation degradation module; the electrocatalytic oxidative degradation module is also communicated with a direct current power supply. The circuit of the self-supporting electrocatalytic oxidation-microbial fuel cell coupling system is described in detail as follows:
in the invention, the microbial fuel cell battery module is sequentially connected with the electric energy storage-regulation module and the electrocatalytic oxidation and degradation module, stores the electric energy generated by the microbial fuel cell battery module in the electric energy storage-regulation module and supplies power to the electrocatalytic oxidation and degradation module.
In the present invention, the electric energy storage-adjustment module preferably includes two charging modules and a control module; the two charging modules are used and prepared one by one, and are charged by using the electric energy generated by the microbial fuel cell battery module so as to achieve the purpose of electric energy storage; the control module functions include: 1) adjusting different microbial fuel cell battery modules to charge the charging modules, and 2) controlling the charging and discharging states of the two charging modules. The invention has no special requirements on the specific equipment of the electric energy storage-regulation module, as long as the electric energy storage-regulation module can comprise two charging modules and one control module, and particularly, the electric energy storage-regulation module is a device similar to a charger baby.
In the present invention, the matching of system parameters between the electrocatalytic oxidative degradation module and the microbial fuel cell stack module is required in the following aspects: (1) the hydraulic residence times (H) of the different modules need to be matched to one another, i.e. HMFC＝nMFC*HElectrocatalytic oxidative degradation moduleWherein: hMFCFor the hydraulic residence time in MFC, nMFCIs the number of MFCs in the microbial fuel cell stack module, HElectrocatalytic oxidative degradation moduleIs the hydraulic retention time in the electrocatalytic oxidative degradation module. (2) The operating (output) voltages (U) of the different modules need to be matched to one another, i.e. UElectrocatalytic oxidative degradation module＝nMFC*UMFCWherein: u shapeElectrocatalytic oxidative degradation moduleOperating voltage, U, for electrocatalytic oxidative degradation of the moduleMFCFor the output voltage, n, of a single microbial fuel cell in stable operationMFCIs the number of MFCs in the microbial fuel cell stack module.
In the invention, the electrocatalytic oxidative degradation module is connected with a direct current power supply besides the electric energy storage-regulation module; at the initial stage of operation of the self-sustaining electrocatalytic oxidation-microbial fuel cell coupling system, the power supply of the electrocatalytic oxidation degradation module needs to be supplied by an external direct current power supply, and the self-sustaining power supply can be switched to after the operation of the microbial fuel cell module is stable.
FIG. 2 is a schematic view of a self-sustaining electro-catalytic oxidation-microbial fuel cell coupling system provided by the present invention, wherein wastewater sequentially passes through a pretreatment module to remove solid impurities, then enters an electro-catalytic oxidation degradation module, and then enters a microbial fuel cell module formed by a plurality of microbial fuel cells connected in parallel, so as to reach a discharge standard, and is directly discharged; meanwhile, electric energy generated by the microbial fuel cell module is collected into the electric energy storage-regulation module and supplies power for the electrocatalytic oxidation degradation module; wherein an external direct current power supply is used as a standby power supply of the electrocatalytic oxidative degradation module.
The invention also provides the application of the self-supporting electrocatalytic oxidation-microbial fuel cell coupling system in the technical scheme in treating dye wastewater difficult to biodegrade.
In the invention, the dye in the dye type wastewater difficult to biodegrade comprises methyl orange, acid red G or aniline yellow.
The self-supporting catalytic oxidation-microbial fuel cell coupling system provided by the invention has excellent biodegradability for dyes in wastewater, so that the self-supporting catalytic oxidation-microbial fuel cell coupling system can be applied to treatment of dye type wastewater difficult to biodegrade.
The self-supporting electrocatalytic oxidation-microbial fuel cell coupling system and the application thereof provided by the present invention will be described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
Example 1
The dye wastewater used in the example is wastewater containing methyl orange, and the concentration of the methyl orange is 1100 mg/L and 540 mg/L.
The anode of the electrocatalytic oxidative degradation module comprises: the titanium substrate sleeve pipe, the Ir/Ru oxide layer deposited on the titanium substrate sleeve pipe, and the magnetic substance attached to the Ir/Ru oxide layer, wherein the magnetic substance is magnetic particles wrapped by a functional layer, and the functional layer is made of Sb-SnO2The magnetic particles are Fe3O4The interior of the titanium substrate sleeve is filled with a magnet; the cathode is a titanium mesh cathode and is carried out by a diaphragm-free two-electrode system. The treatment voltage isAt 4V, the hydraulic retention time is 12h, the dye wastewater decolorization rate is 100%, and the COD removal rate is 12.5%. The obtained wastewater enters a subsequent microbial fuel cell stack module.
The starting process of the Microbial Fuel Cell (MFC) in the microbial fuel cell stack module is divided into three stages, wherein the first stage adopts artificially synthesized wastewater (consisting of 250 mg/L glucose and NaHCO)3100mg/L、(NH4)2SO432mg/L、KH2PO46mg/L、FeCl3·6H2O 1.5mg/L、MgSO4·7H2O2 mg/L and MnCl2·4H2O1.5 mg/L.) as a substrate to accelerate the acclimation of microorganisms, and entering the next stage when the output voltage of the microbial fuel cell stack module is stable, wherein the substrate in the second stage selectively acclimates the electrogenic microorganisms by adopting mixed water distribution of artificially synthesized wastewater and effluent of the electrocatalytic oxidative degradation module (the proportion of the effluent of the electrocatalytic oxidative degradation module can be gradually increased until the volume ratio is 1: 1).
When the MFC runs stably, 8 MFC devices are connected in parallel, the generated electric energy is collected by the electric energy storage-regulation module and fed back and output to the electrocatalytic oxidation degradation module, and the normal running of the electrocatalytic oxidation degradation process is maintained;
the COD content of the final effluent of the microbial fuel cell stack module is 67.5 mg/L, and the removal rate is 87.5%.
Example 2
The wastewater used in the example is wastewater containing acid red G, the concentration of the acid red G is 100 mg/L, and the COD concentration of the wastewater is 27.8 mg/L.
The anode of the electrocatalytic oxidative degradation module comprises: a titanium substrate sleeve, a lead dioxide layer deposited on the titanium substrate sleeve, and a magnetic substance attached on the lead dioxide layer, wherein the magnetic substance is Pb-coated3O4Encapsulated Fe3O4The particles are filled in the magnet inside the titanium substrate sleeve, and the cathode is a copper sheet; the method is carried out by a diaphragm-free two-electrode system. The current density of the treatment used was 5.0mA/cm2(corresponding treatment voltage is 4.7V), the hydraulic retention time is 2h, the dye wastewater decolorization rate is 87.8%, and the wastewater COD removal rate is 8.19%. The obtained wastewater enters a subsequent microbial fuel cell stack module.
The MFC start-up procedure is divided into three stages as in example 1. And after the third stage, the system enters a stable operation stage, and the output voltage is finally stabilized at 0.45 +/-0.05 mV, which indicates that the electrogenic microorganisms adapt to the characteristics of actual wastewater.
When the MFC runs stably, connecting 12 MFC devices in parallel, collecting the generated electric energy by the electric energy storage-regulation module, feeding back and outputting the electric energy to the electrocatalytic oxidation degradation module, and maintaining the normal running of the electrocatalytic oxidation degradation process;
the COD content of the final effluent of the microbial fuel cell stack module is 0.56 mg/L, and the removal rate is 98%.
Example 3
The wastewater used in the example was aniline yellow-containing wastewater, the aniline yellow concentration was 105 mg/L, and the COD concentration of the wastewater was 420 mg/L.
The electrocatalytic oxidative degradation module adopts a graphite anode and a stainless steel cathode, and external magnetic particles are not used on the surface of the anode and are carried out by a diaphragm-free two-electrode system. When the used treatment voltage is 2.0V, the hydraulic retention time is 12h, the dye wastewater decolorization rate is 86.1%, and the wastewater COD removal rate is 20.8%. The obtained wastewater enters a subsequent microbial fuel cell stack module.
The MFC start-up procedure is divided into three stages as in example 1. And after the third stage, the system enters a stable operation stage, and the output voltage is finally stabilized at 0.55 +/-0.05 mV, which indicates that the electrogenic microorganisms adapt to the characteristics of actual wastewater.
When the MFC runs stably, 4 MFC devices are connected in parallel, the generated electric energy is collected by the electric energy storage-regulation module and fed back and output to the electrocatalytic oxidation degradation module, and the normal running of the electrocatalytic oxidation degradation process is maintained;
the COD content of the final effluent of the microbial fuel cell stack module is 59 mg/L, and the removal rate is 86%.
The electrocatalytic oxidation degradation module in the coupling system provided by the invention can improve the biodegradability of dye wastewater, namely, the structural damage (decoloration process) and toxicity reduction of macromolecular organic matters in the wastewater are completed, and the subsequent treatment of a microbial fuel cell Module (MFC) is facilitated. The microbial fuel cell module can remove COD in the wastewater to make the wastewater reach the standard and discharge the wastewater. In addition, the microbial fuel cell battery module can also stably generate electricity, and the electricity is supplied to the electrocatalytic oxidation degradation module through the electric energy storage-regulation module, so that self-sustaining is realized.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A self-supporting electrocatalytic oxidation-microbial fuel cell coupling system is characterized by comprising a pretreatment module, an electrocatalytic oxidation degradation module and a microbial fuel cell module which are sequentially communicated; the microbial fuel cell stack module comprises a plurality of microbial fuel cells, and the electrocatalytic oxidative degradation module is communicated with the plurality of microbial fuel cells in parallel;
the microbial fuel cell module is also sequentially connected with the electric energy storage-regulation module and the electrocatalytic oxidation degradation module; the electrocatalytic oxidative degradation module is also communicated with a direct current power supply.
2. The self-contained electrocatalytic oxidation-microbial fuel cell coupling system of claim 1, wherein the electrocatalytic oxidative degradation module is a 2-dimensional electrocatalytic oxidative degradation system or a 2.5-dimensional electrocatalytic oxidative degradation system.
3. The self-contained electrocatalytic oxidation-microbial fuel cell coupling system of claim 2, wherein the anode of the 2.5-dimensional electrocatalytic oxidation degradation system is composed of a titanium-based casing, an active layer deposited on the titanium-based casing, a magnetic substance attached to the active layer, and a magnet filled inside the titanium-based casing; the magnetic substance is magnetic particles wrapped by a functional layer.
4. The self-supporting electrocatalytic oxidation-microbial fuel cell coupling system of claim 3, wherein the functional layer is made of Sb-SnO2、Pb3O4、PbO2Or TiOX。
5. The self-contained electrocatalytic oxidation-microbial fuel cell coupling system of claim 3, wherein the active layer comprises PbO2、Sb-SnO2Ir/Ru oxide or titanium suboxide.
6. The self-contained electrocatalytic oxidation-microbial fuel cell coupling system of claim 1, wherein the microbial fuel cell is a single-compartment air cathode microbial fuel cell.
7. The self-contained electrocatalytic oxidation-microbial fuel cell coupling system of claim 6, wherein the anode of the single-chamber air cathode microbial fuel cell is a carbon felt electrode.
8. The self-contained electrocatalytic oxidation-microbial fuel cell coupling system of claim 6, wherein the air cathode of the single-chamber air cathode microbial fuel cell comprises a support layer and a diffusion layer and a catalytic layer sequentially attached to the support layer;
the supporting layer is obtained by brushing carbon fiber cloth on a mixture of carbon black and PTFE emulsion;
the diffusion layer is obtained by coating PTFE emulsion on the supporting layer, air-drying and sintering at high temperature;
the catalytic layer is Pt/C.
9. The self-contained electrocatalytic oxidation-microbial fuel cell coupling system of claim 1, wherein said electrical energy storage-conditioning module comprises two charging modules and a control module.
10. The use of the self-supporting electrocatalytic oxidation-microbial fuel cell coupled system of any one of claims 1 to 9 in the treatment of dye-based wastewater difficult to biodegrade.
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