CN114920429B - Pigment effluent treatment plant of MFC coupling electricity Fenton - Google Patents

Pigment effluent treatment plant of MFC coupling electricity Fenton Download PDF

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CN114920429B
CN114920429B CN202210667155.5A CN202210667155A CN114920429B CN 114920429 B CN114920429 B CN 114920429B CN 202210667155 A CN202210667155 A CN 202210667155A CN 114920429 B CN114920429 B CN 114920429B
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mfc
electrode
reaction tank
electric fenton
tank
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CN114920429A (en
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阮仁俊
余成龙
吴海芹
王惠
赵昌爽
李祎多
李泽煜
黄斌
柯凡
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Anhui Polytechnic University
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Anhui Polytechnic University
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/005—Combined electrochemical biological processes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/28—Anaerobic digestion processes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

Abstract

The invention discloses a pigment wastewater treatment device of MFC coupling electric Fenton, which comprises an MFC reaction zone and an electric Fenton reaction zone; the MFC reaction zone comprises an aeration deoxidization chamber and an MFC electrode reaction tank, wherein an aeration pipeline I communicated with an external air pump is arranged in the aeration deoxidization chamber, the aeration deoxidization chamber is communicated with an external wastewater tank through a water inlet valve, and the aeration deoxidization chamber is communicated with the MFC electrode reaction tank through a water outlet; an MFC cathode, an MFC anode and a proton exchange membrane positioned between the MFC cathode and the MFC anode are arranged in the MFC electrode reaction tank; the electric Fenton reaction zone comprises an adjusting tank and an electrode reaction tank, the adjusting tank is communicated with the MFC electrode reaction tank through an MFC water outlet, the adjusting tank is communicated with the electrode reaction tank through an electric Fenton water inlet, an aeration pipeline II communicated with an external air pump is also laid at the lower part of the adjusting tank, a plurality of groups of electrode pairs are arranged in the electrode reaction tank, and each group of electrode pairs comprises an electric Fenton anode and an electric Fenton cathode; the electric energy generated by the MFC electrode reaction tank is connected with an electric Fenton anode and an electric Fenton cathode in the electrode reaction tank through wires; the lower part of the electrode reaction tank is provided with a water outlet valve.

Description

Pigment effluent treatment plant of MFC coupling electricity Fenton
Technical Field
The invention relates to a pigment wastewater treatment device of MFC coupling electricity Fenton.
Background
With the rapid development of industry, pigment waste water generated by pigment production enterprises is more and more various, has complex components and generates great harm to ecological environment, so that the pigment waste water can be discharged after advanced treatment. The MFC method (microbial fuel cell) and the electric Fenton method (electro Fenton method) are advanced pigment wastewater treatment methods at present, and compared with the traditional treatment method, the two methods can treat pigment wastewater better and bring better economic benefit. However, the two methods cannot be applied on a large scale at present, mainly because of certain limitations of the two methods. In the MFC method, the water environment in which microorganisms can normally work has certain requirements on COD content and pH; the electric Fenton device needs to provide larger current support during operation, the energy consumption is high, and the active material hydroxyl free radical (OH) can be greatly changed due to different electrode material selections, so that the treatment effect of the device on wastewater is affected.
Disclosure of Invention
The invention aims to: the invention aims to provide an MFC coupling electric Fenton pigment wastewater treatment device which has good treatment effect on chromaticity, COD and heavy metal of pigment wastewater under low energy consumption.
The technical scheme is as follows: the invention relates to a pigment wastewater treatment device of MFC coupling electric Fenton, which comprises an MFC reaction zone and an electric Fenton reaction zone; the MFC reaction zone comprises an aeration deoxidization chamber and an MFC electrode reaction tank, wherein an aeration pipeline I communicated with an external air pump is arranged in the aeration deoxidization chamber, the aeration deoxidization chamber is communicated with an external wastewater tank through a water inlet valve, and the aeration deoxidization chamber is communicated with the MFC electrode reaction tank through a water outlet; an MFC cathode, an MFC anode and a proton exchange membrane positioned between the MFC cathode and the MFC anode are arranged in the MFC electrode reaction tank; the electric Fenton reaction zone comprises an adjusting tank and an electrode reaction tank, the adjusting tank is communicated with the MFC electrode reaction tank through an MFC water outlet, the adjusting tank is communicated with the electrode reaction tank through an electric Fenton water inlet, an aeration pipeline II communicated with an external air pump is also laid at the lower part of the adjusting tank, a plurality of groups of electrode pairs are arranged in the electrode reaction tank, and each group of electrode pairs comprises an electric Fenton anode and an electric Fenton cathode; the electric energy generated by the MFC electrode reaction tank is connected with an electric Fenton anode and an electric Fenton cathode in the electrode reaction tank through wires; the lower part of the electrode reaction tank is provided with a water outlet valve.
Wherein, the top of the regulating tank is provided with a slag storage tank at one side close to the electric Fenton water inlet, a slit is arranged at the joint of the slag storage tank bottom plate and the side wall, the scum in the regulating tank floats on the surface of the water body under the air floatation effect, and the scum on the surface of the water body flows into the slag storage tank along the slit at the joint of the slag storage tank bottom plate and the side wall; meanwhile, the regulating tank also plays a role in preventing water flow from directly impacting the graphite carbon electrode in the electrode reaction tank and regulating the pH value of water entering the electrode reaction tank.
Wherein the pH value of the water body in the regulating tank is 2-3.
In the electrode reaction tank, the electric Fenton anodes and the electric Fenton cathodes are alternately arranged in sequence along the water body flowing direction.
The electrode reaction tank is internally provided with a water diversion baffle, the height of the water diversion baffle is not lower than that of the electric Fenton anode/electric Fenton cathode, and before the water diversion baffle is arranged at the position of the electrode in the electrode reaction tank, the water diversion baffle cooperates with the regulating tank to realize the protection of the electrode in the electrode reaction tank and prevent water flow from directly impacting the graphite carbon electrode in the electrode reaction tank.
Wherein, the side walls of the lower parts of the MFC electrode reaction tank and the electrode reaction tank are respectively provided with a mud outlet valve.
In the electrode reaction tank, the electric Fenton anode is a cubic iron-nickel composite porous graphite carbon electrode, and the electric Fenton cathode is a cubic porous graphite carbon electrode.
In the MFC electrode reaction tank, an MFC cathode (2) is a cubic porous graphite carbon electrode, and an MFC anode (13) is a cylindrical porous graphite carbon electrode.
The iron-nickel composite porous graphite carbon electrode is prepared by the following method, and specifically comprises the following steps: firstly, soaking a graphite carbon electrode in nitric acid with the concentration of 0.1mol/L for 10 hours, removing metal impurities attached to the surface of the electrode, and then cleaning with deionized water and drying; preparing a ferrous sulfate solution and a nickel sulfate solution with the concentration of 0.1mol/L respectively, and mixing the ferrous sulfate solution and the nickel sulfate solution according to the volume ratio of 4.5:1, mixing to obtain a mixed solution, wherein nickel ions play a role in improving the activity and conductivity of ferrous ions, if no nickel ions exist, the generation rate and the generation amount of hydroxyl radicals are reduced, but the generation rate of the hydroxyl radicals is reduced due to excessive addition of nickel ions; placing the treated graphite carbon electrode into a mixed solution, stirring and soaking for 30min, adding 15mL of NaOH solution with the concentration of 0.4mol/L (ferrous ions and nickel ions deposited on the surface of the graphite electrode (forming precipitates) are combined more firmly after alkaline washing) into the solution, uniformly stirring, and then placing the solution and the electrode together into a 60 ℃ oven for aging for 30min; then taking out the electrode, washing to remove unreacted attachments on the surface, and drying at 110 ℃ to evaporate water contained in the electrode and prevent the electrode from cracking during subsequent roasting; and then placing the electrode into a muffle furnace to heat to 400 ℃, roasting for 3 hours, wherein the roasting aim is to firmly combine iron-nickel ions with graphite and strengthen the structural strength of the electrode, and cooling to obtain the iron-nickel composite porous graphite carbon electrode.
The beneficial effects are that: according to the pigment wastewater treatment device of the MFC coupling electric Fenton, the pigment wastewater is firstly decolorized by using the MFC, organic matters are degraded, electric energy generated in the process is used as current for supplying to an electric Fenton reaction zone, and then heavy metals and organic matters in the wastewater are further deeply treated by using an electric Fenton electrode reaction tank, so that compared with a single reaction device (MFC or electric Fenton), the electricity generation efficiency of the MFC can be effectively improved after the two are cooperated, the electricity generation efficiency is improved, and the hydrogen peroxide yield produced by the electric Fenton device is improved, so that the chromaticity, COD and heavy metal removal rate of the pigment wastewater are greatly improved; in addition, the iron-nickel composite porous graphite carbon is adopted as the anode in the electric Fenton device, and the iron-nickel composite ions are adopted for modification of the anode graphite carbon electrode, so that on one hand, no additional iron is needed in the reaction process, and therefore, the loss of iron element is effectively reduced (because the additional iron is discharged along with water flow along with the progress of the reaction, and continuous supplementation is needed, the waste is caused, meanwhile, the treatment performance of the device is unstable), on the other hand, the nickel element in the electrode is added, so that the electrode activity is further improved, heavy metal ions in the wastewater can be effectively removed, the recycling of heavy metal sludge is facilitated, the removal rate of COD and heavy metal ions in the wastewater is greatly improved by the modified graphite carbon electrode, and the electric Fenton device has a good treatment effect on pigment wastewater with high initial COD; the device solves the problems of poor treatment effect and high energy consumption in the traditional pigment wastewater treatment, and can obtain good wastewater treatment effect only by extremely low energy consumption.
Drawings
FIG. 1 is a top view of the device of the present invention;
FIG. 2 is a side view of the device of the present invention;
fig. 3 is a diagram showing the operation effect of the device of the present invention.
Detailed Description
Example 1
As shown in figures 1-2, the pigment wastewater treatment device of the MFC coupling electric Fenton comprises an MFC reaction zone and an electric Fenton reaction zone; the MFC reaction zone 17 comprises an aeration deoxidization chamber 18 and an MFC electrode reaction tank 19, the aeration deoxidization chamber 18 is provided with a water inlet 15 communicated with an external wastewater tank and a water outlet 14 communicated with the MFC electrode reaction tank 19, a valve is arranged at the water inlet 15, the water inlet 15 is arranged at a position close to the vertical height of the bottom plate of the deoxidization chamber 18, the water outlet 14 is far from the vertical height of the bottom plate of the deoxidization chamber 18, and an aeration pipeline I1 communicated with an external air pump is further arranged in the aeration deoxidization chamber 18 (the aeration deoxidization chamber is filled with nitrogen through the aeration pipeline I1 to remove dissolved oxygen in a water body); an MFC cathode 2, an MFC anode 13 and a proton exchange membrane 3 positioned between the MFC cathode 2 and the MFC anode 13 are arranged in the MFC electrode reaction tank 19; the electric Fenton reaction zone 20 comprises an adjusting tank 21 and an electrode reaction tank 22, the adjusting tank 21 is communicated with the MFC electrode reaction tank 19 through an MFC water outlet 11, the adjusting tank 21 is communicated with the electrode reaction tank 22 through an electric Fenton water inlet 10 (the MFC water outlet and the electric Fenton water inlet are both positioned at a moderate vertical height position from the bottom plate of the adjusting tank), a slag storage tank 16 is arranged at one side of the top of the adjusting tank 21, which is close to the electric Fenton water inlet 10, a slit 23 is arranged at the joint of the bottom plate and the side wall of the slag storage tank 16, an aeration pipeline II4 communicated with an external air pump is also laid at the lower part of the adjusting tank 21 (the aeration pipeline II4 is used for introducing air/oxygen to increase dissolved oxygen in a water body), scum in the adjusting tank 21 floats on the surface of the water body under the action of air floatation, and the scum on the surface of the water body flows into the slag storage tank 16 along the slit 23 at the joint of the bottom plate and the side wall of the slag storage tank 16; meanwhile, the regulating tank 21 also plays a role in preventing water flow from directly impacting the graphite carbon electrode in the electrode reaction tank 22 and regulating the pH value of water entering the electrode reaction tank 22; a plurality of groups of electrode pairs are arranged in the electrode reaction tank 22, each group of electrode pairs comprises an electric Fenton anode 6 and an electric Fenton cathode 7, the electric Fenton anode 6 and the electric Fenton cathode 7 are alternately arranged in sequence along the water flow direction, and the distance between adjacent electrodes is 3cm; the electric energy generated by the MFC electrode reaction tank 19 is connected with the electric Fenton anode 6 and the electric Fenton cathode 7 in the electrode reaction tank 22 through wires, and the MFC cathode 2 and the MFC anode 13 are respectively connected with the electric Fenton anode 6 and the electric Fenton cathode 7 in the electrode reaction tank 22 through wires; the electrode reaction tank 22 is also internally provided with a water diversion baffle plate 5, the height of the water diversion baffle plate 5 is not lower than the height of the electric Fenton anode 6/the electric Fenton cathode 7, the water diversion baffle plate 5 is arranged in front of an electrode in the electrode reaction tank 22, the water diversion baffle plate 5 is cooperated with the regulating tank 21 to realize the protection of the electrode in the electrode reaction tank 22, the water flow is prevented from directly impacting a graphite carbon electrode in the electrode reaction tank 22, mud outlet valves (12 and 9) are respectively arranged on the side walls of the lower parts of the MFC electrode reaction tank 19 and the electrode reaction tank 22, and the lower part of the electrode reaction tank 22 is also provided with a water outlet valve 8.
In the electrode reaction tank 22, the electric Fenton anode 6 is a cubic iron-nickel composite porous graphite carbon electrode, and the electric Fenton cathode 7 is a cubic porous graphite carbon electrode.
In the MFC electrode reaction tank 19, the MFC anode 13 is a cylindrical porous graphite carbon electrode, and the MFC cathode 2 is a cubic porous graphite carbon electrode.
The iron-nickel composite porous graphite carbon electrode is prepared by the following method, and specifically comprises the following steps: firstly, soaking a graphite carbon electrode in nitric acid with the concentration of 0.1mol/L for 10 hours, removing metal impurities attached to the surface of the electrode, and then cleaning with deionized water and drying; preparing a ferrous sulfate solution and a nickel sulfate solution with the concentration of 0.1mol/L respectively, and mixing the ferrous sulfate solution and the nickel sulfate solution according to the volume ratio of 4.5:1, mixing to obtain a mixed solution, wherein nickel ions play a role in improving the activity and conductivity of ferrous ions, if no nickel ions exist, the generation rate and the generation amount of hydroxyl radicals are reduced, but the generation rate of the hydroxyl radicals is reduced due to excessive addition of nickel ions; placing the treated graphite carbon electrode into a mixed solution, stirring and soaking for 30min, adding NaOH solution with the concentration of 0.4mol/L (ferrous ions and nickel ions deposited on the surface of the graphite electrode (forming precipitates) are combined more firmly after alkaline washing) into the solution, uniformly stirring, and placing the solution and the electrode into an oven together for aging for 30min; then taking out the electrode, flushing to remove unreacted attachments on the surface, and drying; and then placing the electrode into a muffle furnace, heating to 400 ℃, roasting for 3 hours, and cooling to obtain the iron-nickel composite porous graphite carbon electrode.
During operation, pigment wastewater enters an MFC reaction area 17 through a water inlet valve 15 after preliminary filtration, in the MFC reaction area 17, the wastewater firstly passes through an aeration deoxidization chamber 18, a large amount of nitrogen is blown into the aeration deoxidization chamber 18 through an aeration pipeline I1 to remove oxygen in the wastewater, the deoxidized wastewater enters an anode area of an MFC electrode reaction tank 19 through a water outlet 14 at the other side of the aeration deoxidization chamber 18, organic pollutants in the wastewater are consumed and decomposed by anaerobic microorganisms as fuel at an MFC anode 13, electric energy is generated, the generated electric energy is transmitted to a current storage device through a wire, and the current storage device adjusts direct current to 200 mA-400 mA and transmits the direct current to an electric Fenton device; h generated during the reaction of the MFC anode 13 + Through proton exchange membrane 3 to MFC cathode 2, where reduction reaction takes place to produce water, anode produced during reactionMud is discharged through a mud outlet valve 12 on the lower side wall of the MFC electrode reaction tank 19. After being treated by the MFC reaction area 17, the wastewater enters an adjusting tank 21 of an electric Fenton reaction area 20 through an MFC water outlet 11, the pH value of the wastewater in the adjusting tank 21 is adjusted to be 2-3, and then the wastewater enters an electric Fenton electrode reaction tank 22, and in the electric Fenton electrode reaction tank 22, the wastewater is split at a water division baffle 5 and slowly flows into an electrode area; an aeration pipeline II4 communicated with an external air pump is also laid at the lower part of the regulating tank 21, air/oxygen is aerated through the aeration pipeline II4, dissolved oxygen in the water body is increased, scum formed by the water body in the regulating tank 21 under the action of air floatation floats on the surface of the water body, scum on the surface of the water body flows into the slag storage tank 16 along a slit 23 at the joint of the bottom plate and the side wall of the slag storage tank 16, the scum enters the slag storage tank 16 under the action of air flow and water flow, and is discharged through a slag outlet at the top of the tank body after extrusion and dehydration; in the electrode reaction zone, the iron compounded on the electric Fenton anode 6 (the electrode is replaced completely by replacing the electrode) will undergo oxidation reaction under the action of current to generate Fe 2+ When the aeration pipeline II4 is inflated with air, the wastewater contains high-concentration O 2 ，O 2 Obtaining electrons on the electric Fenton cathode 7 to generate H 2 O 2 Fe generated by anode 2+ And H is 2 O 2 After combination, hydroxyl free radical (OH) and Fe of active substances are continuously generated in the wastewater 2+ Acting as a catalyst in the reaction, so that the whole reaction can be continuously carried out; the organic pollutant remained in the wastewater is oxidized by OH, and toxic heavy metals can be contained in Fe 2+ 、Fe 3 + Passivation is carried out under the action of the catalyst, precipitation is generated at the cathode to generate cathode mud, the cathode mud is discharged from a mud outlet valve 9 arranged on the side wall of the lower part of the electrode reaction tank 22, and the heavy metal in the cathode mud can be recycled after a series of treatments. The chromaticity, toxicity and COD of the pigment wastewater treated by the device are greatly reduced, and the pigment wastewater is discharged out of the device through the water outlet valve 8 after reaching the discharge standard.
In the wastewater treatment process, the water surface height of wastewater in the whole device needs to be adjusted first. Specifically, the wastewater level in the MFC needs to be adjusted to the submerged electrode reaction chamber by adjusting and controlling the inflow water amount, and the water level also needs to be adjusted to the submerged electrode reaction zone in the electric Fenton device. After the water surface height is adjusted, the water inlet valve 15 and the water outlet valve 8 are required to be closed, the device is started initially, after the device operates stably, the water inlet valve 15 and the water outlet valve 8 are opened, the water inlet and outlet ratio is adjusted, the original water surface height is maintained, and the device can work normally. Firstly, the water surface is required to submerge the MFC electrode reaction tank 19, because the device needs to be started initially, namely microorganisms in the MFC need to adapt to the treated wastewater environment first; secondly, the waste water level of the whole device is controlled so that the liquid level in the regulating tank 21 reaches the height of the slit 23 of the bottom plate of the slag storage tank 16, and the scum can enter the slag storage tank 16 along with the water flow.
For pigment wastewater with initial chromaticity of 1000 times, ammonia nitrogen concentration of 1200mg/L, COD concentration of 12000mg/L and heavy metal ion concentration of 1.5mg/L, the pigment wastewater is treated by adopting an existing MFC device, an electric Fenton device and the coupling device of the invention respectively, and after three hours of treatment, the treatment results of the devices are shown in Table 1 and FIG. 3.
TABLE 1
The output voltage is increased along with the increase of the external resistor, and the maximum power density is obtained when the external resistor of the MFC is similar to the internal resistor, and the internal resistor of the electric Fenton device is relatively similar to the internal resistor of the MFC device, so that the coupling device can improve the power generation.
Comparative example 1
The porous graphite carbon electrode doped with iron is prepared by the following method, and specifically comprises the following steps: firstly, soaking a graphite carbon electrode in nitric acid with the concentration of 0.1mol/L for 10 hours, removing metal impurities attached to the surface of the electrode, and then cleaning with deionized water and drying; preparing ferrous sulfate solution with the concentration of 0.1 mol/L; placing the treated graphite carbon electrode into a ferrous sulfate solution, stirring and soaking for 30min, adding a NaOH solution with the concentration of 0.4mol/L into the solution, uniformly stirring, and placing the solution and the electrode into an oven for aging for 30min; then taking out the electrode, flushing to remove unreacted attachments on the surface, and drying; and then placing the electrode into a muffle furnace, heating to 400 ℃, roasting for 3 hours, and cooling to obtain the porous graphite carbon electrode doped with iron.
Comparative example 2
The porous graphite carbon electrode of the composite iron-nickel is prepared by the following method, and specifically comprises the following steps: firstly, soaking a graphite carbon electrode in nitric acid with the concentration of 0.1mol/L for 10 hours, removing metal impurities attached to the surface of the electrode, and then cleaning with deionized water and drying; preparing a ferrous sulfate solution and a nickel sulfate solution with the concentration of 0.1mol/L respectively, and mixing the ferrous sulfate solution and the nickel sulfate solution according to the volume ratio of 4.5:2, mixing to obtain a mixed solution; placing the treated graphite carbon electrode into a mixed solution, stirring and soaking for 30min, adding NaOH solution with the concentration of 0.4mol/L into the solution, uniformly stirring, and placing the solution and the electrode into an oven for aging for 30min; then taking out the electrode, flushing to remove unreacted attachments on the surface, and drying; and then placing the electrode into a muffle furnace, heating to 400 ℃, roasting for 3 hours, and cooling to obtain the iron-nickel composite porous graphite carbon electrode.
The coupling devices obtained by using the materials of comparative examples 1 and 2 as the electric Fenton anodes and the coupling device of example 1 were treated with respect to pigment wastewater having an initial chromaticity of 1000 times, an ammonia nitrogen concentration of 1200mg/L, a COD concentration of 12000mg/L and a heavy metal ion concentration of 1.5mg/L, and the treatment results are shown in Table 2 after three hours of treatment.
TABLE 2

Claims (8)

1. An MFC coupling electricity Fenton's pigment effluent treatment plant, its characterized in that: comprises an MFC reaction zone (17) and an electric Fenton reaction zone (20); the MFC reaction zone (17) comprises an aeration deoxidization chamber (18) and an MFC electrode reaction tank (19), an aeration pipeline I (1) communicated with an external air pump is arranged in the aeration deoxidization chamber (18), the aeration deoxidization chamber (18) is communicated with an external wastewater tank through a water inlet valve (15), and the aeration deoxidization chamber (18) is communicated with the MFC electrode reaction tank (19) through a water outlet (14); an MFC cathode (2), an MFC anode (13) and a proton exchange membrane (3) positioned between the MFC cathode (2) and the MFC anode (13) are arranged in the MFC electrode reaction tank (19); the electric Fenton reaction zone (20) comprises an adjusting tank (21) and an electrode reaction tank (22), the adjusting tank (21) is communicated with the MFC electrode reaction tank (19) through an MFC water outlet (11), the adjusting tank (21) is communicated with the electrode reaction tank (22) through an electric Fenton water inlet (10), an aeration pipeline II (4) communicated with an external air pump is also laid at the lower part of the adjusting tank (21), a plurality of groups of electrode pairs are arranged in the electrode reaction tank (22), and each group of electrode pairs comprises an electric Fenton anode (6) and an electric Fenton cathode (7); the electric energy generated by the MFC electrode reaction tank (19) is connected with an electric Fenton anode (6) and an electric Fenton cathode (7) in the electrode reaction tank (22) through wires; a water outlet valve (8) is arranged at the lower part of the electrode reaction tank (22);
in the electrode reaction tank (22), the electric Fenton anode (6) is an iron-nickel composite porous graphite carbon electrode, and the preparation method of the iron-nickel composite porous graphite carbon electrode comprises the following steps:
(1) Soaking a graphite carbon electrode by using nitric acid, and then cleaning by using deionized water and drying;
(2) Preparing a ferrous sulfate solution and a nickel sulfate solution with the concentration of 0.1mol/L respectively, and mixing the ferrous sulfate solution and the nickel sulfate solution according to the volume ratio of 4.5:1, mixing to obtain a mixed solution;
(3) Placing the graphite carbon electrode treated in the step (1) into a mixed solution, stirring and soaking for not less than 30min, adding NaOH solution with the concentration of 0.4mol/L into the solution after soaking, stirring uniformly, and placing the solution and the electrode into an oven together for ageing for not less than 30min;
(4) Taking out the electrode, washing to remove unreacted attachments on the surface, washing, drying, heating the electrode to 400 ℃ for roasting after drying, and cooling after roasting to obtain the iron-nickel composite porous graphite carbon electrode;
for pigment wastewater with initial chromaticity of 1000 times, ammonia nitrogen concentration of 1200mg/L, COD concentration of 12000mg/L and heavy metal ion concentration of 1.5mg/L, the chromaticity removal rate is 81%, the COD removal amount is 9386mg/L, the COD removal rate is 78.2%, the ammonia nitrogen removal rate is 86.7%, and the heavy metal removal rate is 75.3%.
2. The pigment wastewater treatment device of MFC-coupled electric Fenton according to claim 1, wherein: the top of the regulating tank (21) is provided with a slag storage tank (16) at one side close to the electric Fenton water inlet (10), and a slit (23) is arranged at the joint of the bottom plate and the side wall of the slag storage tank (16).
3. The pigment wastewater treatment device of MFC-coupled electric Fenton according to claim 2, wherein: the pH value of the water body in the regulating tank (21) is 2-3.
4. The pigment wastewater treatment device of MFC-coupled electric Fenton according to claim 1, wherein: in the electrode reaction tank (22), along the water flow direction, the electric Fenton anodes (6) and the electric Fenton cathodes (7) are alternately arranged in sequence.
5. The pigment wastewater treatment device of MFC-coupled electric Fenton according to claim 4, wherein: the electrode reaction tank (22) is also internally provided with a water diversion baffle plate (5), and the height of the water diversion baffle plate (5) is not lower than the heights of the electric Fenton anode (6) and the electric Fenton cathode (7).
6. The pigment wastewater treatment device of MFC-coupled electric Fenton according to claim 1, wherein: and mud outlet valves are arranged on the side walls of the lower parts of the MFC electrode reaction tank (19) and the electrode reaction tank (22).
7. The pigment wastewater treatment device of MFC-coupled electric Fenton according to claim 1, wherein: in the MFC electrode reaction tank (19), an MFC cathode (2) is a cuboid porous graphite carbon electrode, and an MFC anode (13) is a cylindrical porous graphite carbon electrode.
8. The pigment wastewater treatment device of MFC-coupled electric Fenton according to claim 1, wherein: in the electrode reaction tank (22), the electric Fenton cathode (7) is a cubic porous graphite carbon electrode.
CN202210667155.5A 2022-06-14 2022-06-14 Pigment effluent treatment plant of MFC coupling electricity Fenton Active CN114920429B (en)

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CN104478073B (en) * 2014-12-10 2016-07-06 广西师范大学 A kind of device utilizing ABR-bio electricity Fenton coupling technique to process difficult for biological degradation industrial wastewater
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