WO2019169785A1 - Use of membrane-free microbial fuel cell coupled with cathode catalytic membrane in coking wastewater treatment system - Google Patents

Use of membrane-free microbial fuel cell coupled with cathode catalytic membrane in coking wastewater treatment system Download PDF

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WO2019169785A1
WO2019169785A1 PCT/CN2018/091909 CN2018091909W WO2019169785A1 WO 2019169785 A1 WO2019169785 A1 WO 2019169785A1 CN 2018091909 W CN2018091909 W CN 2018091909W WO 2019169785 A1 WO2019169785 A1 WO 2019169785A1
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membrane
cathode
fuel cell
microbial fuel
coking wastewater
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PCT/CN2018/091909
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French (fr)
Chinese (zh)
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柳丽芬
张艺臻
孙嘉琪
安路阳
王学凯
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大连理工大学
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Publication of WO2019169785A1 publication Critical patent/WO2019169785A1/en
Priority to ZA2020/05265A priority Critical patent/ZA202005265B/en

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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
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/005—Combined electrochemical biological processes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
    • 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
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
    • 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
    • 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
    • C02F2001/46152—Electrodes characterised by the shape or form
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/46115—Electrolytic cell with membranes or diaphragms
    • 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

Definitions

  • the invention belongs to the technical field of sewage treatment and refractory wastewater treatment and resource utilization, and relates to a novel microbial fuel cell reactor coupled with a cathode catalytic membrane and an ion exchange membrane, which exhibits good effects when treating refractory coking wastewater. .
  • Coking wastewater is a kind of typical refractory high-concentration organic wastewater. It is the wastewater generated by the coal chemical industry during the coking process, and its source is concentrated. China is currently the world's number one coke producer and exporter, and the problem of coking wastewater pollution is particularly serious.
  • the coking wastewater has complex composition, high organic matter concentration, high chroma, high toxicity and difficult to be degraded.
  • the treatment of coking wastewater has become a major problem in the water treatment industry. In order to meet the national sewage discharge standards for the coal chemical industry, three-stage treatment methods of pretreatment, biological treatment and advanced treatment are generally adopted. The traditional coking wastewater treatment process is complicated and the treatment effect is poor. Therefore, it is necessary to design an energy-saving and high-efficiency method.
  • the sewage treatment process realizes efficient removal of coking wastewater.
  • Microbial Fuel Cell (MFC) technology is a new technology that integrates wastewater biological treatment and production capacity this year. It can not only purify wastewater, but also convert chemical energy into electrical energy. Under the action of the anode microorganism, the oxidative degradation of the contaminant simultaneously generates protons and electrons. The protons reach the cathode through the proton exchange membrane, and the electrons transferred to the cathode by the external circuit reduce O 2 to form H 2 O or H 2 O 2 .
  • the poor quality of the effluent treated only by a single MFC the low efficiency of the treatment is a bottleneck that limits the development of microbial fuel cells.
  • the membrane separation technology is an energy-efficient water treatment technology, which is widely used in various fields due to its operation at normal temperature, no phase change, no chemical change, and strong adaptability.
  • general microfiltration or ultrafiltration can not trap small molecular pollutants, and can not solve the problem of removal of toxic and difficult-to-degrade pollutants in water. Therefore, catalytic and advanced oxidation technologies (photocatalysis, electrocatalysis, photocatalysis, ozone oxidation, sulfate radical freedom)
  • membrane separation technology it can synergistic membrane filtration and catalytic oxidation to remove contaminants, thereby improving the quality of effluent.
  • the microbial fuel cell technology is coupled with the catalytic membrane for actual sewage treatment. On the one hand, it solves the problem of poor water quality of the microbial fuel cell, and on the other hand, it uses the fuel cell to generate micro electric field and membrane catalysis to reduce membrane fouling.
  • the application of microbial fuel cell technology is subject to the cost of ion exchange membranes and electrodes, and the use of ion exchange membranes will reduce costs.
  • the electrode is coupled to the filter membrane to provide an electrode membrane filtration function, which also reduces additional materials and costs. Further loading of the catalyst helps to achieve catalytic oxidation of refractory pollutants while generating electricity and filtering, improving processing efficiency and reducing costs.
  • the invention constructs a novel cathode catalytic membrane coupled ion-free membrane microbial fuel cell reactor and a coking wastewater treatment system, and utilizes an anode microbial anaerobic treatment wastewater, a cathode catalytic membrane (photo) electrocatalysis and filtration to enhance the water quality; Advantages, continuous and efficient treatment; use quartz sand to fill the intermediate layer instead of proton exchange membrane, reduce process operation cost, improve the service life of catalytic filter membrane; and apply to the treatment of refractory actual coking wastewater, achieving high efficiency treatment and energy saving .
  • the object of the present invention is to provide a novel cathode catalytic membrane coupled with an ion exchange membrane microbial fuel cell reactor and a coking wastewater treatment system, which solves the problem that the effluent water quality of the microbial fuel cell is poor and the coking wastewater is difficult to process and the process flow is complicated.
  • a cathode catalytic membrane coupled with a membrane-free microbial fuel cell for use in a coking wastewater treatment system comprising a reactor, an aeration device and a computer data acquisition system; the reactor is a double chamber, the cathode chamber is provided with an aeration head to expose air, and the cathode is a catalytic membrane electrode; an intermediate chamber filled with quartz sand between the two chambers is substituted for the proton exchange membrane; an activated carbon particle loaded with an electrogenic microorganism is placed in the anode chamber, the filling degree is 75-85%, and the carbon rod is inserted into the activated carbon particles as a conductive anode.
  • the top is sealed and has a water inlet; the external resistance is connected between the anode and the cathode, and the resistance is 1-1200 ⁇ .
  • the external resistor is connected to the data acquisition system to record the generated voltage; the cathode catalytic membrane electrode is connected to the water pump, and the cathode catalytic membrane filters the water.
  • the preparation method of the cathode catalytic membrane is as follows:
  • the cathode catalytic membrane is an electrocatalytic membrane or a photocatalytic membrane.
  • the catalytic material in the cathode catalytic membrane is a semiconductor material having a Fermi level difference from the anode or a material having electrocatalytic activity; a conductive substrate needs to be selected or a conductive material is added. Increasing the conductivity of the electrode to achieve electron transfer; mixing the catalytic material with the film forming material to form a flat film on the substrate, directly growing the catalytic material on the substrate, or adding an adhesive to the substrate, etc. A cathode catalytic membrane is obtained.
  • the conductive substrate of the cathode catalytic membrane is stainless steel mesh, carbon fiber cloth, foamed nickel or carbon felt; the conductive material is carbon nanofiber, carbon nanotube, graphene or iron powder, and the film forming material is polyvinylidene fluoride and acetic acid. Cellulose, etc.;
  • the electrocatalyst in the cathode electrocatalytic film is MnO 2 , CoFe 2 O 4 or FeOOH.
  • the semiconductor catalyst in the cathode photoelectrocatalytic film is TiO 2 , gC 3 N 4 , SiC or WO 3 , and an ultraviolet or visible light source is added outside the cathode.
  • the cathode chamber may be added with a persulfate or peroxodisulfate concentration of (10-200 mg/L) to promote the generation of sulfate radicals and assist in cathodic (photo) electrocatalysis.
  • the above reactor system is used for actually treating coking wastewater: the COD range of the actual coking wastewater treated by the system is 200-2500 mg/L, and the anode microorganism is domesticated by dilution coking wastewater before starting the reactor, and the cathode membrane is driven by a peristaltic pump. Filtration, operation mode is intermittent or continuous, continuous hydraulic retention time 6h-48h.
  • the invention has the beneficial effects that the membrane-free microbial fuel cell system utilizes anode microbial anaerobic treatment of wastewater, cooperates with cathodic catalytic membrane (photo) electrocatalysis and cyclic filtration treatment of refractory coking wastewater, and fully utilizes their respective advantages to solve the traditional
  • the problem of low decomposition efficiency of MFC organic matter is to improve the effluent quality of MFC; the intermediate layer is replaced by quartz sand to replace the proton exchange membrane, and the process operation cost is reduced; the micro-electric field of the coupling system increases the service life of the catalytic filter membrane; the reaction system occupies a small area and has a short process Good processing effect and energy saving and environmental protection, which is conducive to carrying out amplification and pilot experiments to promote the industrialization of results
  • Figure 1 is a diagram of a membrane-free microbial fuel cell coupled cathode catalytic membrane system.
  • Fig. 2 COD removal rate of TiO 2 /PVDF membrane effluent at low treatment temperature for low concentration coking wastewater.
  • the abscissa is time (unit: hour) and the ordinate is COD removal rate.
  • Fig.3 COD removal rate of TiO 2 /PVDF membrane effluent at high treatment temperature for high concentration coking wastewater.
  • the abscissa is time (unit: hour) and the ordinate is COD removal rate.
  • Figure 4 shows the potential of the TiO 2 /PVDF membrane as the cathode system for high-concentration coking wastewater at different treatment times.
  • the abscissa is time (unit: minute) and the ordinate is potential.
  • TiO 2 /PVDF catalytic membrane TiO 2 (15 wt%) and carbon nanofibers (25 wt%) were added to PVDF (10 wt%) DMF casting solution, and after stirring for 6 h, The ultrasonic defoaming was carried out for 30 min, and the carbon nanofiber cloth was used as the substrate. The coating thickness was 300 ⁇ m. After phase transformation for 12 h, the TiO 2 /PVDF catalytic film cathode was obtained.
  • Non-membrane microbial fuel cell coupled cathode catalytic membrane system for processing low-concentration coking wastewater operation the anode chamber is filled with activated carbon particles (filling degree 85%) loaded with electricity-producing microorganisms, and the carbon rod is inserted into the activated carbon particles as a conductive anode.
  • the water sample was taken out from the cathode membrane module by pumping at intervals of 12 h, and the COD removal rate of the water was measured by the potassium dichromate method.
  • the low-concentration wastewater directly passes through the anode microbial interaction coupled with the cathode membrane electrocatalysis, and reaches a 90% removal rate after 12 hours of operation, and the final COD removal rate of the cathode chamber effluent reaches 99%.
  • Non-membrane microbial fuel cell coupled cathode catalytic membrane system for processing high-concentration coking wastewater operation the anode chamber is filled with activated carbon particles (filling degree 85%) loaded with electricity-producing microorganisms, and the carbon rod is a conductive anode inserted into the activated carbon particles, the top Sealing low-concentration coking wastewater (COD about 2000mg/L); replacing the proton exchange membrane with an intermediate chamber filled with quartz sand between the two chambers; installing the catalytic cathode membrane in a rectangular membrane module (double-sided), and exposing the bottom of the cathode chamber Air, providing oxygen for electron activation of oxygen to generate free radicals; pumping the top of the cathode membrane module by pumping water, and the anode and cathode are connected by a 1000 ⁇ external resistor.
  • the actual coking wastewater is diluted 100%, 50%, 0% domesticated anode microorganisms.
  • the peristaltic pump is continuously pumped into the low-concentration coking wastewater, and the hydraulic retention time is 48 hours.
  • Water was taken from above the cathode membrane module by pumping at intervals of 12 h, and the COD removal rate of the water was measured by potassium dichromate method. As shown in Fig. 3, the removal rate of COD in the cathode chamber reaches 80% after 48 hours, and the removal rate after 80 hours is about 75%.
  • the power generation of the system under this condition is shown in Figure 4.
  • the initial battery potential is about 0.45v.
  • the battery potential of the first 5h of the system is stable and decreases with the increase of the pollutant degradation rate of the cathode chamber.

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Abstract

Disclosed is the use of a membrane-free microbial fuel cell coupled with a cathode catalytic membrane in a coking wastewater treatment system, the coking wastewater treatment system comprising a reactor, an aeration device and a computer data acquisition system, wherein a reaction chamber has two chambers; a cathode chamber is provided with an aeration head, a cathode is a catalytic membrane electrode, and an intermediate chamber filled with quartz sand is provided between the two chambers; activated carbon particles loaded with electricity-producing microorganisms are placed in an anode chamber, and a carbon rod is a conductive anode and is inserted into the activated carbon particles; and an external resistance is connected between the cathode and the anode, and water flows out after filtering by means of a cathode catalytic membrane.

Description

一种阴极催化膜耦合无膜微生物燃料电池用于焦化废水处理系统Cathode catalytic membrane coupled membraneless microbial fuel cell for coking wastewater treatment system 技术领域Technical field
本发明属于污水处理与难降解废水处理及资源化利用技术领域，涉及一种新的耦合阴极催化膜、无离子交换膜的微生物燃料电池反应器，在处理难降解焦化废水时，表现出良好效果。The invention belongs to the technical field of sewage treatment and refractory wastewater treatment and resource utilization, and relates to a novel microbial fuel cell reactor coupled with a cathode catalytic membrane and an ion exchange membrane, which exhibits good effects when treating refractory coking wastewater. .
背景技术Background technique
焦化废水是一类典型的难降解高浓度有机废水，是煤化工行业在炼焦工艺阶段产生的废水，其来源较为集中。我国目前是世界第一焦炭生产国和出口国，焦化废水的污染问题尤为严重。焦化废水成分复杂，有机物浓度高，色度高，毒性大，难降解，对焦化废水的处理已成为水处理行业的一大难题。为了达到国家对煤化工行业的污水排放标准，一般采用预处理、生物处理和深度处理三级处理方法，传统的焦化废水处理工艺流程复杂、处理效果较差，因此，需要设计一种节能、高效的污水处理工艺，实现焦化废水高效去除。Coking wastewater is a kind of typical refractory high-concentration organic wastewater. It is the wastewater generated by the coal chemical industry during the coking process, and its source is concentrated. China is currently the world's number one coke producer and exporter, and the problem of coking wastewater pollution is particularly serious. The coking wastewater has complex composition, high organic matter concentration, high chroma, high toxicity and difficult to be degraded. The treatment of coking wastewater has become a major problem in the water treatment industry. In order to meet the national sewage discharge standards for the coal chemical industry, three-stage treatment methods of pretreatment, biological treatment and advanced treatment are generally adopted. The traditional coking wastewater treatment process is complicated and the treatment effect is poor. Therefore, it is necessary to design an energy-saving and high-efficiency method. The sewage treatment process realizes efficient removal of coking wastewater.
微生物燃料电池（Microbial Fuel Cell，简称MFC）技术是今年迅速发展的一种集废水生物处理及产能于一体新技术，不仅能够实现废水的净化处理，还能将化学能转化为电能。在阳极微生物的作用下，氧化降解污染物同时产生质子和电子，质子通过质子交换膜到达阴极，与外电路传递到阴极的电子还原O 2形成H 2O或者H 2O 2。然而，仅经单一MFC处理的出水水质差，处理的效率低是限制微生物燃料电池发展的瓶颈问题。而膜分离技术是一种高效节能的水处理技术，由于具有常温下操作、无相态变化、无化学变化、适应性强等特点被广泛应用各个领域。但一般的微滤或超滤不能截留小分子污染物，不能解决水中毒性难降解污染物的去除问题，因此将催化、高级氧化技术（光催化、电催化、光电催化、臭氧氧化、硫酸根自由基氧化等）与膜分离技术结合，可协同膜过滤及催化氧化作用去除污染物，从而提高出水水质。并克服膜分离技术存在的膜污染问题，膜污染导致处理过程中分离效果下降，常用的膜表面清洗方法及曝气方法的能耗高。本系统中通过结合微电场及催化作用可实现有效控制膜污染问题。微生物燃料电池技术与催化膜耦合用于实际污水处理，一方面，解决微生物燃料电池出水水质差的问题，另一方面利用燃料电池产生微电场及膜催化作用，减轻膜污染。微生物燃料电池技术的应用受制于其中离子交换膜和电极的成本，不使用离子交换膜，将降低成本。并且将电极与过滤膜耦合于一体，赋予电极膜过滤功能，也减少了额外材料和成本。进一步负载催化剂有助于在产电过滤的同时，实现难降解污染物的催化氧化，提升处理效率及降低成本。 Microbial Fuel Cell (MFC) technology is a new technology that integrates wastewater biological treatment and production capacity this year. It can not only purify wastewater, but also convert chemical energy into electrical energy. Under the action of the anode microorganism, the oxidative degradation of the contaminant simultaneously generates protons and electrons. The protons reach the cathode through the proton exchange membrane, and the electrons transferred to the cathode by the external circuit reduce O 2 to form H 2 O or H 2 O 2 . However, the poor quality of the effluent treated only by a single MFC, the low efficiency of the treatment is a bottleneck that limits the development of microbial fuel cells. The membrane separation technology is an energy-efficient water treatment technology, which is widely used in various fields due to its operation at normal temperature, no phase change, no chemical change, and strong adaptability. However, general microfiltration or ultrafiltration can not trap small molecular pollutants, and can not solve the problem of removal of toxic and difficult-to-degrade pollutants in water. Therefore, catalytic and advanced oxidation technologies (photocatalysis, electrocatalysis, photocatalysis, ozone oxidation, sulfate radical freedom) Combined with membrane separation technology, it can synergistic membrane filtration and catalytic oxidation to remove contaminants, thereby improving the quality of effluent. And overcome the membrane fouling problem existing in the membrane separation technology, membrane fouling leads to a decrease in the separation effect during the treatment process, and the common membrane surface cleaning method and the aeration method have high energy consumption. In this system, the problem of effective control of membrane fouling can be achieved by combining micro electric field and catalysis. The microbial fuel cell technology is coupled with the catalytic membrane for actual sewage treatment. On the one hand, it solves the problem of poor water quality of the microbial fuel cell, and on the other hand, it uses the fuel cell to generate micro electric field and membrane catalysis to reduce membrane fouling. The application of microbial fuel cell technology is subject to the cost of ion exchange membranes and electrodes, and the use of ion exchange membranes will reduce costs. And the electrode is coupled to the filter membrane to provide an electrode membrane filtration function, which also reduces additional materials and costs. Further loading of the catalyst helps to achieve catalytic oxidation of refractory pollutants while generating electricity and filtering, improving processing efficiency and reducing costs.
本发明构建一种新型阴极催化膜耦合无离子交换膜微生物燃料电池反应器及焦化废水处理系统，利用阳极微生物厌氧处理废水，阴极催化膜（光）电催化及过滤提升出水水质；充分利用各自优势，实现连续高效处理；利用石英砂填充中间层替代质子交换膜，降低工艺运行成本，提升催化过滤膜使用寿命；并应用于难降解的实际焦化废水的处理，达到了高效处理及节能的目的。The invention constructs a novel cathode catalytic membrane coupled ion-free membrane microbial fuel cell reactor and a coking wastewater treatment system, and utilizes an anode microbial anaerobic treatment wastewater, a cathode catalytic membrane (photo) electrocatalysis and filtration to enhance the water quality; Advantages, continuous and efficient treatment; use quartz sand to fill the intermediate layer instead of proton exchange membrane, reduce process operation cost, improve the service life of catalytic filter membrane; and apply to the treatment of refractory actual coking wastewater, achieving high efficiency treatment and energy saving .
技术问题technical problem
本发明的目的是提供一种新型阴极催化膜耦合无离子交换膜微生物燃料电池反应器及焦化废水处理系统，解决微生物燃料电池出水水质差及焦化废水难处理、工艺流程复杂的问题。The object of the present invention is to provide a novel cathode catalytic membrane coupled with an ion exchange membrane microbial fuel cell reactor and a coking wastewater treatment system, which solves the problem that the effluent water quality of the microbial fuel cell is poor and the coking wastewater is difficult to process and the process flow is complicated.
技术解决方案Technical solution
本发明的技术方案：The technical solution of the invention:
一种阴极催化膜耦合无膜微生物燃料电池用于焦化废水处理系统，包括反应器、曝气装置和计算机数据采集系统；所述反应器为双室，阴极室设置曝气头曝空气，阴极为催化膜电极；两室之间为石英砂填充的中间室取代质子交换膜；阳极室中放置负载有产电微生物的活性炭颗粒，填充度75-85%，碳棒为导电阳极插入活性炭颗粒中，顶端密闭，有进水口；阴阳极之间连外电阻，阻值为1-1200Ω，外电阻连接数据采集系统，记录产生电压；阴极催化膜电极外连出水泵，由阴极催化膜过滤后出水。A cathode catalytic membrane coupled with a membrane-free microbial fuel cell for use in a coking wastewater treatment system, comprising a reactor, an aeration device and a computer data acquisition system; the reactor is a double chamber, the cathode chamber is provided with an aeration head to expose air, and the cathode is a catalytic membrane electrode; an intermediate chamber filled with quartz sand between the two chambers is substituted for the proton exchange membrane; an activated carbon particle loaded with an electrogenic microorganism is placed in the anode chamber, the filling degree is 75-85%, and the carbon rod is inserted into the activated carbon particles as a conductive anode. The top is sealed and has a water inlet; the external resistance is connected between the anode and the cathode, and the resistance is 1-1200 Ω. The external resistor is connected to the data acquisition system to record the generated voltage; the cathode catalytic membrane electrode is connected to the water pump, and the cathode catalytic membrane filters the water.
所述的阴极催化膜的制备方法，步骤如下：The preparation method of the cathode catalytic membrane is as follows:
所述的阴极催化膜为电催化膜或光电催化膜，阴极催化膜中的催化材料是与阳极存在费米能级差的半导体材料或具有电催化活性的材料；需选择导电基底或通过添加导电材料增加电极的导电性，实现电子传递；将催化材料与成膜材料混合刮膜于基底上制备平板膜，直接将催化材料原位生长于基底上，或添加粘结剂涂覆于基底上等方式，得到阴极催化膜。The cathode catalytic membrane is an electrocatalytic membrane or a photocatalytic membrane. The catalytic material in the cathode catalytic membrane is a semiconductor material having a Fermi level difference from the anode or a material having electrocatalytic activity; a conductive substrate needs to be selected or a conductive material is added. Increasing the conductivity of the electrode to achieve electron transfer; mixing the catalytic material with the film forming material to form a flat film on the substrate, directly growing the catalytic material on the substrate, or adding an adhesive to the substrate, etc. A cathode catalytic membrane is obtained.
所述的阴极催化膜导电基底为不锈钢网、碳纤维布、泡沫镍或碳毡；添加导电材料为碳纳米纤维、碳纳米管、石墨烯或铁粉等，成膜材料为聚偏氟乙烯、醋酸纤维素等；The conductive substrate of the cathode catalytic membrane is stainless steel mesh, carbon fiber cloth, foamed nickel or carbon felt; the conductive material is carbon nanofiber, carbon nanotube, graphene or iron powder, and the film forming material is polyvinylidene fluoride and acetic acid. Cellulose, etc.;
所述的阴极电催化膜中的电催化剂为MnO 2、CoFe 2O 4或FeOOH。 The electrocatalyst in the cathode electrocatalytic film is MnO 2 , CoFe 2 O 4 or FeOOH.
所述的阴极光电催化膜中的半导体催化剂为TiO 2、g-C 3N 4、SiC或WO 3，阴极室外需添加紫外或可见光光源。 The semiconductor catalyst in the cathode photoelectrocatalytic film is TiO 2 , gC 3 N 4 , SiC or WO 3 , and an ultraviolet or visible light source is added outside the cathode.
所述的阴极室可添加过硫酸盐或过二硫酸盐浓度为（10-200mg/L），促进硫酸根自由基产生，辅助阴极（光）电催化作用。The cathode chamber may be added with a persulfate or peroxodisulfate concentration of (10-200 mg/L) to promote the generation of sulfate radicals and assist in cathodic (photo) electrocatalysis.
上述反应器系统用于实际处理焦化废水：所述系统处理实际焦化废水COD范围为 200-2500mg/L，在启动反应器前通过稀释焦化废水驯化阳极微生物后进水处理，阴极膜通过蠕动泵驱动过滤，运行模式为间歇式或连续式，连续式水力停留时间6h-48h。The above reactor system is used for actually treating coking wastewater: the COD range of the actual coking wastewater treated by the system is 200-2500 mg/L, and the anode microorganism is domesticated by dilution coking wastewater before starting the reactor, and the cathode membrane is driven by a peristaltic pump. Filtration, operation mode is intermittent or continuous, continuous hydraulic retention time 6h-48h.
有益效果Beneficial effect
本发明的有益效果：该无膜微生物燃料电池系统， 利用阳极微生物厌氧处理废水，协同阴极催化膜（光）电催化作用及循环过滤性处理难降解焦化废水，充分利用各自优势，解决了传统MFC有机物分解效率低的问题，提升MFC的出水水质；利用石英砂填充中间层替代质子交换膜，降低工艺运行成本；耦合系统微电场提升催化过滤膜使用寿命；该反应体系占地小、流程短、处理效果好并且节能环保，利于开展放大和中试实验，以推进成果的产业化The invention has the beneficial effects that the membrane-free microbial fuel cell system utilizes anode microbial anaerobic treatment of wastewater, cooperates with cathodic catalytic membrane (photo) electrocatalysis and cyclic filtration treatment of refractory coking wastewater, and fully utilizes their respective advantages to solve the traditional The problem of low decomposition efficiency of MFC organic matter is to improve the effluent quality of MFC; the intermediate layer is replaced by quartz sand to replace the proton exchange membrane, and the process operation cost is reduced; the micro-electric field of the coupling system increases the service life of the catalytic filter membrane; the reaction system occupies a small area and has a short process Good processing effect and energy saving and environmental protection, which is conducive to carrying out amplification and pilot experiments to promote the industrialization of results
附图说明DRAWINGS
图1 一种无膜微生物燃料电池耦合阴极催化膜系统图。Figure 1 is a diagram of a membrane-free microbial fuel cell coupled cathode catalytic membrane system.
图2低浓度焦化废水在不同处理时间下TiO 2/PVDF膜出水COD去除率，图中横坐标为时间（单位：小时），纵坐标为COD去除率。 Fig. 2 COD removal rate of TiO 2 /PVDF membrane effluent at low treatment temperature for low concentration coking wastewater. The abscissa is time (unit: hour) and the ordinate is COD removal rate.
图3高浓度焦化废水在不同处理时间下TiO 2/PVDF膜出水COD去除率，图中横坐标为时间（单位：小时），纵坐标为COD去除率。 Fig.3 COD removal rate of TiO 2 /PVDF membrane effluent at high treatment temperature for high concentration coking wastewater. The abscissa is time (unit: hour) and the ordinate is COD removal rate.
图4高浓度焦化废水在不同处理时间下TiO 2/PVDF膜作阴极系统电势图，图中横坐标为时间（单位：分钟），纵坐标为电势。 Figure 4 shows the potential of the TiO 2 /PVDF membrane as the cathode system for high-concentration coking wastewater at different treatment times. The abscissa is time (unit: minute) and the ordinate is potential.
本发明的实施方式Embodiments of the invention
以下结合附图和技术方案，进一步说明本发明的具体实施方式。The specific embodiments of the present invention are further described below in conjunction with the drawings and technical solutions.
实施例Example 1 1
(1) 阴极TiO 2/PVDF催化膜的制备：将TiO 2(15 wt%)和碳纳米纤维(25 wt%)添加在PVDF(10 wt%) DMF铸膜液中，经过6 h搅拌后，超声脱泡30min，以碳纳米纤维布为基底，涂覆厚度为300 μm，经相转化12h后得到TiO 2/PVDF催化膜阴极。 (1) Preparation of cathode TiO 2 /PVDF catalytic membrane: TiO 2 (15 wt%) and carbon nanofibers (25 wt%) were added to PVDF (10 wt%) DMF casting solution, and after stirring for 6 h, The ultrasonic defoaming was carried out for 30 min, and the carbon nanofiber cloth was used as the substrate. The coating thickness was 300 μm. After phase transformation for 12 h, the TiO 2 /PVDF catalytic film cathode was obtained.
（2）无膜微生物燃料电池耦合阴极催化膜系统处理低浓度焦化废水运行：阳极室中填充负载有产电微生物的活性炭颗粒（填充度85%），碳棒为导电阳极插入活性炭颗粒中，顶端密闭低浓度焦化废水（COD约200mg/L）；两室之间为石英砂填充的中间室取代质子交换膜；将上述催化膜装于矩形膜组件中（双面），阴极室底部曝入空气，提供氧气用于电子活化氧气产生自由基； 通过泵抽吸阴极膜组件顶端出水，阴阳极之间通过1000Ω外电阻连接。实际焦化废水依次稀释比例为100%，50%，0%驯化阳极微生物。当阳极微生物产电稳定后，经过蠕动泵连续泵入低浓度焦化废水，水力停留时间48h。每间隔12h分别通过泵吸从阴极膜组件上方取出水样，采用重铬酸钾法测定出水COD去除率。如图2所示，低浓度废水直接经过阳极微生物作用耦合阴极膜电催化作用，运行12h达到90%去除率，阴极室出水最终COD去除率达99%。(2) Non-membrane microbial fuel cell coupled cathode catalytic membrane system for processing low-concentration coking wastewater operation: the anode chamber is filled with activated carbon particles (filling degree 85%) loaded with electricity-producing microorganisms, and the carbon rod is inserted into the activated carbon particles as a conductive anode. Sealing low-concentration coking wastewater (COD about 200mg/L); replacing the proton exchange membrane with quartz sand filled intermediate chamber between the two chambers; installing the above catalytic membrane in a rectangular membrane module (double-sided), and injecting air into the bottom of the cathode chamber Providing oxygen for electron activation of oxygen to generate free radicals; pumping the top of the cathode membrane module by pumping water, and the anode and cathode are connected by a 1000Ω external resistor. The actual coking wastewater is diluted 100%, 50%, 0% domesticated anode microorganisms. When the anode microbial production is stable, the peristaltic pump is continuously pumped into the low-concentration coking wastewater, and the hydraulic retention time is 48 hours. The water sample was taken out from the cathode membrane module by pumping at intervals of 12 h, and the COD removal rate of the water was measured by the potassium dichromate method. As shown in Fig. 2, the low-concentration wastewater directly passes through the anode microbial interaction coupled with the cathode membrane electrocatalysis, and reaches a 90% removal rate after 12 hours of operation, and the final COD removal rate of the cathode chamber effluent reaches 99%.
实施例Example 22
(1) 阴极TiO 2/PVDF催化膜的制备：同实施案例1所述。 (1) Preparation of cathode TiO 2 /PVDF catalytic membrane: as described in Example 1.
（2）无膜微生物燃料电池耦合阴极催化膜系统处理高浓度焦化废水运行：阳极室中填充负载有产电微生物的活性炭颗粒（填充度85%），碳棒为导电阳极插入活性炭颗粒中，顶端密闭低浓度焦化废水（COD约2000mg/L）；两室之间为石英砂填充的中间室取代质子交换膜；将上述催化阴极膜装于矩形膜组件中（双面），阴极室底部曝入空气，提供氧气用于电子活化氧气产生自由基； 通过泵抽吸阴极膜组件顶端出水，阴阳极之间通过1000Ω外电阻连接。实际焦化废水依次稀释比例为100%，50%，0%驯化阳极微生物。当阳极微生物产电稳定后，经过蠕动泵连续泵入低浓度焦化废水，水力停留时间48h。每间隔12h分别通过泵吸从阴极膜组件上方取出水，采用重铬酸钾法测定出水COD去除率。如图3所示，阴极室出水COD去除率经过48h后达80%, 80h后去除率约为75%。该条件下系统产电情况如图4所示，起始电池电势约0.45v，系统运行的前5h电池电势随着阴极室污染物降解率升高而降低后稳定。(2) Non-membrane microbial fuel cell coupled cathode catalytic membrane system for processing high-concentration coking wastewater operation: the anode chamber is filled with activated carbon particles (filling degree 85%) loaded with electricity-producing microorganisms, and the carbon rod is a conductive anode inserted into the activated carbon particles, the top Sealing low-concentration coking wastewater (COD about 2000mg/L); replacing the proton exchange membrane with an intermediate chamber filled with quartz sand between the two chambers; installing the catalytic cathode membrane in a rectangular membrane module (double-sided), and exposing the bottom of the cathode chamber Air, providing oxygen for electron activation of oxygen to generate free radicals; pumping the top of the cathode membrane module by pumping water, and the anode and cathode are connected by a 1000Ω external resistor. The actual coking wastewater is diluted 100%, 50%, 0% domesticated anode microorganisms. When the anode microbial production is stable, the peristaltic pump is continuously pumped into the low-concentration coking wastewater, and the hydraulic retention time is 48 hours. Water was taken from above the cathode membrane module by pumping at intervals of 12 h, and the COD removal rate of the water was measured by potassium dichromate method. As shown in Fig. 3, the removal rate of COD in the cathode chamber reaches 80% after 48 hours, and the removal rate after 80 hours is about 75%. The power generation of the system under this condition is shown in Figure 4. The initial battery potential is about 0.45v. The battery potential of the first 5h of the system is stable and decreases with the increase of the pollutant degradation rate of the cathode chamber.

Claims (10)

  1. 一种阴极催化膜耦合无膜微生物燃料电池用于焦化废水处理系统，其特征在于，所述的阴极催化膜耦合无膜微生物燃料电池及焦化废水处理系统包括反应器、曝气装置和计算机数据采集系统；所述反应器为双室，阴极室设置曝气头曝空气，阴极为催化膜电极；两室之间为石英砂填充的中间室取代质子交换膜；阳极室中放置负载有产电微生物的活性炭颗粒，填充度75-85%，碳棒为导电阳极插入活性炭颗粒中，顶端密闭，有进水口；阴阳极之间连外电阻，阻值为1-1200Ω，外电阻连接数据采集系统，记录产生电压；阴极催化膜电极外连出水泵，由阴极催化膜过滤后出水。Cathode catalytic membrane coupled membraneless microbial fuel cell for coking wastewater treatment system, characterized in that the cathode catalytic membrane coupled with membraneless microbial fuel cell and coking wastewater treatment system comprises reactor, aeration device and computer data acquisition The reactor is a double chamber, the cathode chamber is provided with an aeration head to expose air, and the cathode is a catalytic membrane electrode; an intermediate chamber filled with quartz sand between the two chambers is substituted for the proton exchange membrane; and the anode chamber is placed with a load generating microorganism The activated carbon granules have a filling degree of 75-85%. The carbon rod is a conductive anode inserted into the activated carbon granules, the top is sealed, and there is a water inlet; the external resistance between the anode and the cathode is connected, the resistance is 1-1200 Ω, and the external resistance is connected to the data acquisition system. The generated voltage is recorded; the cathode catalytic membrane electrode is connected to the water pump, and is filtered by the cathode catalytic membrane to discharge water.
  2. 根据权利要求1所述的阴极催化膜耦合无膜微生物燃料电池用于焦化废水处理系统，其特征在于，所述的阴极催化膜的制备方法，步骤如下：The cathode catalytic membrane-coupled membrane-free microbial fuel cell according to claim 1 is used in a coking wastewater treatment system, characterized in that the method for preparing the cathode catalytic membrane is as follows:
    所述的阴极催化膜为电催化膜或光电催化膜，阴极催化膜中的催化材料是与阳极存在费米能级差的半导体材料或具有电催化活性的材料；通过选择导电基底或通过添加导电材料增加电极的导电性，实现电子传递；将催化材料与成膜材料混合刮膜于基底上制备平板膜，直接将催化材料原位生长于基底上，或添加粘结剂涂覆于基底上，得到阴极催化膜。The cathode catalytic membrane is an electrocatalytic membrane or a photocatalytic membrane, and the catalytic material in the cathode catalytic membrane is a semiconductor material having a Fermi level difference from the anode or a material having electrocatalytic activity; by selecting a conductive substrate or by adding a conductive material Increasing the conductivity of the electrode to realize electron transfer; mixing the catalytic material with the film forming material to form a flat film on the substrate, directly growing the catalytic material on the substrate, or adding an adhesive to the substrate, thereby obtaining Cathode catalytic membrane.
  3. 根据权利要求1或2所述的阴极催化膜耦合无膜微生物燃料电池用于焦化废水处理系统，其特征在于，所述的阴极催化膜导电基底为不锈钢网、碳纤维布、泡沫镍或碳毡。The cathode catalytic membrane-coupled membrane-free microbial fuel cell according to claim 1 or 2 is used in a coking wastewater treatment system, characterized in that the cathode catalytic membrane conductive substrate is a stainless steel mesh, a carbon fiber cloth, a foamed nickel or a carbon felt.
  4. 根据权利要求1或2所述的阴极催化膜耦合无膜微生物燃料电池用于焦化废水处理系统，其特征在于，所述的导电材料为碳纳米纤维、碳纳米管、石墨烯或铁粉，所述的成膜材料为聚偏氟乙烯或醋酸纤维素。The cathode catalytic membrane-coupled membrane-free microbial fuel cell according to claim 1 or 2, wherein the conductive material is carbon nanofiber, carbon nanotube, graphene or iron powder. The film-forming material described is polyvinylidene fluoride or cellulose acetate.
  5. 根据权利要求3所述的阴极催化膜耦合无膜微生物燃料电池用于焦化废水处理系统，其特征在于，所述的导电材料为碳纳米纤维、碳纳米管、石墨烯或铁粉，所述的成膜材料为聚偏氟乙烯或醋酸纤维素。The cathode catalytic membrane-coupled membrane-free microbial fuel cell according to claim 3, wherein the conductive material is carbon nanofiber, carbon nanotube, graphene or iron powder, The film forming material is polyvinylidene fluoride or cellulose acetate.
  6. 根据权利要求1、2或5所述的阴极催化膜耦合无膜微生物燃料电池用于焦化废水处理系统，其特征在于，所述的阴极电催化膜中的电催化剂为MnO 2、CoFe 2O 4或FeOOH；所述的阴极光电催化膜中的半导体催化剂为TiO 2、g-C 3N 4、SiC或WO 3，阴极室外添加紫外或可见光光源。 The cathode catalytic membrane-coupled membrane-free microbial fuel cell according to claim 1, 2 or 5, wherein the electrocatalyst in the cathode electrocatalytic membrane is MnO 2 or CoFe 2 O 4 . Or FeOOH; the semiconductor catalyst in the cathode photoelectrocatalytic film is TiO 2 , gC 3 N 4 , SiC or WO 3 , and an ultraviolet or visible light source is added outside the cathode.
  7. 根据权利要求3所述的阴极催化膜耦合无膜微生物燃料电池用于焦化废水处理系统，其特征在于，所述的阴极电催化膜中的电催化剂为MnO 2、CoFe 2O 4或FeOOH；所述的阴极光电催化膜中的半导体催化剂为TiO 2、g-C 3N 4、SiC或WO 3，阴极室外添加紫外或可见光光源。 The cathode catalytic membrane-coupled membrane-free microbial fuel cell according to claim 3, wherein the electrocatalyst in the cathode electrocatalytic membrane is MnO 2 , CoFe 2 O 4 or FeOOH; The semiconductor catalyst in the cathode photoelectrocatalytic film is TiO 2 , gC 3 N 4 , SiC or WO 3 , and an ultraviolet or visible light source is added outside the cathode.
  8. 根据权利要求4所述的阴极催化膜耦合无膜微生物燃料电池用于焦化废水处理系统，其特征在于，所述的阴极电催化膜中的电催化剂为MnO 2、CoFe 2O 4或FeOOH；所述的阴极光电催化膜中的半导体催化剂为TiO 2、g-C 3N 4、SiC或WO 3，阴极室外添加紫外或可见光光源。 The cathode catalytic membrane-coupled membrane-free microbial fuel cell according to claim 4, wherein the electrocatalyst in the cathode electrocatalytic membrane is MnO 2 , CoFe 2 O 4 or FeOOH; The semiconductor catalyst in the cathode photoelectrocatalytic film is TiO 2 , gC 3 N 4 , SiC or WO 3 , and an ultraviolet or visible light source is added outside the cathode.
  9. 根据权利要求1、2、5、7或8所述的阴极催化膜耦合无膜微生物燃料电池用于焦化废水处理系统，其特征在于，所述的阴极室中添加浓度为10-200mg/L的过硫酸盐或过二硫酸盐促进硫酸根自由基产生，辅助阴极催化作用。The cathode catalytic membrane-coupled membrane-free microbial fuel cell according to claim 1, 2, 5, 7 or 8 for use in a coking wastewater treatment system, characterized in that the cathode chamber is added at a concentration of 10-200 mg/L. Persulfate or peroxodisulfate promotes the generation of sulfate radicals and assists in cathodic catalysis.
  10. 根据权利要求9所述的阴极催化膜耦合无膜微生物燃料电池用于焦化废水处理系统，其特征在于，所述的焦化废水的COD为 200-2500mg/L，在启动反应器前通过稀释焦化废水驯化阳极微生物后进水处理，阴极膜通过蠕动泵驱动过滤，运行模式为间歇式或连续式，连续式水力停留时间6h-48h。The cathode catalytic membrane-coupled membrane-free microbial fuel cell according to claim 9 for use in a coking wastewater treatment system, characterized in that the COD of the coking wastewater is 200-2500 mg/L, and the coking wastewater is diluted before starting the reactor. The domesticated anode microorganisms are treated with water, and the cathode membrane is driven by a peristaltic pump. The operation mode is intermittent or continuous, and the continuous hydraulic retention time is 6h-48h.
PCT/CN2018/091909 2018-03-06 2018-06-20 Use of membrane-free microbial fuel cell coupled with cathode catalytic membrane in coking wastewater treatment system WO2019169785A1 (en)

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