WO2011006448A1 - 一种底泥原位削减同时微生物产电的方法及装置 - Google Patents

一种底泥原位削减同时微生物产电的方法及装置 Download PDF

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WO2011006448A1
WO2011006448A1 PCT/CN2010/075216 CN2010075216W WO2011006448A1 WO 2011006448 A1 WO2011006448 A1 WO 2011006448A1 CN 2010075216 W CN2010075216 W CN 2010075216W WO 2011006448 A1 WO2011006448 A1 WO 2011006448A1
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Prior art keywords
cathode
sediment
anode
fuel cell
microbial fuel
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PCT/CN2010/075216
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English (en)
French (fr)
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周顺桂
张礼霞
庄莉
王跃强
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广东省生态环境与土壤研究所
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Priority to US13/510,173 priority Critical patent/US9149845B2/en
Publication of WO2011006448A1 publication Critical patent/WO2011006448A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C1/00—Reclamation of contaminated soil
    • B09C1/10—Reclamation of contaminated soil microbiologically, biologically or by using enzymes
    • 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
    • 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
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/006—Electrochemical treatment, e.g. electro-oxidation or electro-osmosis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/007—Contaminated open waterways, rivers, lakes or ponds
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention belongs to the field of environment and new energy technology, and relates to a technology for treating and treating sediment by using a microbial fuel cell, and particularly relates to a black odorous mud bio-electricity utilizing water bodies such as rivers, ponds, ditches and the like, and reducing the bottom in situ.
  • Mud chemical oxygen demand ( COD) method and device relates to a technology for treating and treating sediment by using a microbial fuel cell, and particularly relates to a black odorous mud bio-electricity utilizing water bodies such as rivers, ponds, ditches and the like, and reducing the bottom in situ.
  • Mud chemical oxygen demand ( COD) method and device a method for treating and treating sediment by using a microbial fuel cell, and particularly relates to a black odorous mud bio-electricity utilizing water bodies such as rivers, ponds, ditches and the like, and reducing the bottom in situ.
  • COD Mud chemical oxygen demand
  • Black body odor and eutrophication are common phenomena in China's water pollution. Due to long-term pollution, black muddy sediments in rivers, ponds, ditches and other water bodies are deposited. In the above water treatment, when the water quality is significantly improved or the water body is disturbed, the pollutants in the sediment will be released upwards, making the sediment become The intrinsic source of pollution of water bodies. Therefore, sediment management is the fundamental to improve water quality, and it is the fundamental problem to be solved in China's water pollution. The situation is urgent, and it is imperative to vigorously develop sediment management technology.
  • the main methods of sediment management include sediment dredging, chemical masking, and microbial remediation.
  • Dredging of sediment that is, using engineering measures to remove contaminated sediment and remove the endogenous source of polluted water. It is the most commonly used method in sediment management, but its cost is high, including many steps such as dredging, transportation, treatment and disposal of sediment, and the disposal of the sediment is easy to cause odor emission and leachate pollution.
  • Contamination 2) Sediment cover means placing a large amount of masking material on the contaminated sediment to isolate the sediment from the water body and prevent secondary pollution caused by nutrients, heavy metals and organic pollutants in the sediment entering the water body.
  • 200710191195.2 discloses an eutrophic water body sediment masking repairing method, which requires a large amount of clay masking materials and additives, and the materials need to be sifted, sieved, and dried at a high temperature. Work, put it into the lake water body, can only block the release of nutrients such as nitrogen and phosphorus in the existing sediments and the algae organisms to float and reproduce, and can not fundamentally reduce pollution, with the sedimentation and accumulation of water pollutants, still It will form a black odor sediment; 3) Microbial remediation refers to the use of naturally occurring or domesticated microorganisms to cause in situ degradation of pollutants in the sediment into CO 2 and water, or into harmless substances.
  • Microbial remediation technology has the advantages of low engineering cost, simple implementation, good effect, less disturbance to the environment, and safety and reliability.
  • the sediment in the water contains a large amount of organic matter (2 to 45%), which is the main cause of anaerobic black odor and harmful water quality.
  • There are three main sediment management methods such as sediment dredging, chemical masking and microbial remediation. It is only by various measures to eliminate the pollutants in the sediment by ectopic or in situ, mainly to reduce the chemical oxygen demand (COD) in the sediment, but does not consider the conversion of abundant biomass in the sediment. Collected and utilized, the abundant biomass contained in the sediment organic matter can be wasted.
  • COD chemical oxygen demand
  • MFC microbial fuel cells
  • MFC It is a product of microbial technology and battery technology. It is a power generation device that uses microorganisms as a catalyst to directly convert chemical energy in organic matter into electrical energy. It has the dual functions of electricity generation and waste disposal.
  • MFC The basic principle is that organic matter is oxidized by microorganisms in the anaerobic anode chamber as a fuel, and the generated electrons are captured by the microorganisms and transmitted to the anode of the battery. The electrons pass through the external circuit to reach the cathode, thereby forming a loop to generate electric current, and the protons pass through the exchange membrane to reach the cathode. Reacts with oxygen to form water.
  • MFC can also generate electricity from pollutants such as domestic sewage and human waste. Therefore, it is an advanced biomass energy utilization technology with great development potential and is expected to become the pillar technology for future organic waste treatment.
  • Application number is 200510011855.5 and 00810805.6
  • the invention patents respectively disclose a single-cell biofuel cell for treating organic wastewater and a double-cell biofuel cell for treating wastewater and activated sludge, but they are only laboratory-scale single cells (open circuit voltage does not exceed 0.8V ), the expansion and amplification of a plurality of single cells are not involved.
  • the applicant's application number is 200810029221.6
  • the invention patent application discloses a microbial fuel cell stack, which provides a multi-stage serial/parallel MFC battery stack with a common anode fuel, which solves the problem of uniform fuel in/out and realizes voltage /
  • the increase in current solves the problem of expansion and amplification of microbial fuel cells.
  • the device is still only suitable for fuels with low solid content and good fluidity, liquid or slurry organic waste, and the fuel is pumped into the anode chamber of the stack, and is biooxidized and discharged.
  • the COD flows out to the other end to achieve the purpose of processing and electricity generation.
  • the above-mentioned microbial fuel cell device is not suitable for treating sediment, because: 1 The sediment must be pumped and pumped into the anode chamber of the microbial fuel cell. The amount of work is extremely large, and it is difficult to achieve in the presence of overlying water, and it also achieves the purpose of in-situ treatment in the absence of mud; 2 The sediment has a high solid content and the particulate matter is likely to cause blockage; 3) If it is to be treated in situ, it is necessary to immerse the MFC in the sediment of the water body so that the sediment contacts the anode; the existing MFC If immersed in water, the cathode cannot be exposed to the air, making it impossible to achieve MFC. The necessary cathode oxygen reduction reaction process. These technical difficulties make existing microbial fuel cells not directly applied to the sludge treatment to produce clean electrical energy.
  • the object of the present invention is to overcome the deficiencies of the existing sludge treatment technology and to provide a new method for reducing sludge pollution and generating electricity in situ by using a microbial fuel cell.
  • the method of the invention can oxidize and decompose organic matter in the sediment into CO 2 and water in situ, and simultaneously generate clean electric energy, and has the dual effects of in-situ reduction of sediment and microbial electricity generation.
  • Another object of the present invention is to provide a microbial fuel cell device capable of realizing in-situ reduction of sediment while producing electricity, which can be easily installed in water bodies such as rivers, ponds, ditches, etc., and utilizes sediment in situ.
  • the organic matter is fuel, and the generated electricity can be used to expose oxygen to water.
  • the microbial fuel cell comprising a cathode chamber, a cathode, an anode, and a cathode respectively
  • the lead wire is drawn from the anode; the cathode chamber is filled with air, the cathode is exposed to oxygen through the cathode chamber air, one side of the anode is in close contact with the cathode, and the other side is in contact with the bottom mud.
  • the method for in situ reduction of the above-mentioned sediment and simultaneous microbial electricity production specifically includes the following steps:
  • the microbial fuel cell is placed in the sediment to ensure that the cathode chamber is filled with air, the other side of the anode contacts the sediment, the battery circuit is connected, and the microorganism is domesticated to generate electricity.
  • the method for ensuring that the cathode chamber is filled with air is preferably a method in which one end of the battery bobbin is open and the other end is sealed, and one end of the open end communicates with the air, the hollow section of the skeleton is wrapped by the cathode and is treated with water proof, and the other end is sealed. . Insert one end of the battery skeleton seal into the bottom mud, the top of the open end is exposed to the water surface, and the anode contacts the sediment to construct the battery.
  • the sealed end is inserted into the bottom of the river, the pond and the ditch, and the hollow section of the membrane cathode and the anode is not inserted into the sediment, and the top of the insulating tube is exposed to the water surface to ensure that the cathode chamber is filled with air and is connected.
  • Battery circuit domesticated microbial electricity.
  • the method may further comprise the step (1)
  • the microbial fuel cell is constructed as a microbial fuel cell stack, and the above step (2) is performed after the cell stack is constructed.
  • the effect can be verified by detecting the sediment COD removal effect and the output power density.
  • the insulating battery skeleton of the microbial fuel cell may be a PVC with a hollow section
  • the cathode adopts a membrane cathode.
  • the hollow section may be more than one section, and may be two sections or several sections, each of which is first wrapped with a film cathode, and the two ends of the membrane cathode are in contact with the insulating tube. Anti-seepage treatment, and then wrapped around the cathode of the membrane with an anode.
  • the present invention also provides a more preferred solution, in which one end of two or more sealed sealing tubes of the microbial fuel cell is unsealed, and the originally closed ends are connected to form a closed loop through a connecting tube to constitute a microbial fuel cell. stack.
  • the battery stack includes a plurality of microbial fuel cells and a plurality of connecting tubes, and the sealed end of the microbial fuel cell insulating tubes is connected by a connecting pipe; the plurality of connecting tubes can communicate with each other to form a closed loop, and the loops are It is filled with air; it may not be connected to each other, but it only serves to seal the skeleton and ensure that the open end of the battery skeleton is exposed to the water surface.
  • the connecting pipe is also made of an insulating material, for example PVC pipe. It may also be a fixed plate, and two or more of the above microbial fuel cells are sealed and fixed on the fixed plate to form a battery stack.
  • the plurality of microbial fuel cells Vertically disposed on a plurality of connected straight pipes connected in cross section, a plurality of connected straight pipes are connected to form a closed circuit, the circuit is filled with air, and each battery is erected in the sediment to be treated, and the top end is exposed to the water surface to ensure that the cathode chamber is filled Air and air can flow smoothly between the cathode compartments of each battery to form a microbial fuel cell stack.
  • each microbial fuel cell pipe opening is exposed to the water surface to ensure that the air fills the cathode chamber; depending on the situation, the number of straight and connecting pipes of the battery can be increased, and each MFC Connecting the series or parallel increases the size of the stack and achieves better amplification.
  • the battery insulating tube and the connecting pipe can be processed by using an inexpensive insulating pipe, preferably PVC Tube.
  • the hollowing can be carried out in a manner conventional in the prior art, such as opening a groove, drilling, etc., and the shape and size of the groove and the hole are not particularly required.
  • the present invention is preferably drilled, and a PVC pipe having a diameter of 5 to 20 cm can be selected.
  • a pipe section with a length of 10 to 30 cm is selected as a hollow section on the PVC pipe, and the hole is drilled in the hollow section, the hole diameter is 0.5 to 2 cm, and the density is about 100 to 3000 holes per square meter.
  • the membrane cathode can be formed by hot pressing of a catalyst-attached carbon cloth and a separator.
  • the present invention employs a low-cost membrane such as an anion exchange membrane and a cation exchange membrane.
  • the cloth cathode described in the applicant's application No. 200910040920.5 can also be used.
  • the catalyst is selected according to conventional techniques such as pyrolysis of ferrous phthalocyanine (pyr-FePc), tetramethoxyphenyl cobalt porphyrin (CoTMPP) or manganese dioxide (MnO 2 ).
  • One of the methods for fabricating the cathode of the membrane weighing pyr-FePc, CoTMPP or MnO 2 , conductive materials (graphite, acetylene black, carbon black or activated carbon, etc.) and binder (polytetrafluoroethylene (PTFE) or polydisperse Fluorine (PVDF) is mixed at a weight ratio of 65:20:15, and mixed with N-methylpyrrolidone solvent to form a paste. After ultrasonic dispersion, it is uniformly applied to a dry carbon cloth, and dried under vacuum to obtain a cathode; The membrane is hot pressed at 115 to 120 ° C for 3 to 10 minutes to obtain a membrane cathode.
  • conductive materials graphite, acetylene black, carbon black or activated carbon, etc.
  • binder polytetrafluoroethylene (PTFE) or polydisperse Fluorine (PVDF) is mixed at a weight ratio of 65:20:15, and mixed
  • the anode material is mainly a carbon material having a larger specific area, such as carbon felt, carbon fiber or the like.
  • the film cathode is wrapped around the hollow section of the pipe, and the carbon cloth side of the film cathode is tightly attached to the PVC.
  • the tube contacts the air in the skeleton through the hollow space on the pipe, and the anode material is wrapped on the outside of the cathode of the film, and is closely attached to the film side of the cathode of the film, and the wires are respectively led out from the cathode and the anode, thereby obtaining a microbial fuel cell stack.
  • the invention overcomes the deficiencies of the prior art bottom mud treatment technology, such as high cost, complicated steps, cumbersome steps, secondary pollution, chemical masking materials and complicated process processing, and cannot fundamentally reduce pollution defects.
  • Microbial remediation does not consider the insufficiency of conversion, collection and utilization of abundant biomass in the sediment.
  • the microbial fuel cell method is used to solve the problem of in situ reduction of sediment, and the organic matter in the sediment is used as fuel. In-situ reduction of pollution can generate electricity at the same time, and the generated electricity can be used to expose oxygen to water.
  • the invention provides a device for realizing the method, which does not need to pump the sediment into the anode chamber of the microbial fuel cell, and the cathode can also be exposed to the air, thereby solving the technical problem that the microbial fuel cell technology is applied to the sediment treatment, and realizing The effective treatment of the black odor sludge with high solid content, and can turn waste into treasure to achieve energy recycling.
  • the device can be extended horizontally and vertically according to specific conditions, and is easy to maintain and can be recycled for a long time, and has the advantages of compact structure, flexible operation, low cost, high output power density, and chemical oxygen demand of the sediment ( COD) has good cutting effect, does not affect river circulation, and is environmentally friendly. It is suitable for engineering application.
  • Figure 1 Schematic diagram of microbial fuel cell stack structure
  • FIG. 2 Schematic diagram of membrane cathode-wrapped hollow skeleton structure of microbial fuel cell
  • FIG. 3 Schematic diagram of the structure of the anode coated membrane cathode of microbial fuel cell
  • FIG. 4 Schematic diagram of the cross-section of a microbial fuel cell
  • Fig. 7 The performance of tubular microbial fuel cell unit in the treatment of river bottom sediment
  • a tubular microbial battery is used to realize a method for in situ reduction of microorganisms and microbial electricity generation, comprising the following steps:
  • FIG. 3 is a schematic structural view of a membrane cathode encapsulating hollow skeleton of a microbial fuel cell
  • FIG. 3 is a schematic structural view of a microbial fuel cell anode encapsulating cathode
  • FIG. 4 is a schematic diagram of a cross section of a battery cell
  • FIG. It is an example of a physical example of a microbial fuel cell, in which one end of the seal is omitted and not shown.
  • the battery comprises a skeleton 2 provided with a hollow section 9, a membrane cathode 3 and an anode 4, and a membrane cathode 3 enclosing a skeleton 2 hollow section 9
  • the cathode chamber is formed, see Fig. 2, and the anode 4 encloses the membrane cathode 3, see Fig. 3; the wires are taken out from the cathode and the anode, respectively (conventional technology, not shown).
  • the hollow section 9, the cathode 3, and the anode 4 are configured as a structure, and the structure can be disposed in a plurality of places on one tubular battery cell.
  • the skeleton 2 is processed by an insulating pipe, preferably PVC Tube, cheap and good.
  • the hollowing can adopt the manner conventionally used in the prior art.
  • the present invention preferably drills holes, and a PVC pipe having a diameter of 5 to 20 cm can be selected, and the length of the PVC pipe is selected to be 10 ⁇ .
  • the 30cm pipe segment is used as a single MFC hollow skeleton, and the hole is drilled in the skeleton hollow pipe section.
  • the hole 8 has a diameter of 0.5 to 2 cm and a density of about 100 to 3000 per square meter of the outer surface area of the skeleton. Hole.
  • the catalyst-carrying carbon cloth layer 6 is prepared as follows: MnO 2 , carbon black conductive material and polyvinylidene fluoride (PVDF) binder are weighed and mixed at a weight ratio of 65:20:15, and N-methylpyrrolidone is added. The solvent is stirred into a paste, ultrasonically dispersed, uniformly coated on a dry carbon cloth, and vacuum-dried to obtain a catalyst-bearing carbon cloth layer 6 .
  • the membrane 7 is preferably a cation exchange membrane.
  • the film cathode 3 was prepared by hot-pressing the catalyst-carrying carbon cloth layer 6 and the separator 7 at 115 ° C for 5 minutes.
  • the anode 4 is preferably a carbon felt.
  • the closed end of the battery is inserted into the bottom of the river, pond, and ditch.
  • Experimental simulation device see Figure 6 .
  • the anode is in contact with the sediment to form an anode chamber, and the anaerobic microorganisms are enriched, propagated, and domesticated in the anode chamber.
  • the top of the skeleton 2 is exposed to the water surface and is not submerged by water, ensuring that the cathode chamber is filled with air and cannot have water.
  • the epoxy resin sealing film can be used at both ends of the cathode and the PVC pipe, and the film 7 is on the outside, and the catalyst carbon cloth layer is 6 On the inside of the contact pipe and facing the air in the frame, air is in contact with the cathode through the small holes.
  • the anode and cathode are drawn by wires according to conventional techniques to form a loop.
  • the organic pollutants in the sediment are oxidized by anaerobic microbial microorganisms to generate electrons and protons.
  • the protons pass through the membrane and electrons to the cathode through the external circuit to react with oxygen, thereby outputting electric current.
  • one end of the insulating tube seal is unsealed, and is vertically (or vertically) disposed on the same connecting straight tube, and the two ends of the connecting straight tube are sealed to form a battery stack. .
  • the connecting tube is also made of an insulating material.
  • the present invention provides a microbial fuel cell stack as shown in Figures 8 and 9 of the accompanying drawings.
  • Figure 8 Is an example of a tubular microbial fuel cell stack skeleton
  • Figure 9 is an illustration of an assembled tubular microbial fuel cell stack.
  • the microbial fuel cell stack is composed of a plurality of battery cells and a connecting tube, and the cathode chambers are connected to each other.
  • the battery cell is as shown in Figure 2 and the drawing 3, Figure 4 and Figure 5 are the same as in Embodiment 1.
  • the plurality of microbial fuel cells Vertically placed on a plurality of connected straight pipes connected in cross section, a plurality of connected straight pipes are connected to form a closed circuit, and each battery is erected in the sediment to be treated, and the top end is exposed to the water surface to ensure that the cathode chamber is filled with air, and the air can be
  • the cathode chambers of each battery are smoothly circulated to form an efficient microbial fuel cell stack.
  • the battery stack is placed in the bottom mud of the river, pond and ditch, and the anode and the bottom mud contact to form an anode chamber, and the anaerobic microorganisms are enriched, propagated and domesticated in the anode chamber.
  • the top of the skeleton of each monomer is exposed to the water surface to ensure that the cathode chamber is filled with air.
  • Membrane cathode wrapped with small holes On the PVC pipe (the film is outside, the carbon cloth is inside, that is, the carbon cloth layer contacts the pipe), and the air contacts the cathode through the small hole.
  • Individual monomer MFC Both the anode and the cathode have lead wires, and a plurality of single cells can be connected in series or in parallel as needed.
  • the organic pollutants in the sediment are oxidized by anaerobic microbial microorganisms to generate electrons and protons.
  • the protons pass through the membrane and electrons to the cathode through the external circuit to react with oxygen, thereby outputting electric current.
  • the cathode and the cation exchange membrane (the side coated with the catalyst are in contact with the membrane) are hot pressed at a temperature of 115 ° C and a pressure of 14 MPa for 5 minutes, and are taken out to cool to room temperature, which is a membrane cathode; reference may also be made to other existing membrane cathodes. Preparation.
  • FIG. 4 is a schematic diagram of a cross-sectional structure of the battery cell
  • the battery is inserted into the river bottom mud, and the anode and the bottom mud contact to form an anode chamber, and the anaerobic electricity-generating microorganisms are enriched, propagated, and domesticated in the anode chamber, and the top of the hollow skeleton is exposed to the water surface to ensure that the cathode chamber is filled with air.
  • the organic matter in the sediment is oxidized by the electrogenetic microorganism to generate electrons and protons, and the protons are passed through the membrane and electrons to the cathode through the external circuit to react with oxygen to form an electric current.
  • the 30 ⁇ external resistance is connected to the cathode and cathode of the MFC for a half-year sediment production test.
  • the power output of the battery, the redox potential of the sediment before and after the reaction, the chemical oxygen demand (COD) and the acid volatile sulfide are determined by conventional techniques. AVS), the results are shown in Figure 6, Figure 7 and Table 1. The results show that the black stinky mud is 6 After the in-situ electric power restoration treatment of the month, the color of the sediment changed from dark black to yellowish brown due to oxidation of the organic matter in the sediment, and the odor was basically eliminated. As can be seen from Table 1, the COD removal rate of the sediment was 36.2%. The acid volatile sulfide removal rate was 94.4%, and the redox potential of the sediment increased from the initial -169.5mV to +237.2mV.
  • Oxidation reduction potential (mV) COD (mg/L) AVS (mg/g) Original sediment -169.5 31850 6.61 MFC processing (external resistance 30 ⁇ ) +237.2 20320 0.37
  • the output power of the sediment MFC increases first and then decreases.
  • the power increase in the early stage ie, the first one after start-up
  • the power is reduced later.
  • the maximum output power of the sediment MFC is about 100.4 mW/m 2 (that is, the output power converted into the cathode surface area), and the open circuit voltage is 0.84 V.
  • Example 5 Treatment of microbial fuel cell stacks on pond sediment and electricity production effect
  • the tubular MFC stack was constructed and assembled according to the method of Example 4 except that the hollow skeleton was changed from one of the examples 4 to 10, and the oxygen reduction catalyst of the membrane cathode was changed from manganese dioxide (MnO 2 ) to tetramethoxy. Phenyl cobalt porphyrin (CoTMPP).
  • Each of the unit cells is connected by a hollow connecting pipe of the same diameter, and each of the cathode chambers communicate with each other, that is, a tubular microbial fuel cell stack, as shown in FIG. 8 and FIG.
  • the above-mentioned battery stack is inserted into the bottom sediment of the pond to form an anode chamber, and the anaerobic electricity-generating microorganisms are enriched, propagated, and domesticated in the anode chamber, and the top of the hollow skeleton is exposed to the water surface to ensure that the cathode chamber is filled with air, but is not submerged by water.
  • Individual monomer MFC The connection was made in parallel (external resistance was 5 ⁇ ), and the in-situ power generation repair test of the sediment was carried out for half a year.
  • the power output of the battery, the redox potential of the sediment before and after the reaction, the chemical oxygen demand (COD) and the acid volatile sulfide (AVS) were measured by conventional techniques. The results showed that the black odor pond sediment was passed through the original for 6 months. After the production and repair of electricity, the color of the sediment changed from dark black to yellowish brown due to oxidation of the organic matter in the sediment, and the odor was basically eliminated.
  • the COD of the sediment decreased from the initial 23680mg/L to 14560mg/L, the removal rate was 38.5%; the acid volatile sulfide (AVS) decreased from the initial 5.35mg/g to 0.46mg/L. The removal rate was 91.4.
  • the redox potential of the sediment increased from the initial -151.2mV to +245.5mV.
  • the 6-month electricity production data showed that the maximum output power of the sediment MFC was about 56.1mW/m 2 (that is, converted into cathode). Surface area output power), open circuit voltage is 0.76V.

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Description

一种底泥原位削减同时微生物产电的方法及装置 一种底泥原位削减同时微生物产电的方法及装置
技术领域
本发明属于环境与新能源技术领域，涉及一种利用微生物燃料电池处理和治理底泥的技术，具体涉及一种利用河涌、池塘、沟渠等水体的黑臭底泥生物发电并原位降低底泥化学需氧量（ COD ）的方法及装置。
背景技术
水体黑臭和富营养化是我国水污染的普遍现象。由于长期纳污，导致河涌、池塘、沟渠等水体黑臭底泥淤积，在上述水体治理中，当水质明显改善或水体受到扰动时，底泥中的污染组分会向上释放，使底泥成为水体的内在污染源。因此，底泥治理是改善水质的根本，是我国水污染要解决的根本问题，形势急迫，大力发展底泥治理技术势在必行。
目前底泥治理的主要方法有底泥疏浚、化学掩蔽、微生物修复等三种。 1 ）底泥疏浚，即采用工程措施挖除污染的底泥，清除污染水体的内源。它是底泥治理中最常用的方法，但其费用高昂，包括底泥疏挖、运输、处理、处置等诸多步骤，而且疏出底泥的处置易造成臭味散发、渗滤液污染等二次污染； 2 ）底泥掩蔽，是指在污染底泥上投置大量的掩蔽材料，使底泥与水体隔离，防止底泥中的营养物、重金属与有机污染物进入水体造成二次污染。例如，申请号为 200710191195.2 的发明专利公开了一种富营养化水体底泥掩蔽修复方法，此方法需要采用大量的粘土掩蔽材料和添加剂，对其材料还需粉碎过筛、高温烘干等预处理工作，将其投入湖泊水体中，只能阻挡已有沉积物中氮、磷等营养盐的释放和藻类生物上浮繁殖，并不能从根本上削减污染，随着水体污染物的沉降、积累，仍然会形成黑臭底泥淤积； 3 ）微生物修复，是指利用天然存在或经过驯化的微生物，使底泥中的污染物原位降解成 CO2 和水、或转化成无害物质，它不是对污染物的分离或简单转移，而是将污染物就地消除的处理技术。微生物修复技术具有工程费用低、实施简单、效果好、对环境扰动少、安全可靠的优点。水体底泥中含有大量的有机物（ 2 ～ 45% ），是底泥厌氧黑臭与危害水质的主要原因，现有的底泥疏浚、化学掩蔽、微生物修复等三种主要底泥治理方法，只是采用各种措施异位或原位消除底泥中的污染物，主要是削减底泥中的化学需氧量（ COD ），但未考虑对底泥中蕴含着丰富的生物质能加以转化、收集与利用，蕴含在底泥有机物中丰富的生物质能被白白浪费了。
近些年来，一项新的技术 -- 微生物燃料电池（ MFC ）蓬勃兴起，它是微生物技术与电池技术相结合的产物，是一种 利用微生物作为催化剂 将有机物中的化学能直接转化为电能的发电装置，具有产电与废弃物处置双重功效。 MFC 的基本原理是：有机物作为燃料在厌氧阳极室中被微生物氧化，产生的电子被微生物捕获并传递给电池阳极，电子通过外电路到达阴极，从而形成回路产生电流，而质子通过交换膜到达阴极，与氧反应生成水。除高浓度有机废水外， MFC 还能以生活污水、人畜粪便等污染物作为燃料发电。因此它是一项发展潜力巨大的先进生物质能利用技术，有望成为未来有机废物处理的支柱性技术。申请号为 200510011855.5 和 00810805.6 的发明专利分别公开了一种处理有机废水的单池式生物燃料电池与一种处理废水和活性污泥的双池式生物燃料电池，但它们只是实验室规模的单体电池（开路电压不超过 0.8V ），未涉及到多个单体电池的扩展与放大。本申请人在申请号为 200810029221.6 的发明专利申请中公开了一种微生物燃料电池堆，它提供了一种共阳极燃料的多级串 / 并联的 MFC 电池堆，解决了燃料统一进 / 出的问题，实现了电压 / 电流的提升，解决了微生物燃料电池扩展与放大的问题。但是，该装置仍然只适合以含固率低、流动性好的、液态或浆状有机废弃物作为燃料，燃料通过泵输入电池堆阳极室，经生物氧化产电与去除 COD ，至另一端流出，达到处理与产电的目的。
但是，上述的微生物燃料电池装置不适合处理底泥，原因是： 1 ）底泥必须抽吸并泵入微生物燃料电池阳极室，工程量极大，在存在上覆水的条件下很难做到，而且也达不到底泥的原位就地处理的目的； 2 ）底泥含固率高，所含的颗粒物容易造成堵塞； 3 ）若要做到原位处理，就必需将 MFC 浸入水体底泥中，以使底泥接触阳极；现有的 MFC 若浸入水体中，阴极就不能曝露于空气中，从而无法实现 MFC 所必须的阴极氧还原反应过程。这些技术难题，使得现有的微生物燃料电池不能直接应用于底泥处理产生清洁电能。
现有文献中，未见利用微生物燃料电池技术治理底泥同时产生电能的报道。
发明内容
本发明的目的是克服现有底泥治理技术的不足，提供一种利用微生物燃料电池原位削减底泥污染同时产电的新方法。本发明方法可将底泥中的有机物就地氧化降解成 CO2 和水，并同时产生清洁电能，具有底泥原位削减与微生物产电的双重功效。
本发明的另一个目的是提供一种可实现底泥原位削减同时产电的微生物燃料电池装置，所述装置可简便地安装于河涌、池塘、沟渠等水体中，就地利用底泥中的有机物为燃料，产生的电力可用于水体曝氧。
本发明的目的是通过以下技术方案予以实现的：
提供一种底泥原位削减同时微生物产电的方法，将微生物电池安装于水体底泥中，以底泥中的有机物为燃料；所述微生物燃料电池包括阴极室、阴极、阳极和分别由阴极、阳极引出的导线；所述阴极室内充满空气，阴极通过阴极室内空气曝氧，阳极一面紧贴阴极，另一面接触底泥。
上述底泥原位削减同时微生物产电的方法具体包括以下步骤：
（ 1 ）设一绝缘带镂空段的电池骨架，骨架内腔为阴极室，阴极室内充满空气，阴极包裹骨架镂空段并通过镂空处曝露于骨架内空气，阳极的一面包裹阴极外侧，导线分别由阴极和阳极引出，构建微生物燃料电池；
（ 2 ）将所述微生物燃料电池置于底泥中，保证阴极室充满空气，阳极另一面接触底泥，接通电池回路，驯化微生物产电。
步骤（ 1 ）所述保证阴极室充满空气优选的方案是可以采取电池骨架一端敞口、另一端密封的方法，敞口一端与空气相通，骨架镂空段被阴极包裹并做好防渗水处理，另一端密封。将电池骨架密封一端插入底泥，敞口的顶端露出水面，阳极接触底泥，构建好电池。上述微生物燃料电池在使用时，将密封一端插入河涌、池塘、沟渠底泥中，包裹了膜阴极和阳极的镂空段没入底泥中，绝缘管顶端露出水面，保证阴极室充满空气，接通电池回路，驯化微生物产电。
所述方法还可以包括将步骤（ 1 ）所述微生物燃料电池构建成为微生物燃料电池堆的步骤，构建好电池堆以后再进行上述步骤（ 2 ）。
可以通过检测底泥 COD 去除效果以及输出功率密度来检验效果。
步骤（ 1 ）所述微生物燃料电池的绝缘电池骨架可以是带有镂空段的 PVC 管，所述阴极采用膜阴极，当然，所述镂空段可以不仅仅是一段，可以是两段或者若干段，每一段都先用膜阴极包裹，并做好膜阴极与绝缘管接触的两端的防渗水处理，然后用阳极包裹在膜阴极外侧。
本发明同时提供了一种更为优选的方案，将两个以上的所述微生物燃料电池绝缘管密封的一端取消密封，通过连接管将原封闭的一端相接组成一个封闭回路，构成微生物燃料电池堆。具体地说，所述电池堆包括若干个微生物燃料电池和若干条连接管，所述微生物燃料电池绝缘管原应该密封的一端通过连接管连接；若干条连接管可相互连通形成封闭回路，回路内充满空气；也可以不相互连通，只是起到密封骨架和保证电池骨架敞口一端露出水面的作用即可。
根据上述方案，有多种具体的微生物燃料电池堆：
例如，两个或两个以上的上述微生物燃料电池， PVC 管密封的一端取消密封，竖直（或垂直）设置于同一条连接直管上，连接直管的两端密封，形成电池堆。适用于空间比较狭长的水体或沟渠中。所述连接管也是采用绝缘材料制备的，例如 PVC 管。还可以是一块固定板，两个以上的上述微生物燃料电池密封固定于固定板上形成电池堆。
还可以将所述若干个微生物燃料电池（ MFC ）竖直设置于交叉连接的多条连接直管上，多条连接直管相连通组成一个封闭回路，回路中充满空气，各个电池竖立于待处理底泥中，顶端露出水面，保证阴极室充满空气，空气能在各个电池阴极室间顺畅流通，形成微生物燃料电池堆。
每个微生物燃料电池管道开口的顶端露出水面，保证空气充满阴极室；根据具体情况，可增加电池直管和连接管的数量，将各个 MFC 串联或并联即扩大电池堆的规模，获得更好的放大效果。
所述电池绝缘管和连接管道可采用廉价绝缘管材加工而成，优选 PVC 管。所述镂空可采用现有技术惯用的方式，例如开通槽、钻孔等，槽和孔的形状、尺寸无特殊要求。本发明优选钻孔，并且可选用直径为 5 ～ 20cm 的 PVC 管，在 PVC 管上选取长为 10 ～ 30cm 的管段作为镂空段，在镂空段上钻孔，孔直径 0.5 ～ 2cm ，密度约为每平方米 100 ～ 3000 孔。
所述膜阴极可采用附载催化剂的碳布与隔膜热压而成，为了降低成本，本发明采用低成本膜，如阴离子交换膜与阳离子交换膜。也可以采用本申请人在申请号为 200910040920.5 的申请中所描述的布阴极。催化剂按照现有常规技术选用，例如热解酞菁亚铁（ pyr-FePc ）、四甲氧基苯基钴卟啉（ CoTMPP ）或二氧化锰（ MnO2 ）等。
所述膜阴极制作方法之一：称取 pyr-FePc 、 CoTMPP 或 MnO2 、导电材料（石墨、乙炔黑、炭黑或活性炭等）和粘结剂（聚四氟乙烯（ PTFE ）或聚偏二氟乙烯（ PVDF ）按重量比为 65:20:15 混匀，加 N-甲基吡咯烷酮溶剂搅成糊状，超声分散后均匀涂敷于干燥碳布，真空干燥即得阴极；将此阴极与隔膜在 115 ～ 120℃ 下热压 3 ～ 10 分钟即得膜阴极。
所述阳极材料主要为比面积较大的碳材料，如碳毡、碳纤维等。
将膜阴极包裹管材镂空段，膜阴极的碳布侧在内，紧贴 PVC 管，通过管材上的镂空处接触骨架内空气，阳极材料包裹于膜阴极外侧，与膜阴极的膜侧相紧贴，导线分别从阴、阳极导出，即得微生物燃料电池堆。
本发明的有益效果是：
本发明克服了现有技术底泥治理技术的不足，例如底泥疏浚方法费用高昂、步骤繁琐、易造成二次污染的缺陷、化学掩蔽材料和工艺处理复杂、不能从根本上削减污染的缺陷、微生物修复未考虑对底泥中蕴含着丰富的生物质能加以转化、收集与利用的不足，利用微生物燃料电池方法来解决底泥原位削减的问题，就地利用底泥中的有机物为燃料，原位削减污染的同时能产生电能，产生的电力可用于水体曝氧。
本发明提供了实现所述方法的装置，既不需要将底泥泵入微生物燃料电池的阳极室，阴极也可以曝于空气中，解决了微生物燃料电池技术应用于底泥处理的技术难题，实现了对含固率高的黑臭底泥的有效处理，并能变废为宝达到能源回收利用的效果。所述装置根据具体情况可横纵扩展，维护简便，可长期循环使用，具有结构紧凑、操作灵活简单、造价低廉、输出功率密度高、底泥化学需氧量（ COD ）削减效果好、不影响河道流通、环境友好等优点，适合工程化推广应用
附图说明
图 1 微生物燃料电池堆结构示意图
图 2 微生物燃料电池的膜阴极包裹镂空骨架构造示意图
图 3 微生物燃料电池阳极包裹膜阴极的构造示意图
图 4 微生物燃料电池单体的横切面构造示意图
图 5 微生物燃料电池单体实物示例图
图 6 管式微生物燃料电池单体处理河涌底泥的功率输出动态
图 7 管式微生物燃料电池单体处理河涌底泥的产电性能
图 8 管式微生物燃料电池堆骨架实物示例图
图 9 装配好的管式微生物燃料电池堆实物示例图
具体实施方式
下面结合附图和具体实施例来进一步详细说明本发明。
实施例 1
本实施例采用一种管式微生物电池来实现底泥原位削减同时微生物产电的方法，包括以下步骤：
（ 1 ）设一绝缘带镂空段的电池骨架，骨架内腔为阴极室，保证阴极室充满空气；阴极包裹骨架镂空段并通过镂空处曝露于骨架内空气，阳极包裹阴极外侧并接触底泥，导线分别由阴极和阳极引出，构建微生物燃料电池；
（ 2 ）将所述微生物燃料电池置于底泥中，接通电池回路，驯化微生物产电。
具体是：如附图 2 、附图 3 、附图 4 和附图 5 所示，附图 2 是微生物燃料电池的膜阴极包裹镂空骨架构造示意图，附图 3 是微生物燃料电池阳极包裹膜阴极的构造示意图，附图 4 是电池单体横切面构造示意图，附图 5 是微生物燃料电池单体实物示例图，其中密封一端省略未画出。 1 为电池单体，箭头所指处为阳极包裹阴极处； 2 为骨架， 9 为骨架镂空段， 8 为骨架镂空段孔； 3 为膜阴极，包括载催化剂碳布层 6 和隔膜 7 ； 4 为阳极， 5 为连接管。
所述电池包括设有镂空段 9 的骨架 2 、膜阴极 3 和阳极 4 ，膜阴极 3 包裹骨架 2 镂空段 9 形成阴极室，见附图 2 ，阳极 4 包裹膜阴极 3 ，见附图 3 ；分别以导线从阴、阳极引出（常规技术，图中未标出）。
所述镂空段 9 、阴极 3 、阳极 4 作为一个结构，所述结构可以在一个管式电池单体上设置多处。
所述骨架 2 采用绝缘管材加工而成，优选 PVC 管，价廉物美。所述镂空可采用现有技术惯用的方式，本发明优选钻孔，并且可选用直径为 5 ～ 20cm 的 PVC 管，在 PVC 管上间隔选取长为 10 ～ 30cm 的管段作为单体 MFC 镂空骨架，在骨架镂空管段上钻孔 8 ，孔 8 直径 0.5 ～ 2cm ，密度约为每平方米骨架外表面积 100 ～ 3000 孔。
所述载催化剂碳布层 6 制备如下：称取 MnO2 、炭黑导电材料和聚偏二氟乙烯（ PVDF ）粘结剂按重量比为 65:20:15 混匀，加 N-甲基吡咯烷酮溶剂搅成糊状，超声分散后均匀涂敷于干燥碳布，真空干燥即得载催化剂碳布层 6 。所述隔膜 7 优选阳离子交换膜。所述膜阴极 3 由载催化剂碳布层 6 和隔膜 7 在 115℃ 下热压 5 分钟制得。
所述阳极 4 优选碳毡。
将所述电池封闭的一端插入河涌、池塘、沟渠底泥中。实验模拟装置见附图 6 。阳极与底泥接触即形成阳极室，厌氧微生物在阳极室富集、繁殖、驯化。骨架 2 顶端露出水面不被水淹没，保证阴极室充满空气、不能有水。膜阴极 3 包裹钻有小孔 8 的 PVC 管材上，可采用环氧树脂密封膜阴极两端与 PVC 管材接触处，膜 7 在外侧，载催化剂碳布层 6 在接触管材的内侧并面向骨架内空气，空气通过小孔与阴极接触。阴阳极均按照常规技术设导线引出，构成回路。底泥中的有机污染物被厌氧产电微生物催化氧化产生电子与质子，质子通过膜、电子通过外电路传递到阴极与氧气反应，从而输出电流。
实施例 2 微生物燃料电池堆的构建
两个或两个以上的实施例所述的微生物燃料电池，绝缘管密封的一端取消密封，竖直（或垂直）设置于同一条连接直管上，连接直管的两端密封，形成电池堆。适用于空间比较狭长的水体或沟渠中。所述连接管也是采用绝缘材料制备的。
实施例 3 微生物燃料电池堆的构建
本发明提供一种微生物燃料电池堆如附图 8 和附图 9 所示。附图 8 是管式微生物燃料电池堆骨架示例图，附图 9 是装配好的管式微生物燃料电池堆示例图。
所述的微生物燃料电池堆由若干个电池单体和连接管相接构成，各阴极室相互连通。所述电池单体如附图 2 、附图 3 、附图 4 和附图 5 所示，同实施例 1 。
将所述若干个微生物燃料电池（ MFC ）竖直设置于交叉连接的多条连接直管上，多条连接直管相连通组成一个封闭回路，各个电池竖立于待处理底泥中，顶端露出水面，保证阴极室充满空气，空气能在各个电池阴极室间顺畅流通，形成高效的微生物燃料电池堆。
将所述电池堆置于河涌、池塘、沟渠底泥中，阳极与底泥接触即形成阳极室，厌氧微生物在阳极室富集、繁殖、驯化。各个单体的骨架顶端露出水面，保证阴极室充满空气。膜阴极包裹钻有小孔的 PVC 管材上（膜在外，碳布在内，即碳布层接触管材），空气通过小孔与阴极接触。各单体 MFC 阴阳极均有导线引出，并可根据需要进行多个单体电池的串联或并联。底泥中的有机污染物被厌氧产电微生物催化氧化产生电子与质子，质子通过膜、电子通过外电路传递到阴极与氧气反应，从而输出电流。
实施例 4 微生物燃料电池对河涌底泥的处理与产电效果实验
1 、管式 MFC 单体的构建与装配步骤如下：
1 ）镂空骨架 制备： 取一段聚氯乙烯（ PVC ）水管（ 20cm 长× 5cm 直径）作为 MFC 骨架， 在骨架管段上钻孔，孔直径 1cm ，密度约为每平方米 骨架外表面积 2000 孔 ；
2 ）膜阴极制备： 将二氧化锰粉末、石墨粉、聚偏二氟乙烯（ PVDF ）按 65:20:15 的质量比混匀，向混合物中加入 N-甲基吡咯烷酮，搅拌成糊状，然后将糊状混合物均匀地涂抹于碳纤维布（ 15cm 长 × 12cm 宽 ） 上，于 100 ℃ 烘干，即得载催化剂的阴极 （ MnO2 载量 5.0 mg/cm2 ）； 将载有 MnO 2 催化剂阴极与阳离子交换膜（涂有催化剂的一面与膜接触）在温度为 115℃ ，压强为 14 MPa 下热压 5 分钟，取出冷却至室温，即为膜阴极；也可以参照现有的其它膜阴极的制备。
3 ）将上述膜阴极包裹于 镂空 的 PVC 骨架上， 膜在外侧，碳布在接触管材的内侧并面向空气 ，密封（可采用环氧树脂密封），用 一根钛丝连接导电层作为阴极导线；
4 ）取一块碳毡（ 16 cm 长× 12cm 宽× 0.5cm 厚）卷曲成圆筒状，包裹于膜阴极上 ， 用一根钛丝连接碳毡作为阳极导线，即为构建好的管式微生物燃料电池单体，附图 4 为电池单体横切面构造示意图；
2 、将上述电池插入于河涌底泥中，阳极与底泥接触形成阳极室，厌氧产电微生物在阳极室富集、繁殖、驯化，镂空骨架顶端露出水面，保证阴极室充满空气。底泥中的有机物被产电微生物氧化产生电子与质子，质子通过膜、电子通过外电路传递到阴极与氧气反应，从而形成电流。采用 30Ω 外阻连接 MFC 的阴、阳两极，进行为期半年的底泥产电试验。
采用常规技术测定电池的功率输出、反应前后底泥的氧化还原电位、化学需氧量（ COD ）与酸可挥发性硫化物（ AVS ），结果见附图 6 、附图 7 与表 1 。结果表明，黑臭底泥经 6 个月的原位产电修复处理后，由于底泥有机物氧化产电，底泥颜色由深黑色转变为黄褐色，臭味基本消除，由表 1 可以看出，底泥 COD 去除率为 36.2% 、酸可挥发性硫化物去除率达 94.4% ，底泥的氧化还原电位由起始的 -169.5mV 上升至 +237.2mV 。
表 1 河涌底泥经 MFC 原位产电处理前后的性质变化
氧化还原电位 (mV) COD (mg/L) AVS (mg/g)
原始底泥 -169.5 31850 6.61
MFC 处理（外阻 30 Ω ） +237.2 20320 0.37
由附图 6 与附图 7 可以看出，底泥 MFC 的输出功率呈先上升后下降的趋势，前期（即启动后的第一个）功率增加是产电微生物驯化的结果，而后期功率下降主要是阴极氧还原催化剂活性下降的结果，底泥 MFC 的最大输出功率约为 100.4mW/m2 （即折算成阴极表面积的输出功率），开路电压为 0.84V 。
实施例 5 微生物燃料电池堆对池塘底泥的处理与产电效果
按照实施例 4 的方法构建与装配管式 MFC 电池堆，只是镂空骨架由实施例 4 的一根改为 10 根，膜阴极的氧还原催化剂由二氧化锰（ MnO2 ）改为四甲氧基苯基钴卟啉（ CoTMPP ）。各单体电池通过相同管径的空心连接管道相接，各阴极室相互连通，即为管式微生物燃料电池堆，见附图 8 与附图 9 所示。
将上述电池堆插入于池塘底泥中，即形成阳极室，厌氧产电微生物在阳极室富集、繁殖、驯化，镂空骨架顶端露出水面，保证阴极室充满空气，但又不被水淹没。各单体 MFC 间采用并联方式连接（外阻为 5Ω ），进行为期半年的底泥原位产电修复试验。
采用常规技术测定电池的功率输出、反应前后底泥的氧化还原电位、化学需氧量（ COD ）与酸可挥发性硫化物（ AVS ），结果表明，黑臭池塘底泥经 6 个月的原位产电修复处理后，由于底泥有机物氧化产电，底泥颜色由深黑色转变为黄褐色，臭味基本消除。底泥的 COD 由起始的 23680mg/L 降低至 14560mg/L ，去除率为 38.5% ；酸可挥发性硫化物（ AVS ）由起始的 5.35mg/g 降低至 0.46mg/L 去除率达 91.4% ，底泥的氧化还原电位由起始的 -151.2mV 上升至 +245.5mV ，为期 6 个月的产电数据表明，底泥 MFC 的最大输出功率约为 56.1mW/m2 （即折算成阴极表面积的输出功率），开路电压为 0.76V 。

Claims (10)

  1. 一种底泥原位削减同时微生物产电的方法，其特征在于将微生物电池安装于水体底泥中，以底泥中的有机物为燃料；所述微生物燃料电池包括阴极室、阴极、阳极和分别由阴极、阳极引出的导线；所述阴极室内充满空气，阴极通过阴极室内空气曝氧，阳极一面紧贴阴极，另一面接触底泥。
  2. 根据权利要求 1 所述方法，其特征在于包括以下步骤：
    （ 1 ）设一绝缘带镂空段的电池骨架，骨架内腔为阴极室，阴极室内充满空气，阴极包裹骨架镂空段并通过镂空处曝露于骨架内空气，阳极的一面包裹阴极外侧，导线分别由阴极和阳极引出，构建微生物燃料电池；
    （ 2 ）将所述微生物燃料电池置于底泥中，保证阴极室充满空气，阳极另一面接触底泥，接通电池回路，驯化微生物产电。
  3. 根据权利要求 2 所述底泥原位削减同时微生物产电的方法，其特征在于所述电池骨架一端敞口，另一端密封，敞口一端与空气相通；阴极包裹骨架镂空段并做防渗水处理，阳极包裹阴极外侧并接触底泥；电池骨架密封一端插入底泥，敞口顶端露出水面，保证阴极室充满空气。
  4. 根据权利要求 2 所述底泥原位削减同时微生物产电的方法，其特征在于还包括将微生物燃料电池构建成为微生物燃料电池堆的步骤，构建好电池堆以后再进行上述步骤（ 2 ）。
  5. 一种实现权利要求 1 或 2 所述方法的装置，其特征在于包括带有镂空段的绝缘管，所述绝缘管的一端密封、一端敞开与空气相通，膜阴极包裹绝缘管的镂空段，所述阳极包裹在膜阴极外侧；导线从膜阴极、阳极分别导出。
  6. 根据权利要求 5 所述的装置，其特征在于所述镂空段为若干段；若干镂空段分别采用膜阴极包裹后再用阳极包裹。
  7. 根据权利要求 5 所述装置，其特征在于所述管道采用 PVC 管。
  8. 根据权利要求 5 所述装置，其特征在于所述膜阴极采用阴离子交换膜、阳离子交换膜或布阴极；所述阳极采用碳毡或碳纤维。
  9. 一种实现权利要求 4 所述方法的装置，其特征在于包括若干个微生物燃料电池和固定板，所述微生物燃料电池绝缘管密封一端 固定于 固定板上。
  10. 一种实现权利要求 4 所述方法的装置，其特征在于包括若干个微生物燃料电池和若干条连接管，所述微生物燃料电池绝缘管一端 竖直连接 于 连接管；连接管相互连通形成封闭回路。
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CN101315985A (zh) * 2008-07-04 2008-12-03 广东省生态环境与土壤研究所 一种微生物燃料电池堆
CN101615685A (zh) * 2009-07-17 2009-12-30 广东省生态环境与土壤研究所 一种底泥原位削减同时微生物产电的方法及装置

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