CN104064794A - Microbial fuel cell capable of repairing nitrate polluted underground water in situ - Google Patents
Microbial fuel cell capable of repairing nitrate polluted underground water in situ Download PDFInfo
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- CN104064794A CN104064794A CN201410331214.7A CN201410331214A CN104064794A CN 104064794 A CN104064794 A CN 104064794A CN 201410331214 A CN201410331214 A CN 201410331214A CN 104064794 A CN104064794 A CN 104064794A
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- 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
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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
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/163—Nitrates
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
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- 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
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- 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
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- Hydrology & Water Resources (AREA)
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Abstract
The invention provides a microbial fuel cell capable of repairing nitrate polluted underground water in situ. The microbial fuel cell comprises an anode chamber, a cathode chamber, anion exchange membranes at the two sides of the cathode chamber and an external circuit system, wherein the anode chamber is provided with a water inlet pipe, a water outlet pipe and an exhaust pipe and is internally provided with a biological anode, and anaerobic electro-microorganisms are attached to the biological anode; the anode chamber is fully filled with anode liquor, and efficient anaerobic digestion sludge is inoculated in the anode chamber; the cathode chamber is provided with an exhaust pipe and is internally provided with a biological cathode, and electroactive denitrifying microorganisms are attached to the biological cathode; the cathode chamber is fully filled with cathode liquor, and denitrifying sludge is inoculated in the cathode chamber; the external circuit system comprises an external resistor, a lead and an electrical signal acquisition recorder. The microbial fuel cell has three functions of organic waste water treatment, biological electricity production and in-situ repair of nitrate polluted underground water, solves the problem of secondary pollution, caused by organic matter, microorganisms and the like, on underground water in the in-situ repair process and is compact in structure and low in running cost as well as economic and efficient.
Description
Technical field
The invention belongs to groundwater azotate pollution and administer technical field, relate to biological fuel cell, relate in particular to a kind of Biocathode microbial fuel cell of original position reparation groundwater azotate pollution.
Background technology
Underground water is abundant because of its reserves, has become one of topmost drinking water source of China.In recent years, due to discharge and the seepage of industrial wastewater and sanitary sewage, the excessive use of chemical fertilizer, under solid waste leaching, ooze, sewage unreasonable recharged etc., causes nitrate pollution to become global environmental problem, Drinking Water in China constituted a threat to safely, and health is formed to harm, need the groundwater azotate removal technology of high-efficiency and economic badly.
At present, groundwater azotate pollution improvement technology is divided into dystopy removal, original position reparation and monitoring Natural Attenuation technology.The advantages such as based technique for in-situ remediation is thorough with its reparation, little to groundwater environment disturbance, cost is relatively cheap are shown up prominently in groundwater azotate pollution reparation field; Wherein biology in situ recovery technique enjoys researcher to pay close attention to because of advantages such as its efficient stable, reaction condition gentleness and operating cost are low.But in biology in situ recovery technique application process, there is limitation at present, because of content of organics in underground water low, for keeping heterotrophic denitrifying Bacteria activity, need the extra organic substance that adds as denitrification process electron donor, in process, residual organic substances causes secondary pollution to underground water, and repair process denitrifying bacterium growing amount is large, can cause microbial contamination to underground water, stop up water-bearing layer, reduce water-bearing media permeability; Autotrophic denitrification microorganism in situ recovery technique is by adding H
2or S
0as electron donor, can reduce microbe growing amount, but add H
2or S
0be subject to the restriction of on-the-spot place and rock stratum, enforcement difficulty is large, cost is high, utilance is low and underground mass transfer difficulty, and underground water is existed to SO
4 2-, the pollution such as microbe.
Microbiological fuel cell (Microbial Fuel Cell, MFC) provide a kind of new way for solving energy regeneration and refuse reclamation problem, be that one utilizes microbe for catalyst, the chemical energy in fuel (organic substance) be converted into the bioreactor of electric energy.Utilize MFC to process organic wastewater, electric energy is reclaimed in pollution treatment simultaneously, is the great innovation of Technologies for Organic Wastewater Treatment, has become the research and development focus of field of environment engineering.Utilize MFC to process organic wastewater and obtained major progress, and by less for biological denitrificaion research MFC, the research of also not repairing for groundwater azotate original position at present; MFC reaction condition gentleness and economical and efficient, be a kind of pollutant biologic treating technique of high-efficiency cleaning, uses it for the reparation of groundwater azotate pollution original position and have good development potentiality and application prospect.
Summary of the invention
Not enough and the existing MFC that the object of the invention is to overcome existing groundwater azotate pollution based technique for in-situ remediation is applied to the technology barrier of groundwater azotate pollution original position in repairing, and provides a kind of original position to repair the Biocathode microbial fuel cell of groundwater azotate pollution.
For solving the problems of the technologies described above, the present invention is achieved by the following technical solutions:
Original position is repaired a microbiological fuel cell for groundwater azotate pollution, and whole microbiological fuel cell is placed in the residing in situ environment of underground water, comprises anode chamber, cathode chamber, anion-exchange membrane and external circuit system;
Bottom, described anode chamber is provided with water inlet pipe, and top is provided with outlet pipe, and top is provided with blast pipe, is provided with biological anode in anode chamber, adheres to anaerobism electrogenesis microbe on biological anode, and anode chamber is full of anolyte, and the digested sludge of anode chamber's inoculation efficient anaerobic;
Described cathode chamber top is provided with blast pipe, is provided with biological-cathode in cathode chamber, adheres to electroactive denitrifying microorganism on biological-cathode, and cathode chamber is full of catholyte, and cathode chamber inoculation denitrification mud;
Described anion-exchange membrane is positioned at cathode chamber both sides;
Described external circuit system comprises external resistance, wire and electrical signal collection recorder, and external resistance two ends connect respectively biological anode and biological-cathode by wire, and electrical signal collection recorder is parallel to external resistance two ends real time record voltage.
Further, described anolyte is organic wastewater, and pH is 7 ~ 7.5, and catholyte is phosphate buffer solution, and pH is 7.4 ~ 8.
Further, the electric conducting material of described biological anode and biological-cathode is carbon cloth, carbon paper, carbon felt, the one in graphite rod or graphite disc.
Further, described anion-exchange membrane comprises the first anion-exchange membrane and the second anion-exchange membrane, described the first anion-exchange membrane is arranged between anode chamber and cathode chamber, and be communicated with anode chamber and cathode chamber, described the second anion-exchange membrane is fixed on cathode chamber outside, be communicated with cathode chamber and underground water in situ environment of living in, nitrate in groundwater enters cathode chamber by the second anion-exchange membrane.Described first, second anion-exchange membrane, only allows anion to pass through, and does not allow other microbe of molecular level to pass through.
Further, described first or second membrane area of anion-exchange membrane and the volume ratio of anode chamber are 2 ~ 4m
2: 1m
3, the distance between the first anion-exchange membrane and biological anode is 0.5 ~ 1cm, the distance between the second anion-exchange membrane and biological-cathode is 0.5 ~ 1cm.
Further, described the first anion-exchange membrane adopts sealing ring to be fixed between anode chamber and cathode chamber, because anode chamber can consume anionic part, the first anion-exchange membrane allows the anionic part of cathode chamber to enter anode chamber, maintains the charge balance of anode chamber and cathode chamber;
Described the second anion-exchange membrane is fixed on cathode chamber outside by flange and sealing ring, and contacts with the residing in situ environment of underground water.
Further, described anode chamber and cathode chamber volume ratio are 2 ~ 4:1, and anode chamber's length-width ratio is 4 ~ 6:2, and length to height ratio is 1:1; Cathode chamber length-width ratio is 4 ~ 6:0.5 ~ 1, and length to height ratio is 1:1.
Further, described biological anode lower end is far from the distance from bottom 2 ~ 4cm of anode chamber, described biological-cathode lower end is apart from cathode chamber distance from bottom 2 ~ 4cm, and the distance between described biological anode and biological-cathode is 1 ~ 2cm, and biological anode surface area is 2 ~ 6 m with the ratio of anode chamber's volume
2: 1 m
3, biological-cathode surface area is 2 ~ 6 m with the ratio of cathode chamber volume
2: 1 m
3.
Microorganism fuel cell is removed the operation principle of nitrate in groundwater:
Biocathode microbial fuel cell is placed in to underground water in situ environment, anode chamber is continuously pumped into organic wastewater, oxidized and discharge electronics under the catalytic action of anaerobism electrogenesis microbe in anode chamber, electronics arrives biological anode and reaches biological-cathode by external circuit, under the catalytic action of the electroactive denitrifying microorganism of cathode chamber, thereby enter nitrate in the underground water of cathode chamber obtains electronics on biological-cathode and is reduced to nitrogen by anion-exchange membrane, nitrogen is discharged by cathode chamber blast pipe, thereby nitrate in groundwater is removed.
This microbial fuel cell unit has organic wastewater improvement, biological electrogenesis and groundwater azotate pollution original position simultaneously and repairs triple functions, can overcome microbiological fuel cell original position and repair the technical barrier of groundwater azotate pollution, can realize the continuous operation of nitrate in groundwater original position repair process, can avoid, in original position reparation, underground water is caused to the secondary pollution such as organic substance, microbe problem, and this apparatus structure compactness, operating cost is low, economical and efficient.
Compared with prior art, advantage of the present invention and good effect are:
(1) underground water that can original position reparation be subject to azotate pollution, does not destroy the natural conditions of underground water, and have speed fast, disturb little, efficiency is high, low cost and other advantages.
(2) repair in position groundwater azotate pollution electrogenesis simultaneously, realize simultaneous denitrification and biological electrogenesis, reduce groundwater azotate pollution treatment cost.
(3) can overcome that the enforcement difficulty existing in extra interpolation electron donor process is large, cost is high, utilance is low and the problem such as underground mass transfer difficulty, can effectively avoid the secondary pollution of original position repair process to underground water.
(4) this microbiological fuel cell economical and efficient stable operation continuously, and easy to operate, easy care, is convenient to long-term use.
Brief description of the drawings
Fig. 1 is the structural representation that original position of the present invention is repaired the microbiological fuel cell specific embodiment of groundwater azotate pollution.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is further detailed explanation.
The present invention utilizes Biocathode microbial fuel cell original position to repair groundwater azotate pollution.Enter the passage of MFC cathode chamber using anion-exchange membrane as nitrate in groundwater, stop microbe in MFC to enter groundwater environment simultaneously, can effectively avoid the secondary pollution to underground water such as microbe, organic substance; Taking denitrifying bacterium in cathode chamber as catalyst, entering the electron reduction that the nitrate in groundwater of cathode chamber accepts on negative electrode is that nitrogen is removed.The concrete structure of this microbiological fuel cell is as follows:
Shown in figure 1, a kind of original position is repaired the Biocathode microbial fuel cell of groundwater azotate pollution, comprise anode chamber 1, cathode chamber 2, external circuit system 3, between anode chamber 1 and cathode chamber 2, adopt sealing ring to be fixedly installed the first anion-exchange membrane 4, be fixedly installed the second anion-exchange membrane 5 in cathode chamber 2 outsides by flange and sealing ring;
The outer lower portion of anode chamber 1 is provided with water inlet pipe 11, and outer upper is provided with outlet pipe 12, and top is provided with blast pipe 13, in anode chamber 1, be provided with biological anode 14, on biological anode 14, adhere to anaerobism electrogenesis microbe, in anode chamber 1, be full of anolyte 15, and anode chamber 1 inoculates efficient anaerobic digested sludge;
Cathode chamber 2 tops are provided with blast pipe 21, are provided with biological-cathode 22 in cathode chamber 2, adhere to electroactive denitrifying microorganism on biological-cathode 22, be full of catholyte 23, and cathode chamber 2 are inoculated denitrification mud in cathode chamber 2;
Biological anode 14 is carbon cloth with the electric conducting material of biological-cathode 22, carbon paper, carbon felt, the one in graphite rod or graphite disc.
The first anion-exchange membrane 4 use sealing rings are fixed between anode chamber 1 and cathode chamber 2, and the second anion-exchange membrane 5 is fixed on cathode chamber 2 opposite sides by flange and sealing ring, and contact with the residing in situ environment 6 of underground water.Because anode chamber 1 can consume anionic part, the first anion-exchange membrane 4 allows the anionic part of cathode chamber 2 to enter anode chamber 1, maintains the charge balance of anode chamber 1 and cathode chamber 2;
External circuit system 3 is provided with wire 31, external resistance 32 and electrical signal collection recorder 33, and external resistance 32 is connected with biological-cathode 22 respectively at biological anode 14 by wire 31, and electrical signal collection recorder 33 is connected in parallel on external resistance 32 two ends can its magnitude of voltage of real time record; Whole microbiological fuel cell is placed in underground water in situ environment 6 of living in.
Wherein, anolyte is organic wastewater, and pH is 7 ~ 7.5, and catholyte is phosphate buffer solution, and pH is 7.4 ~ 8.
Wherein, the first anion-exchange membrane 4 is communicated with anode chamber 1 and cathode chamber 2, the second anion-exchange membranes 5 are communicated with cathode chamber 2 and underground water in situ environment 6 of living in, and nitrate in groundwater enters cathode chamber 2 by the second anion-exchange membrane 5.The volume ratio of the membrane area of the first or second anion-exchange membrane and anode chamber 1 is 2m
2: 1m
3, the distance between the first anion-exchange membrane 4 and biological anode 14 is 1cm, the distance between the second anion-exchange membrane and biological-cathode is 1cm.
Anode chamber 1 and cathode chamber 2 are rectangular configuration, and anode chamber 1 and cathode chamber 2 volume ratios are 2:1, and anode chamber's 1 length, width and height are than being 5:2:5, and cathode chamber 2 length, width and height are than being 5:1:5; Anolyte 15 is full of respectively anode chamber 1 and cathode chamber 2 with catholyte 23.
Biological anode 14 lower ends are far from the 1 distance from bottom 4cm of anode chamber, and biological-cathode 22 lower ends are apart from cathode chamber 2 distance from bottom 4cm, and the distance between biological anode 14 and biological-cathode 22 is 2cm, and biological anode surface area is 2 ~ 6 m with the ratio of anode chamber's volume
2: 1 m
3, biological-cathode surface area is 2 ~ 6 m with the ratio of cathode chamber volume
2: 1 m
3.
Specific works principle:
In the digested sludge of anode chamber inoculation efficient anaerobic, taking organic wastewater as fuel, cathode chamber inoculation denitrification mud, enters nitrate in the underground water of cathode chamber as electron acceptor to see through the second anion-exchange membrane.Anaerobism electrogenesis microbial degradation organic wastewater discharges electronics simultaneously, arrive after negative electrode through anode, external circuit, under the catalytic action of denitrifying microorganism, accepted and generation current by nitrate, nitrate is reduced to nitrogen simultaneously, removes thereby make nitrate in groundwater be able to original position.
Evidence, electrogenesis when Biocathode microbial fuel cell of the present invention can be realized original position reparation groundwater azotate pollution, and this device volume is little, usefulness is high, good economy performance, can continuous and steady operation, can avoid the secondary pollution to underground water in original position repair process.
The above, be only preferred embodiment of the present invention, is not the restriction of the present invention being made to other form, and any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the equivalent embodiment of equivalent variations.But every technical solution of the present invention content that do not depart from, any simple modification, equivalent variations and the remodeling above embodiment done according to technical spirit of the present invention, still belong to the protection range of technical solution of the present invention.
Claims (8)
1. original position is repaired a microbiological fuel cell for groundwater azotate pollution, it is characterized in that: whole microbiological fuel cell is placed in the residing in situ environment of underground water, comprises anode chamber, cathode chamber, anion-exchange membrane and external circuit system;
Bottom, described anode chamber is provided with water inlet pipe, and top is provided with outlet pipe, and top is provided with blast pipe, is provided with biological anode in anode chamber, adheres to anaerobism electrogenesis microbe on biological anode, and anode chamber is full of anolyte, and anode chamber's inoculation anaerobically digested sludge;
Described cathode chamber top is provided with blast pipe, is provided with biological-cathode in cathode chamber, adheres to electroactive denitrifying microorganism on biological-cathode, and cathode chamber is full of catholyte, and cathode chamber inoculation denitrification mud;
Described anion-exchange membrane is positioned at cathode chamber both sides;
Described external circuit system comprises external resistance, wire and electrical signal collection recorder, and external resistance two ends connect respectively biological anode and biological-cathode by wire, and electrical signal collection recorder is parallel to external resistance two ends real time record voltage.
2. microbiological fuel cell according to claim 1, is characterized in that: described anolyte is organic wastewater, pH is 7 ~ 7.5, and described catholyte is phosphate buffer solution, and pH is 7.4 ~ 8.
3. microbiological fuel cell according to claim 1, is characterized in that: described biological anode and biological-cathode adopt carbon cloth, carbon paper, carbon felt, the one in graphite rod or graphite disc.
4. microbiological fuel cell according to claim 1, it is characterized in that: described anion-exchange membrane comprises the first anion-exchange membrane and the second anion-exchange membrane, described the first anion-exchange membrane is arranged between anode chamber and cathode chamber, and be communicated with anode chamber and cathode chamber, described the second anion-exchange membrane is fixed on cathode chamber outside, be communicated with cathode chamber and underground water in situ environment of living in, nitrate in groundwater enters cathode chamber by the second anion-exchange membrane.
5. microbiological fuel cell according to claim 4, is characterized in that: described first or second membrane area of anion-exchange membrane and the volume ratio of anode chamber are 2 ~ 4m
2: 1m
3, the distance between the first anion-exchange membrane and biological anode is 0.5 ~ 1cm, the distance between the second anion-exchange membrane and biological-cathode is 0.5 ~ 1cm.
6. microbiological fuel cell according to claim 4, it is characterized in that: described the first anion-exchange membrane adopts sealing ring to be fixed between anode chamber and cathode chamber, described the second anion-exchange membrane is fixed on cathode chamber outside by flange and sealing ring, and contacts with the residing in situ environment of underground water.
7. microbiological fuel cell according to claim 1, is characterized in that: described anode chamber and cathode chamber volume ratio are 2 ~ 4:1, anode chamber's length-width ratio is 4 ~ 6:2, and length to height ratio is 1:1; Cathode chamber length-width ratio is 4 ~ 6:0.5 ~ 1, and length to height ratio is 1:1.
8. microbiological fuel cell according to claim 1, it is characterized in that: described biological anode lower end is far from the distance from bottom 2 ~ 4cm of anode chamber, described biological-cathode lower end is apart from cathode chamber distance from bottom 2 ~ 4cm, distance between described biological anode and biological-cathode is 1 ~ 2cm, and biological anode surface area is 2 ~ 6 m with the ratio of anode chamber's volume
2: 1 m
3, biological-cathode surface area is 2 ~ 6 m with the ratio of cathode chamber volume
2: 1 m
3.
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| CN104773827A (en) * | 2015-04-13 | 2015-07-15 | 中国科学院过程工程研究所 | System and method for treating wastewater produced by production of bio-cathode type microbial fuel cells |
| CN105293688A (en) * | 2015-10-22 | 2016-02-03 | 大连理工大学 | System for removing nitrate nitrogen in water in electro-catalysis mode through coupling biology positive electrode |
| CN106885833A (en) * | 2016-12-28 | 2017-06-23 | 清华大学 | A kind of microbiological fuel cell and its preparation and the application in water quality early-warning |
| CN107576706A (en) * | 2017-10-25 | 2018-01-12 | 盐城工学院 | A kind of nitrate concentration sensor based on biological fuel cell and electricity production bacterium |
| CN107902763A (en) * | 2017-10-18 | 2018-04-13 | 浙江工商大学 | It is a kind of to be used to eliminate denitrogenation electrode material of groundwater azotate and its preparation method and application |
| CN108339846A (en) * | 2018-01-18 | 2018-07-31 | 青岛科技大学 | Fuel cell handles the system and method that organic wastewater synchronizes repairing heavy metal in soil |
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