CN101710626B - Single-chamber microbial fuel cell and application thereof in wastewater treatment - Google Patents
Single-chamber microbial fuel cell and application thereof in wastewater treatment Download PDFInfo
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- CN101710626B CN101710626B CN2009102126836A CN200910212683A CN101710626B CN 101710626 B CN101710626 B CN 101710626B CN 2009102126836 A CN2009102126836 A CN 2009102126836A CN 200910212683 A CN200910212683 A CN 200910212683A CN 101710626 B CN101710626 B CN 101710626B
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- 239000000446 fuel Substances 0.000 title claims abstract description 21
- 230000000813 microbial effect Effects 0.000 title claims abstract description 16
- 238000004065 wastewater treatment Methods 0.000 title abstract description 8
- 239000002351 wastewater Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000004888 barrier function Effects 0.000 claims abstract description 13
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 7
- 239000010802 sludge Substances 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims description 20
- 230000000721 bacterilogical effect Effects 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000010405 anode material Substances 0.000 claims description 3
- 239000010406 cathode material Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 238000011081 inoculation Methods 0.000 claims description 3
- 230000004103 aerobic respiration Effects 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 7
- 239000012528 membrane Substances 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000005202 decontamination Methods 0.000 abstract description 2
- 230000003588 decontaminative effect Effects 0.000 abstract description 2
- 238000005192 partition Methods 0.000 abstract 3
- 230000001580 bacterial effect Effects 0.000 abstract 2
- 238000005265 energy consumption Methods 0.000 abstract 1
- 230000010354 integration Effects 0.000 abstract 1
- 238000010248 power generation Methods 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 21
- 239000001301 oxygen Substances 0.000 description 21
- 229910052760 oxygen Inorganic materials 0.000 description 21
- 230000005611 electricity Effects 0.000 description 11
- 241000894006 Bacteria Species 0.000 description 10
- 239000010410 layer Substances 0.000 description 9
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 6
- 235000017281 sodium acetate Nutrition 0.000 description 6
- 239000001632 sodium acetate Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 239000010865 sewage Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000004099 anaerobic respiration Effects 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- 230000002906 microbiologic effect Effects 0.000 description 2
- -1 polyoxy Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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Classifications
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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
Abstract
The invention discloses a single-chamber microbial fuel cell, which belongs to the field of biological cells. The biological fuel cell comprises an anode and a cathode, wherein the anode is completely immersed in wastewater in a container which is taken as an anode chamber, one side of the cathode is in contact with the wastewater in the anode chamber, the other side is in direct contact with the air, the anode is fixed at the bottom of the anode chamber, the cathode directly floats on the water, a hydrophobic layer is coated on the side which is near to the air, a partition board which can adjust the horizontal height is added in the position which is separated from the cathode by 1/4-1/2 of the height of the container, a hollow hole is arranged in the middle of the partition board, and a bacterial filter membrane is covered on the hole for constituting a barrier of the partition board and the bacterial filter membrane, thereby dividing the container into an upper part and a lower part. The single-chamber microbial fuel cell promotes the traditional water treatment process and the novel energy integration technology, and realizes the combination of decontamination and energy production. The single-chamber microbial fuel cell is applied in the wastewater treatment and can not only improve the power generation efficiency and reduce the energy consumption, but also reduce the aerobic respiration role, reduce the output of sludge and have high economic benefits and extensive application prospect.
Description
Technical field
The present invention relates to microbiological fuel cell and the application in waste water treatment thereof, say more specifically a kind of and pollutant can be converted into the single-chamber microbial fuel cell of electric energy and the application in the waste water treatment thereof.
Background technology
Microbiological fuel cell (Microbial Fuel Cell is called for short MFC) is a kind of wastewater treatment equipment that organic substance in the waste water is converted into electric energy.Occurring in nature ubiquity one quasi-microorganism, they can be with electrode as its final electron acceptor when carrying out anaerobic respiration, and this quasi-microorganism is referred to as the electrogenesis bacterium.MFC namely utilizes such principle: at the anode of anaerobism, by the anaerobic respiration effect of electrogenesis bacterium, with substrate digestion, electronics is passed on the anode, electronics is collected by anode electrode, spreads out of by external circuit, and the proton of generation transfers to negative electrode by proton exchange membrane; And at aerobic negative electrode, accept the electronics that transmits by external circuit from anode, and the proton that transmits of proton exchange membrane, cathode reaction O occurs
2+ H
++ e
-The H of----→
2O.
At present, single chamber MFC becomes the focus of this area research because simple structure, cost are low, electrogenesis can high advantage.Typical single chamber MFC structure is: in the electrode chamber (anode chamber) of anaerobism, be full of waste water to be processed, anode and negative electrode lay respectively at the battery both sides, and its Anodic all immerses in the waste water of anode chamber, and negative electrode one side contacts with waste water in the anode chamber, and opposite side directly contacts with air.Itself and traditional two chamber MFC difference mainly are to have cancelled proton exchange membrane, and a side of negative electrode is exposed in the air.Like this, owing to having reduced the internal resistance of cell and having improved the negative electrode oxygen partial pressure, single chamber MFC is greatly improved at more traditional MFC aspect the electrogenesis energy.
But, air cathode has improved oxygen partial pressure, so that too much oxygen infiltrates the anode chamber of anaerobism, causes microbe to do aerobic breathing and greatly reduces efficiency of fuel cell generation------is referred to as coulombic efficiency usually,, actually obtains electric weight Q and theory should obtain electric weight Q that is
ThThe ratio.The infiltration of oxygen so that in the waste water too much COD utilized with aerobic respiration by bacterium, and be not that the electrogenesis of anaerobism is breathed, namely so that in the waste water COD utilance reduce.For this problem, have a lot of research reports both at home and abroad, as adopt the methods such as the nitrogen that exposes to the sun, the deoxygenation of interpolation reducing agent in the anode chamber.But little on the impact that COD utilance in the waste water improves.
Summary of the invention
1. invent the technical problem that will solve
For the lower efficiency of fuel cell generation of existing single chamber MFC, the invention provides the application in a kind of single-chamber microbial fuel cell and the waste water treatment thereof, can reduce microbe and the oxygen touch opportunity in device, limited the aerobic respiration of microbe, reduce the aerobic respiration consumption of COD, improved the utilance to COD in the waste water, i.e. the coulombic efficiency of battery.Can be at a high speed, process efficiently.
2. technical scheme
Principle of the present invention:
The present invention adopts and add dividing plate and the membrane-bound method of bacteriological filtration in the anode chamber, comes the aerobic respiration of restriction micro-organisms in single chamber MFC.This device anode bottom set, negative electrode swims on the water surface of top.At air cathode place, distance top, add the dividing plate of the middle hollow out of one deck, hollow part loads the bacteriological filtration film, forms " dividing plate-bacteriological filtration film " barrier, and barrier is divided into device two-layer up and down.The oxygen gear that dividing plate can be to a certain extent infiltrates the top is on the upper strata, reduces contacting of oxygen and lower floor microbe, although namely the lower floor bacterium is many, oxygen is few, has reduced the bacterium aerobic respiration; And the existence of bacteriological filtration film can stop microbe to float up to the high upper strata of DO, and microbe is limited in lower floor, although namely upper strata oxygen is many, does not have bacterium, has also reduced the bacterium aerobic respiration.Like this, the comprehensive function of dividing plate and bacteriological filtration film has reduced microbe and the oxygen touch opportunity in device dramatically, limited the aerobic respiration of microbe, reduce the aerobic respiration consumption of COD, improved the utilance to COD in the waste water, i.e. the coulombic efficiency of battery.In addition, for common single chamber MFC, higher concentration COD waste water can consume water oxygen gas in a large number, even so that near the oxygen the negative electrode of top is depleted, has therefore reduced cathode potential, affects the battery electrogenesis.And the MFC of this invention of process, the transformation of " dividing plate-bacteriological filtration film " barrier; with near the oxygen the negative electrode of upper strata and lower floor's microbe isolation; oxygen is protected, has ensured the partial pressure of oxygen of negative electrode, alleviated to a certain extent the impact of high concentration COD waste water on electricity generation ability.
Technical scheme of the present invention is:
A kind of single-chamber microbial fuel cell, comprise anode and negative electrode, its Anodic all immerses as in the waste water in the container of anode chamber, and negative electrode one side contacts with waste water in the anode chamber, opposite side directly contacts with air, its bottom fixed anode, negative electrode directly swims on the water surface, it scribbles hydrophobic layer near air one side, is 1/4 of container height～～1/2 place at the distance negative electrode, adds the adjustable dividing plate of level height, cut-out openings is arranged in the middle of the dividing plate, cover on the hole and carry the bacteriological filtration film, consist of " dividing plate-bacteriological filtration film " barrier, container is divided into up and down two parts.
The top of the anode of said vesse inside, inoculation has anaerobic sludge.Anode material is the porous carbon felt, and cathode material is carbon cloth, and the upper strata of negative electrode ingress of air scribbles polytetrafluorethylecoatings coatings as hydrophobic layer.The area of the upper and lower surface of anode and negative electrode is consistent with the container cross section area.
Separator material is polymethyl methacrylate for the material with container, and the optimum position is from negative electrode 1/3 place, and the volume ratio of the upper and lower that separate is 1: 2.
In this experiment, the material of bacteriological filtration film is the CAM of aperture 0.22um, form " dividing plate-bacteriological filtration film " barrier with dividing plate, device is divided into " the polyoxy aseptic layer " on top and " few oxygen has the bacterium layer " of bottom, so that still keep abundant oxygen to keep cathode potential near the negative electrode place, because this place does not have bacterium, limited aerobic respiration simultaneously.
Behind the sewage access to plant, carry out sewage disposal and electricity generation process in lower floor, lower floor's DO value is low, is conducive to the electricity generation process of anaerobism, raises the efficiency.And the hydrogen ion that lower floor produces can freely pass through " dividing plate-bacteriological filtration film " barrier arrival upper strata, and therefore the oxygen reaction generation water with negative electrode form extrinsic current.Simultaneously, reaction substrate, macromolecular substances etc. can equally with hydrogen ion freely pass through " dividing plate-bacteriological filtration film " barrier, and their mass transfer is not subjected to the impact of barrier, and namely the internal resistance of cell is unaffected.Simultaneously, by the upper strata------" polyoxy aseptic layer " that barrier forms, the oxygen that has cushioned the top air cathode infiltrates, and himself there is not bacterium, can not carry out aerobic respiration, reduce consumption of raw materials, also avoid near the oxygen expenditure (when especially influent COD is higher) of negative electrode.That is: lower floor is the main body of single chamber MFC of the present invention; the upper strata is MFC " oxygen separator, oxygen protective layer and raw material storage layer "; no matter the substrate on upper strata (COD) is that aerobic respiration or anaerobism electrogenesis are breathed if directly not being utilized------; all need to transfer to lower floor and just can be utilized, and lower floor is through after the upper strata buffering, the DO value is lower; the aerobic respiration amount seldom; therefore, as the lower floor of MFC main body, the utilance of substrate is improved in the waste water.
3. beneficial effect
The invention provides the application in a kind of single-chamber microbial fuel cell and the waste water treatment thereof, facts have proved, " dividing plate-bacteriological filtration film " barrier is less to internal resistance of cell contribution, on the own electricity generation ability impact of battery and little, the present invention has advanced the integrated technology of traditional water treatment technology and novel energy, has realized the combination of " decontamination " and " production capacity ".The present invention is applied to sewage disposal, and not only the electrogenesis energy efficiency improves, and reduces energy resource consumption, and the aerobic respiration effect reduces, and sludge yield is few, has higher economic benefit and application prospect widely.
Description of drawings
Fig. 1 is structural representation of the present invention, the anode of 1-bottom set wherein, the negative electrode that 2-is floating, 3-outer meeting resistance, 4-horizontal baffle, 5-bacteriological filtration film, 6-anode chamber, 7-anaerobic sludge
Embodiment
Further specify the present invention below in conjunction with accompanying drawing
Adopt two covering devices, do not add film device and add film device and compare experiment.The structure that wherein adds film device is: single-chamber microbial fuel cell, comprise anode 1 and negative electrode 2, its Anodic all immerses as in the waste water in the container of anode chamber 6, and negative electrode one side contacts with waste water in the anode chamber, opposite side directly contacts with air, its bottom fixed anode, and negative electrode directly swims on the water surface, it scribbles hydrophobic layer near air one side, device floor space 50cm
2, cumulative volume 470cm
3, hollow out baffle plate 4 in the middle of adding apart from top, 1/3 place that cylindrical drum is high, hole diameter 2cm covers on the hole and carries a bacteriological filtration film 5, consists of " dividing plate-bacteriological filtration film " barrier, and container is divided into up and down two parts.Above anode, inoculation has anaerobic sludge 7.Anode material is the porous carbon felt, and cathode material is carbon cloth, and the upper strata of negative electrode ingress of air scribbles polytetrafluorethylecoatings coatings as hydrophobic layer.The area of the upper and lower surface of anode and negative electrode is consistent with the container cross section area.The container bottom is provided with sewage inlet.
Do not add film device and its difference and only be to lack the middle bacteriological filtration film that has on the cut-out openings of dividing plate.Add CAM that film device adds aperture 0.22um at the dividing plate hollow part as the bacteriological filtration film, do not have and add film device.Stream oriented device is carried out the comparison of electricity generation ability and coulombic efficiency.
First dividing plate being fixed on apart from negative electrode is 1/3 place of container height, and then with the simulated wastewater of sodium acetate preparation COD=300mg/L, for stream oriented device advances the water supply, external resistance 3 is fixed as 1000 ohm.At the device mezzanine level, namely not yet reach production capacity stable the startup stage, carry out the comparison of both coulombic efficiencies with 24-48 hour the period that each device brings into operation.As a result, the average voltage that does not add film device is V=41mV, and average current is A=0.041mA, and the COD removal amount is 91mg/L, coulombic efficiency CE=0.69%; And the average voltage that adds film device is V=39mV, and average current is A=0.039mA, and the COD removal amount is 54mg/L, coulombic efficiency CE=1.10%.
Device basic structure is with embodiment 1, and difference is, the stage difference of investigation is that two devices start later stages, the comparison of stable operation stage.(later embodiment is stable operation stage) prepares the simulated wastewater of COD=300mg/L with sodium acetate, for each device advances the water supply, external resistance is fixed as 1000 ohm.In the ripe stable operation stage of device, carry out the comparison of both coulombic efficiencies with 192-216 hour the period that each device brings into operation.As a result, the average voltage that does not add film device is V=338mV, and average current is A=0.338mA, and the COD removal amount is 67mg/L, coulombic efficiency CE=7.7%; And the average voltage that adds film device is V=320mV, and average current is A=0.32mA, and the COD removal amount is 27mg/L, coulombic efficiency CE=17.9%.
The employing of device is with embodiment 2, and difference is, behind disposable make-up water, compares total electrogenesis time and total coulombic efficiency of stream oriented device.With the simulated wastewater of sodium acetate preparation COD=300mg/L, as the disposable water inlet of device, external resistance is fixed as 1000 ohm.In the stable operation stage of device, compare both total electrogenesis total time and total coulombic efficiencies.As a result, not adding the film device gross output electricity time is 92hr, total coulombic efficiency CE=6.2%; Time be 139hr and add film device gross output electricity, total coulombic efficiency CE=9.2%.
The employing of device and comparative approach are with embodiment 3, and difference is, it is 1/4 place of container height that dividing plate is transferred at the distance negative electrode.With the simulated wastewater of sodium acetate preparation COD=300mg/L, as the disposable water inlet of device, external resistance is fixed as 1000 ohm.In the stable operation stage of device, compare both total electrogenesis total time and total coulombic efficiencies.As a result, not adding the film device gross output electricity time is 92hr, total coulombic efficiency CE=6.1%; Time be 122hr and add film device gross output electricity, total coulombic efficiency CE=8.1%.
The employing of device and comparative approach are with embodiment 3, and difference is, it is 1/2 place of container height that dividing plate is transferred at the distance negative electrode.With the simulated wastewater of sodium acetate preparation COD=300mg/L, as the disposable water inlet of device, external resistance is fixed as 1000 ohm.In the stable operation stage of device, compare both total electrogenesis total time and total coulombic efficiencies.As a result, not adding the film device gross output electricity time is 89hr, total coulombic efficiency CE=6.1%; Time be 141hr and add film device gross output electricity, total coulombic efficiency CE=9.0%.
The employing of device is with embodiment 3.Difference is, has improved the COD value of moisturizing.With the simulated wastewater of sodium acetate preparation COD=2000mg/L, as the disposable water inlet of device, external resistance is fixed as 1000 ohm.In the stable operation stage of device, compare both gross output abilities.As a result, not adding the film device average voltage is V=296mV, and average current is A=0.296mA; Be V=322mV and add the film device average voltage, average current is A=0.322mA.
Claims (5)
1. single-chamber microbial fuel cell, comprise anode and negative electrode, its Anodic all immerses as in the waste water in the container of anode chamber, and negative electrode one side contacts with waste water in the anode chamber, opposite side directly contacts with air, it is characterized in that the container bottom fixed anode, negative electrode directly swims on the water surface, it scribbles hydrophobic layer near air one side, is 2/5～1/4 place of container height at the distance negative electrode, adds horizontal baffle, cut-out openings is arranged in the middle of the dividing plate, cover on the hole and carry the bacteriological filtration film, consist of " dividing plate-bacteriological filtration film " barrier, container is divided into up and down two parts.
2. single-chamber microbial fuel cell according to claim 1 is characterized in that the top of the bottom anode of internal tank, and inoculation has anaerobic sludge.
3. single-chamber microbial fuel cell according to claim 2 is characterized in that anode material is the porous carbon felt, and cathode material is carbon cloth, and the upper strata of negative electrode ingress of air scribbles polytetrafluorethylecoatings coatings as hydrophobic layer.
4. each described single-chamber microbial fuel cell according to claim 1～3 is characterized in that the area of upper and lower surface of anode and negative electrode is consistent with the container cross section area.
5. each described single-chamber microbial fuel cell according to claim 1～3 is characterized in that in the container bottom water inlet being arranged.
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| CN102219299B (en) * | 2011-04-01 | 2012-12-19 | 中国科学院成都生物研究所 | Wastewater anaerobic oxidation and negative oxygen ion coupled generation device and method |
| CN102249397A (en) * | 2011-05-16 | 2011-11-23 | 合肥工业大学 | Bio-electrochemical enhanced waste water treatment device |
| CN102263279A (en) * | 2011-07-06 | 2011-11-30 | 武汉理工大学 | Microbial fuel cell device with artificial wetland aquatic plant electrodes |
| CN103811790B (en) * | 2012-11-07 | 2016-07-06 | 江苏常环环境科技有限公司 | The microbial fuel cell unit of packing type plant electrode |
| US20140255729A1 (en) * | 2013-03-05 | 2014-09-11 | Honeywell International Inc. | Microbial fuel cell having electrically conductive foam electrode |
| CN106898792B (en) * | 2017-02-17 | 2019-09-06 | 中国科学院理化技术研究所 | Cellulose base single-chamber microbial fuel cell air cathode and preparation method thereof |
| CN108775858A (en) * | 2018-05-12 | 2018-11-09 | 中国科学院南京地理与湖泊研究所 | A kind of sensor and its application method of monitoring water depth |
| CN110148771A (en) * | 2019-05-17 | 2019-08-20 | 天津大学 | A kind of appositional pattern microbiological fuel cell for oil-sludge treatment |
| TWI826170B (en) * | 2022-12-07 | 2023-12-11 | 蘇忠楨 | Upright benthic microbial fuel cell module |
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| JP2006114375A (en) * | 2004-10-15 | 2006-04-27 | Mie Tlo Co Ltd | Microorganism battery for sludge treatment, and sludge purifying device using it |
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