CN102315469A - Microbial fuel cell and application thereof to degradation of azo dye pollutant - Google Patents
Microbial fuel cell and application thereof to degradation of azo dye pollutant Download PDFInfo
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- CN102315469A CN102315469A CN2010102203623A CN201010220362A CN102315469A CN 102315469 A CN102315469 A CN 102315469A CN 2010102203623 A CN2010102203623 A CN 2010102203623A CN 201010220362 A CN201010220362 A CN 201010220362A CN 102315469 A CN102315469 A CN 102315469A
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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
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Abstract
The invention discloses a microbial fuel cell and application thereof to degradation of azo dye pollutants. The microbial fuel cell comprises an anode chamber, a cathode chamber, an anode electrode, a cathode electrode, a proton permeable membrane and an external circuit. Electrochemical active microbes are inoculated in the anode chamber. Culture solution for the microbes, a carbon source and electron donors are also contained in the anode chamber. Cathode reaction liquid is contained in the cathode chamber and consists of Shewanella decolorationis and culture solution thereof. Electron acceptors of the Shewanella decolorationis are also contained in the cathode chamber. The microbial fuel cell oxidizes an organic substrate in the solution through the microbes in the anode chamber, generated electrons are transferred to the anode electrode and the electrons on the anode electrode are transferred to the cathode electrode through the external circuit. In the cathode chamber, the Shewanella decolorationis accepts the electrons on the cathode electrode, grows and metabolizes. The electrons are transferred to end electron acceptors such as the azo dye pollutants through a respiratory chain to reduce and degrade the azo dye pollutants. Therefore, the microbial fuel cell can be used for the treatment of the pollutants.
Description
Technical field:
The present invention relates to a kind of microbiological fuel cell and application thereof; Be specifically related to a kind of with the microbiological fuel cell of Shewanella decolorationis (Shewanella decolorationis) as the electron acceptor of negative electrode, with and application on the degrade azo dyestuff pollutant.
Background technology:
Azo dyes is widely used in weaving, printing and dyeing, and the industrial circle of pharmacy and food, and along with the discharging of waste water gets in the environment.Because it is artificial synthetic that most azo dyes is, chemical property is stable, thus in natural environment than difficult degradation.Along with azo dyes and potential " three cause " effect of relevant intermediate product come to light, the degraded of azo dyes receives concern more and more widely.
Traditional azo dyes biodegrading process comprises electrochemical process and microbiological anaerobic-aerobic coupling edman degradation Edman, but exists power consumption big respectively, shortcomings such as cost height and complicated operation.(Microbial fuel cell's microbiological fuel cell in recent years MFC) is widely used in researchs such as environmental pollution improvement and energy.This technology can be passed through action of microorganisms, and the chemical energy of organic pollution is converted into electric energy.MFC has been applied to the Study on degradation of multiple unmanageable environmental contaminants, and demonstrates application promise in clinical practice, comprising multiple industry and sanitary wastewater, percolate, aromatic compounds, trichloroethylene etc.
Existing research shows; Certain micro-organisms can carry out the deoxidization, degradation of pollutant with electrode as electron donor; And be considered in environmental improvement, to have peculiar advantage, mainly comprise the following aspects: 1, microbe directly contacts with electrode surface and accepts the electronics that electrode can more high efficiencyly utilize electrode to provide; 2, under this specific conditions, can avoid the side reaction or the harmful substance that occur easily in some reduction processes; 3, with the electrode of solid form during as electron donor reducing heavy metal ion (uranium, manganese etc.), product can be deposited in electrode surface and conveniently from environment, remove.In addition, some environmental contaminants of the electrode pair of carbon have adsorption effect preferably such as hydrogen sulfide.But above-mentioned is that the Pollutant Treatment research of electron donor all needs external power source that the electrode in the equipment is equilibrated at a certain fixed potential with the electrode, and this method is being difficult to greatly realize in practical application because of power consumption.
Summary of the invention:
First purpose of the present invention provides a kind of with the microbiological fuel cell of Shewanella decolorationis as the electron acceptor of cathode electrode; This microbiological fuel cell is with the electron acceptor of Shewanella decolorationis as cathode electrode; Accept the electronics of cathode electrode; Carry out metabolism, give its final electron acceptor with electron transport again, like the azo dyes pollutant.
The inventor finds that through experiment Shewanella decolorationis can be accepted the electronics of cathode electrode as the electron acceptor of negative electrode, carries out metabolism, gives its electron acceptor with electron transport again, thereby has realized the object of the invention.
Microbiological fuel cell of the present invention; Comprise that anode chamber, cathode chamber, anode electrode, cathode electrode, proton see through film and external circuits, the electro-chemical activity microbe is arranged, nutrient solution, carbon source and the electron donor of this microbe also is housed at the anode indoor inoculation; Cathode reaction liquid is housed in cathode chamber; It is characterized in that described cathode reaction liquid is Shewanella decolorationis and nutrient solution thereof, also have the electron acceptor of Shewanella decolorationis.
Described anode electrode or cathode electrode are carbon paper, graphite or metallic conduction material.
Described electro-chemical activity microbe can be any microbe with electricity generation ability; Be preferably Shewanella oneidensis MR-1, S.decoloritonis, S.putrefaciens IR-1, Geobacter sulfurreducens, Geothrix fermentans etc. or contain the environmental sample (soil, bed mud, waste water etc.) of mixed bacterial; The electron donor of the microbe of inserting in can the oxidation anode chamber; With electron transport to anode; Pass to cathode electrode through external circuits again, S.decoloritonis more preferably, its nutrient solution is preferably: improvement M9 inorganic salts (5.7mmol/L Na
2HPO
412H
2O, 3.3mmol/LKH
2PO
4And 18.0mmol/LNH
4Cl), mineral element (1.01mmol/L MgSO
4, 0.5g/L MnSO
4, 0.1g/L ZnSO
4, 0.01g/L CuSO
4, 0.01g/L AlK (SO
4)
2, 1.0g/L NaCl, 0.1g/L FeCl
2, 0.1g/L CaCl
2And CoCl
20.1g/L), vitamin mixture (2mg/L Biotin, 2mg/L folic acid, 10mg/L pyridoxine hydrochloride (V
B6), 5mg/Lriboflavin, 5mg/L thiamine, 5mg/L nicotinic acid, 5mg/L pantothenic acid, 0.1mg/L vitamin BE, 5mg/L p-aminobenzoic acid and 5mg/L thioctic acid), solvent is a water.Its sole carbon source is a sodium succinate, and final concentration is 10mmol/L, and unique electron donor is a sodium lactate, and final concentration is 20mmol/L.The nutrient solution of the Shewanella decolorationis in the said cathode chamber is preferably: improvement M9 inorganic salts (5.7mmol/L Na
2HPO
412H
2O, 3.3mmol/L KH
2PO
4And 18.0mmol/LNH
4Cl), mineral element (1.01mmol/L MgSO
4, 0.5g/L MnSO
4, 0.1g/L ZnSO
4, 0.01g/LCuSO
4, 0.01g/L AlK (SO
4)
2, 1.0g/L NaCl, 0.1g/L FeCl
2, 0.1g/L CaCl
2And CoCl
20.1g/L), vitamin mixture (2mg/L Biotin, 2mg/L folic acid, 10mg/L pyridoxine hydrochloride (V
B6), 5mg/Lriboflavin, 5mg/L thiamine; 5mg/L nicotinic acid, 5mg/L pantothenic acid, 0.1mg/L vitaminBE, 5mg/L p-aminobenzoic acid and 5mg/L thioctic acid), solvent is a water.
The electron acceptor of described negative electrode Shewanella decolorationis is preferably azo dyes.Shewanella decolorationis is accepted the electronics of cathode electrode and is carried out growth metabolism, gives its electron acceptor through respiratory chain with the electron transport on the cathode electrode again, like azo dyes, then with the efficient deoxidization, degradation of azo dyes.The present invention finds through experiment; Use microbiological fuel cell of the present invention in deoxidization, degradation pollutant process; In azo dyes decolouring reduction-decolor process, this microbiological fuel cell need not external power source the electrode in the equipment is equilibrated to a certain fixed potential, just degradation of contaminant efficiently; And output electric energy; Therefore energy savings greatly makes things convenient for practical application, and its catabolite can further be degraded to environmentally safe compound through microbial action under aerobic condition.
Therefore second purpose of the present invention provides the application of microbiological fuel cell of the present invention on the degrade azo dyestuff pollutant.
Microbiological fuel cell of the present invention in use, anode chamber and cathode chamber all pass to nitrogen and move under anaerobic environment to guarantee this microbiological fuel cell.
Be used for Shewanella decolorationis of the present invention (Shewanella decolorationis) and be kept at Chinese typical culture collection center (CCTCC) on November 24th, 2003; Deposit number is CCTCC M 203093, and this preservation information in the patent No. is: announce in the patent of ZL200310112361.7.
Microbiological fuel cell of the present invention passes through the microbe in the anode chamber, the organic substrates in the oxidizing solution, and with electron transport to the anode electrode that produces; And then pass through external circuit and give cathode electrode with the electron transport on the anode electrode, in cathode chamber, Shewanella decolorationis is accepted the electronics on the cathode electrode; Carry out growth metabolism; Through respiratory chain electron transport is not held electron acceptor to it, make the electron acceptor reduction, this receptor can be the azo dyes pollutant; Therefore can be used in the processing of above-mentioned pollutant the particularly processing of azo dyes.Compare as the microbiological fuel cell of the processing pollutant of electron donor with cathode electrode with of the prior art; Microbiological fuel cell of the present invention need not external power source the electrode in the equipment is equilibrated at a certain fixing electromotive force; Overcome since external power source the electrode in the equipment is equilibrated at a certain fixing power consumption that electromotive force brought, and cause in the actual shortcoming that is difficult to use.When microbiological fuel cell of the present invention carries out Pollutant Treatment; Do not need extra power supply; Thereby be environmental contaminants; Processing degraded like various waste water and other polluted-waters provides a kind of new microbiological fuel cell, and this microbiological fuel cell can derive from the metabolic activity of anode microbe owing to its electron donor, thereby is particularly useful for the lower polluted-water of nutrition degree.Can also biological electrogenesis in process of treating pollutants, realized carrying out synchronously of contaminant degradation and biological electrogenesis.
Description of drawings:
Fig. 1 is the structural representation of microbiological fuel cell;
Wherein 1, extrernal resistance; 2, external circuit lead; 3, anode electrode; 4, anode chamber, 5, cathode electrode; 6, cathode chamber; 7, Nafion 112 selectivity protons see through film; 8, universal instrument.
Fig. 2 is the output voltage curve chart of the microbiological fuel cell of embodiment 1;
Fig. 3 is the reduction curve chart of the amaranth in the cathode chamber in the microbiological fuel cell of embodiment 1.
Embodiment:
Below be to further specify to of the present invention, rather than limitation of the present invention.
Embodiment 1:
Step 1: make up microbiological fuel cell, as shown in Figure 1: anode chamber 4 is glass material with cathode chamber 6, and volume is 250ml, sees through film 7 with Nafion 112 selectivity protons and separates.
Step 2: respectively anode electrode 3 and cathode electrode 5 are inserted in anode chamber 4 and the cathode chamber 6, the electrode material of anode electrode 3 and cathode electrode 5 is 2.5 * 4cm
2Carbon paper (east is beautiful, Japan) connects anode electrode 3 and cathode electrode 5 through external circuit lead 2, inserts the extrernal resistance 1 reaction electrogenesis situation in 1000 Europe outside in the circuit lead 2, inserts universal instrument 8 to collect the electrogenesis data.
Step 3: anode chamber and cathode chamber add the 200ml nutrient solution respectively, and its composition is: improvement M9 inorganic salt solution (5.7mmol/L Na
2HPO
412H
2O, 3.3mmol/L KH
2PO
4With 18.0mmol/L NH
4Cl), mineral element (1.01mmol/L MgSO
4, 0.5g/L MnSO
4, 0.1g/L ZnSO
4, 0.01g/L CuSO
4, 0.01g/LAlK (SO
4)
2, 1.0g/LNaCl, 0.1g/L FeCl
2, 0.1g/L CaCl
2And CoCl
20.1g/L), vitamin mixture (2mg/L Biotin, 2mg/L folic acid, 10mg/L pyridoxine hydrochloride (V
B6), 5mg/L riboflavin, 5mg/L thiamine, 5mg/Lnicotinic acid, 5mg/L pantothenic acid, 0.1mg/L vitamin BE, 5mg/L p-aminobenzoic acid and 5mg/L thioctic acid), solvent is a water.Wherein, the anode chamber also adds unique electron donor-sodium lactate to final concentration 20mmol/L, and sole carbon source-sodium succinate does not contain any electron acceptor except that electrode to final concentration 10mmol/L.Cathode chamber does not add sodium lactate or other any electron donors except that negative electrode, adds 1mmol azo dyes amaranth as electron acceptor.
Step 4: in anode chamber and cathode chamber, all pass to nitrogen to guarantee anaerobic environment.
Step 5: in the solution of anode chamber and cathode chamber, add the incubated overnight Shewanella decolorationis respectively, inoculum concentration is 1% (v/v), and 30 ℃ of reactions of anaerobism start and move this microbiological fuel cell.
The output voltage curve of this microbiological fuel cell is as shown in Figure 2, because the breeding of microbe and the reduction gradually of cathode chamber azo dyes amaranth finish, cathode potential reduces gradually, and voltage also decreases.The about 10.5mV of ceiling voltage in this instance, output power density is about 0.5mW/m
3Get different time sample determination azo dyes amaranth degraded situation, the result is as shown in Figure 3.MFC cathode chamber microbe is being under unique electron donor situation with electrode; The azo dyes amaranth is carried out reduction-decolor, and along with the carrying out of reaction, visible solution redness is taken off gradually; Reaction operation 48 hours; Can be with almost all (99%) dye decolored reduction, react about 50 hours after, the azo dyes amaranth is by reduction fully.
The microbiological fuel cell of present embodiment does not need the extra external power source that provides that the electrode in the equipment is equilibrated at a certain fixing electromotive force in the process of whole deoxidization, degradation azo dyes amaranth, just can efficiently completely the azo dyes amaranth be reduced completely.
Present embodiment method of operation and embodiment 1 basically identical just add 0.5mmol azo dyes amaranth as electron acceptor in cathode chamber.
The result shows: because azo dyes is lower as the final electron acceptor concentration of negative electrode, MFC output ceiling voltage is 3mV.Simultaneously, because azo dyes concentration is lower, decoloring reaction is accomplished within a short period of time, needs 36h just the azo dyes amaranth to be reduced fully approximately.
The microbiological fuel cell of present embodiment does not need the extra external power source that provides that the electrode in the equipment is equilibrated at a certain fixing electromotive force in the process of whole deoxidization, degradation azo dyes amaranth, just can efficiently completely the azo dyes amaranth be reduced completely.
Claims (6)
1. microbiological fuel cell; Comprise that anode chamber, cathode chamber, anode electrode, cathode electrode, proton see through film and external circuits, the electro-chemical activity microbe is arranged, nutrient solution, carbon source and the electron donor of this microbe also is housed at the anode indoor inoculation; Cathode reaction liquid is housed in cathode chamber; It is characterized in that described cathode reaction liquid is Shewanella decolorationis (Shewanella decolorationis) and nutrient solution thereof, also have the electron acceptor of Shewanella decolorationis.
2. microbiological fuel cell according to claim 1 is characterized in that, the electron acceptor of described Shewanella decolorationis is azo dyes or the pollutant that contains azo dyes.
3. microbiological fuel cell according to claim 1 is characterized in that, described electro-chemical activity microbe is a Shewanella decolorationis, and its nutrient solution composition is improvement M9 inorganic salts: 5.7mmol/L Na
2HPO
412H
2O, 3.3mmol/LKH
2PO
4With 18.0mmol/L NH
4Cl, mineral element: 1.01mmol/L MgSO
4, 0.5g/L MnSO
4, 0.1g/LZnSO
4, 0.01g/L CuSO
4, 0.01g/L AlK (SO
4)
2, 1.0g/L NaCl, 0.1g/L FeCl
2, 0.1g/L CaCl
2And CoCl
20.1g/L, vitamin mixture: 2mg/L Biotin, 2mg/L folic acid, 10mg/L pyridoxine hydrochloride (V
B6), 5mg/L riboflavin, 5mg/L thiamine, 5mg/L nicotinic acid, 5mg/Lpantothenic acid, 0.1mg/L vitamin BE, 5mg/L p-aminobenzoic acid and 5mg/L thioctic acid, solvent is a water; Its sole carbon source is a sodium succinate, and final concentration is 10mmol/L, and unique electron donor is a sodium lactate, and final concentration is 20mmol/L.
4. microbiological fuel cell according to claim 1 is characterized in that, its nutrient solution of described Shewanella decolorationis is improvement M9 inorganic salts: 5.7mmol/LNa
2HPO
412H
2O, 3.3mmol/LKH
2PO
4With 18.0mmol/L NH
4Cl, mineral element: 1.01mmol/L MgSO
4, 0.5g/L MnSO
4, 0.1g/L ZnSO
4, 0.01g/L CuSO
4, 0.01g/LAlK (SO
4)
2, 1.0g/LNaCl, 0.1g/L FeCl
2, 0.1g/L CaCl
2And CoCl
20.1g/L, vitamin mixture: 2mg/LBiotin, 2mg/L folic acid, 10mg/L pyridoxine hydrochloride (V
B6), 5mg/L riboflavin, 5mg/Lthiamine, 5mg/L nicotinic acid, 5mg/L pantothenic acid, 0.1mg/L vitamin BE, 5mg/Lp-aminobenzoic acid and 5mg/L thioctic acid, solvent is a water.
5. microbiological fuel cell according to claim 1 is characterized in that, described anode electrode or cathode electrode are carbon paper, graphite or metallic conduction material.
6. the application of the described microbiological fuel cell of claim 1 on the degrade azo dyestuff pollutant.
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Cited By (9)
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|---|---|---|---|---|
| CN102593469A (en) * | 2012-02-23 | 2012-07-18 | 常州水木环保科技有限公司 | Method for accelerating reduction decolorization of azo dyes wastewater at microbial fuel cell cathode |
| CN103304037A (en) * | 2012-03-16 | 2013-09-18 | 北京大学深圳研究生院 | Method for treating sewage, generating electric energy and assisting fermentation by virtue of bioelectrochemical system |
| CN103427102A (en) * | 2013-08-30 | 2013-12-04 | 华南理工大学 | Phycomycetes microbial fuel cell and preparation method and application of phycomycetes microbial fuel cell |
| CN107010714A (en) * | 2017-05-22 | 2017-08-04 | 东北大学 | Waste Water Treatment and method that biological electro catalysis are coupled with photocatalytic contact oxidation |
| CN107777842A (en) * | 2017-11-20 | 2018-03-09 | 大连理工大学 | A kind of method of clean and effective mineralising azo dyes |
| CN108358282A (en) * | 2018-03-07 | 2018-08-03 | 北京师范大学 | A kind of modified gas diffusion electrode and preparation method thereof |
| CN111115816A (en) * | 2020-01-06 | 2020-05-08 | 广东电科院能源技术有限责任公司 | Bioelectrochemical device and method for treating organic pollutants containing azobenzene |
| CN112162013A (en) * | 2020-09-28 | 2021-01-01 | 福建农林大学 | Microbial fuel cell for monitoring electron transfer between direct inoculation and application method |
| CN114836346A (en) * | 2022-04-25 | 2022-08-02 | 华南理工大学 | Method for reducing and fixing Cr (VI) by poly-dopamine modified Shewanella under electron mediation |
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| CN102593469A (en) * | 2012-02-23 | 2012-07-18 | 常州水木环保科技有限公司 | Method for accelerating reduction decolorization of azo dyes wastewater at microbial fuel cell cathode |
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| CN108358282A (en) * | 2018-03-07 | 2018-08-03 | 北京师范大学 | A kind of modified gas diffusion electrode and preparation method thereof |
| CN108358282B (en) * | 2018-03-07 | 2020-05-26 | 北京师范大学 | Modified gas diffusion electrode and preparation method thereof |
| CN111115816A (en) * | 2020-01-06 | 2020-05-08 | 广东电科院能源技术有限责任公司 | Bioelectrochemical device and method for treating organic pollutants containing azobenzene |
| CN112162013A (en) * | 2020-09-28 | 2021-01-01 | 福建农林大学 | Microbial fuel cell for monitoring electron transfer between direct inoculation and application method |
| CN114836346A (en) * | 2022-04-25 | 2022-08-02 | 华南理工大学 | Method for reducing and fixing Cr (VI) by poly-dopamine modified Shewanella under electron mediation |
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