CN103159331A - Method and device for simultaneously carrying out wastewater treatment and power generation by using photocatalysis associated microbial fuel cell technology - Google Patents
Method and device for simultaneously carrying out wastewater treatment and power generation by using photocatalysis associated microbial fuel cell technology Download PDFInfo
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- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention discloses a method and a device for simultaneously carrying out wastewater treatment and power generation by using a photocatalysis associated microbial fuel cell technology. The device takes conductive glass coated with an n-type semiconductor photocatalyst film as an outside wall of a cathode chamber and takes conductive glass coated with an n-type semiconductor photocatalyst film as an outside wall of an anode chamber, a conductive filler respectively connected on the outside walls of the cathode chamber and the anode chamber is used as an electrode of a microbial fuel cell. The conductive filler is a carbon fiber rope for microbial growth. Denitrifying bacteria and nitrifying bacteria are respectively cultivated at the cathode and anode of the microbial fuel cell, and mainly used for the degradation of organic matters and the removal of ammonia nitrogen. Under the irradiation of ultraviolet light, electrons flow from the anode to the cathode, so that the anode has strong oxidability, and the cathode has strong reducibility. In the invention, the functions of microbial fuel cells and a photocatalysis technology are mutually associated, so that the wastewater treatment cost is low, and the generating capacity is large.
Description
Technical field
The present invention relates to photocatalysis technology and microbiological fuel cell technology, be specifically related to method and device that the collaborative microbiological fuel cell technical finesse sewage of a kind of photochemical catalysis generates electricity simultaneously.
Technical background
Microbiological fuel cell (Microbial Fuel Cell is called for short MFC) is to utilize microorganism the chemical energy in organism to be converted into the device of electric energy.Under anolyte compartment's anaerobic environment, organism decomposes under microbial process and discharges electronics and proton.Electronics relies on suitable electron transfer mediator effectively to transmit between biological components and anode, and is delivered to negative electrode formation electric current by external circuit, and proton is delivered to negative electrode by proton exchange membrane.Oxygenant obtains electronics at negative electrode and is reduced with proton and is combined into water.Research finds that biological-cathode type MFC has the ability of denitrogenation, and it provides new approaches for bio-denitrification technology.Think that at present the denitrification functions of MFC can occur respectively in anolyte compartment and cathode compartment.Because nitrification and denitrification in traditional denitrification process is different to the requirement of environment, both carry out in different reactors often, also develop thus various configuration.Present denitrogenation MFC goes processing rate more satisfactory to ammonia nitrogen, but its structure is comparatively complicated, and power generation capacity is lower.
Photocatalyst (photocatalyst) is a based semiconductor material, and it can lack the successive zone by interband, has certain energy gap.When being equal to or greater than the rayed photocatalyst of semi-conductive energy gap with energy, electronics transits to conduction band (conduction band, CB) from valence band (valence band, VB), produces hole-electron pair.Under the potential field effect, photohole (h
+) and light induced electron (e
-) can migrate to catalyst surface.Hole (h
+) have extremely strong oxidisability, be splendid electron acceptor(EA).Electronics (e
-) have extremely strong reductibility, be splendid electron donor.The present invention combines photocatalysis technology and microbiological fuel cell, dispose of sewage middle organism and ammonia nitrogen, generating simultaneously.Under the solar light irradiation condition, electronics stays the hole from the valence of photocatalyst to conduction band in valence band.Valence band is as the electron acceptor(EA) of nitrifying process, realizes the nitrated of ammonia nitrogen under nitrifier collaborative.Conduction band is as the electron donor of denitrification process, realizes the denitrification of nitric nitrogen under denitrifying bacterium collaborative.
Summary of the invention
For solving existing microorganism cathode microbial fuel cell complex structure, the problem such as the few and waste water COD clearance of generated energy is low the invention provides method and device that the collaborative microbiological fuel cell technical finesse sewage of a kind of photochemical catalysis generates electricity simultaneously.
Technical scheme of the present invention is as follows:
The device that the collaborative microbiological fuel cell technical finesse sewage of a kind of photochemical catalysis generates electricity simultaneously, comprise anolyte compartment and cathode compartment, separated by ion-exchange membrane between anolyte compartment and cathode compartment, ion-exchange membrane respectively accounts for half area by anionic membrane and cationic membrane and jointly forms a film, and ion-exchange membrane makes proton and the nitric nitrogen that in the anolyte compartment, nitration reaction produces transfer to cathode compartment;
The outer side wall of anolyte compartment take the conductive glass that scribbles p-type semiconductor light-catalyst film as the anolyte compartment, place conductive filler material and nitrobacteria in the anolyte compartment, the conductive glass that scribbles p-type semiconductor light-catalyst film connects conductive filler material as the anode of microbiological fuel cell; Under ultra violet lamp, the electronics of p-type semi-conductor conductive glass is to cathodic migration, and enrichment makes anode be oxidisability from the hole that cathodic migration is come, can the oxidation removal organism, and ammonia nitrogen can be oxidized to nitric nitrogen;
The outer side wall of cathode compartment take the conductive glass that scribbles N-shaped semiconductor light-catalyst film as cathode compartment, so-called outer side wall refers to the sidewall relative with ion-exchange membrane, place conductive filler material and denitrifying bacterium in cathode compartment, the conductive glass that scribbles N-shaped semiconductor light-catalyst film connects conductive filler material as the negative electrode of microbiological fuel cell; Under ultra violet lamp, the migration of the hole anode of N-shaped semi-conductor conductive glass, and the enrichment electronics of coming from the anode migration make negative electrode be reductibility, can be nitrogen with nitrate-nitrogen reduction;
Conductive filler material in described cathode and anode chamber is connected by external circuit, and under UV-irradiation, electronics flows to the N-shaped semi-conductor by the p-type semi-conductor through external circuit, and extrinsic current flows to the anolyte compartment by cathode compartment;
Bottom at cathode compartment is provided with water intake, and the top arranges the cathode compartment water outlet, and anolyte compartment's water-in is arranged on the bottom, anolyte compartment, and the cathode compartment water outlet directly imports the anolyte compartment, at the top of anolyte compartment, anolyte compartment's water outlet is set.
This device adopts the collaborative microbiological fuel cell technical finesse sewage of photochemical catalysis, obtain simultaneously electric energy, in cathode compartment, a part of organic substance in sewage provides carbon source for denitrifying bacterium, for the denitrifying bacterium growth, make in sewage original nitric nitrogen be reduced to nitrogen and remove, remove simultaneously partial organic substances.The anolyte compartment is directly sent in the cathode compartment water outlet.Ammonia nitrogen is oxidized to nitric nitrogen by nitrobacteria in the anolyte compartment, and nitric nitrogen infiltrates cathode compartment by ion-exchange membrane, is reduced to nitrogen at cathode compartment by denitrifying bacterium, discharges reactor, and ammonia nitrogen is removed; The oxidized removal of organism discharges proton and electronics.Proton enters cathode compartment by the anolyte compartment by cationic membrane, thus electric current in producing, and the interior sense of current flows to negative electrode from anode; Electronics is passed to anode by conductive filler material, then is passed to negative electrode from external circuit, and the extrinsic current direction is from the cathode system anode.
The method that adopts described device to carry out sewage disposal and generating simultaneously comprises the following steps:
(1) microorganism culturing: cultivate nitrobacteria in the anolyte compartment, cultivate denitrifying bacterium at cathode compartment;
(2) interior electric current produces: in the anolyte compartment, the proton that organic matter degradation produces changes cathode compartment over to by cationic exchange membrane, carries out anti-nitration reaction for denitrifying bacterium in cathode compartment; Proton turns to cathode compartment by the anolyte compartment, electric current in producing, and the interior sense of current is for to flow to negative electrode from anode;
(3) removal of organism and ammonia nitrogen: send sewage to cathode compartment from the cathode compartment water-in, a part of organic substance in sewage provides carbon source for denitrifying bacterium, for denitrifying bacterium growth, make in sewage original nitric nitrogen be reduced to nitrogen and remove, remove simultaneously partial organic substances; The cathode compartment water outlet is directly sent into the anolyte compartment by anolyte compartment's water-in, and the oxidized removal of organism, discharge proton in the anolyte compartment, and proton infiltrates cathode compartment by cationic exchange membrane; Ammonia nitrogen is oxidized to nitric nitrogen in the anolyte compartment by nitrobacteria, and nitric nitrogen infiltrates cathode compartment by anion-exchange membrane, is reduced to nitrogen at cathode compartment by denitrifying bacterium, discharges reactor, and ammonia nitrogen is removed;
(4) extrinsic current produces: under the ultraviolet light irradiation, electronics scribbles the semi-conductive negative electrode of N-shaped by being coated with the semi-conductive anode utmost point flow direction of p-type, forms extrinsic current, and the extrinsic current direction is the cathode system anode; Simultaneously, organism and ammonia nitrogen are oxidized in the anolyte compartment, discharge electronics.Microorganism is passed to anode with electronics by conductive filler material, then is passed to negative electrode from external circuit.Nitric nitrogen is at the negative electrode trapped electron, and self is reduced to nitrogen; Like this, photochemical catalysis and microbiological fuel cell are completed the generation of extrinsic current jointly, and the extrinsic current direction is from the cathode system anode.
Advantage of the present invention is as follows:
(1) increase the electrogenesis amount.This device combines microbiological fuel cell and photocatalysis technology, and synergistic effect has both occured, and has greatly increased the electrogenesis amount of microbiological fuel cell originally.
(2) simple in structure.To scribble the conductive glass of photocatalyst in this device as the wall of microbiological fuel cell, in the anode chamber and the cathode chamber of MFC with the ion-exchange membrane of a zwitterion film half and half, proton and nitric nitrogen that anode is produced can directly enter cathode compartment internally, have simplified the structure of reactor.
(3) remove organism denitrogenation simultaneously.In the microorganism cathode compartment, the nitric nitrogen that denitrifying bacterium utilizes the organism in sewage that cathode compartment is infiltrated in the anolyte compartment is converted into the nitrogen eliminating.In the microorganism anolyte compartment, further degradation of organic substances and will intake in mineralized nitrogen be nitric nitrogen.Under the dual function of anolyte compartment and cathode compartment, increased the organic matter removal effect, completed simultaneously the nitration denitrification denitrogenation effect.
Microbiological fuel cell in the present invention and photocatalysis technology can be realized having complementary advantages, and function is coordinated mutually, makes cost of sewage disposal low, and generated energy is large.
Description of drawings
Fig. 1 is the collaborative microbiological fuel cell of the photochemical catalysis structural representation of power generation assembly simultaneously of disposing of sewage.
In figure: 1-water intake; 2-cathode compartment water outlet; 3-anolyte compartment water-in; 4-anolyte compartment water outlet; 5-be coated with the silicon-dioxide conductive glass; 6-be coated with the titanium dioxide conductive glass; 7-conductive filler material; 8-electrical appliance; A-anion-exchange membrane; B-cationic exchange membrane; A-MFC anolyte compartment; B-MFC cathode compartment.
Embodiment
The present invention will be further described with specific embodiment by reference to the accompanying drawings, but the present invention is not limited to this.
Following embodiment electrode used therein: the outer side wall by the cathode and anode chamber connects indoor separately conductive filler material as the electrode of microbiological fuel cell respectively, wherein the cathode compartment outer side wall is for scribbling the conductive glass of titanium dioxide (N-shaped semi-conductor), and anolyte compartment's outer side wall is for scribbling the conductive glass of silicon-dioxide (p-type semi-conductor).Cationic membrane and anionic membrane are all bought from Japan AGC company; Remaining reaction crust of the device material is synthetic glass except conductive glass.
Referring to Fig. 1, this device has the MFC A of anolyte compartment and MFC cathode compartment B.Be placed with conductive filler material and nitrobacteria in the A of anolyte compartment, be placed with conductive filler material and denitrifying bacterium in cathode compartment B.Outer side wall take the conductive glass that scribbles photocatalytic titania thin film as the MFC cathode compartment, outer side wall take the conductive glass that scribbles the silicon-dioxide photocatalyst film as the MFC anolyte compartment connects respectively conductive filler material as the electrode of microbiological fuel cell on the outer side wall of cathode and anode device.
The A of anolyte compartment and the cathode compartment B of microbiological fuel cell are separated by ion-exchange membrane, and ion-exchange membrane forms one whole by anion-exchange membrane a and cationic exchange membrane b each half.The major function of ion-exchange membrane is to make proton and the nitric nitrogen that in the anolyte compartment, nitration reaction produces transfer to cathode compartment.
Be provided with water intake 1 in the bottom of cathode compartment, the top arranges cathode compartment water outlet 2, and anolyte compartment's water-in 3 is arranged on the bottom, anolyte compartment, connects cathode compartment and anolyte compartment, at the top of anolyte compartment, anolyte compartment's water outlet 4 is set.Sewage enters cathode compartment by water-in 1, then enters the anolyte compartment through cathode compartment water port 2 and anolyte compartment's water-in 3, at last by water outlet 4 water outlets.
Microorganism in this device Anodic chamber is nitrobacteria, and major function is the organic pollutant in degradation of sewage and is nitric nitrogen with mineralized nitrogen, simultaneously with transfer transport to electrode, thereby generating.The microorganism of cathode compartment is denitrifying bacterium, and major function is that nitric nitrogen is converted into nitrogen, discharges reactor.
The photocatalysis technology of this device is partly for to scribble the conductive glass of photocatalyst as wall of reactor.Under UV-irradiation, electronics flows to the N-shaped semi-conductor by the p-type semi-conductor through external circuit, and extrinsic current flows to the anolyte compartment by cathode compartment.Specific as follows:
Anode is to scribble the conductive glass 5 of silicon-dioxide and the conductive filler material 7 that connects.Under UV-irradiation, the electronics of p-type semi-conductor conductive glass is to cathodic migration, and enrichment makes anode be oxidisability from the hole that cathodic migration is come, and under anaerobic, can be carbonic acid gas and proton with the oxidation operation in sewage.The nitrobacteria that grows on the anode conducting filler can be oxidized to nitric nitrogen with ammonia nitrogen, and the electronics of generation reaches external circuit through conductive filler material.
Negative electrode is to scribble the conductive glass 6 of titanium dioxide and the conductive filler material 7 that connects.Under UV-irradiation, the hole anode migration of N-shaped semi-conductor conductive glass, titanium dioxide can be assembled electronics, make negative electrode be reductibility, for anti-nitration reaction provides electronics, be nitrogen with nitrate-nitrogen reduction under the denitrifying bacterium effect of growing on conductive filler material, discharge reactor.
The conductive filler material of microbiological fuel cell is carbon fiber rope, supplies microorganism apposition growth in the above.
External circuit is equipped with electrical appliance 8, is used for observing and calculating the electrogenesis amount.
The sewage disposal of this device and the method for generating are as follows:
(1) microorganism culturing: cultivate nitrobacteria in the anolyte compartment, cultivate denitrifying bacterium at cathode compartment;
(2) interior electric current produces: in the anolyte compartment, the proton that organic matter degradation produces changes cathode compartment over to by cationic exchange membrane, carries out anti-nitration reaction for denitrifying bacterium in cathode compartment.Proton turns to cathode compartment by the anolyte compartment, thus electric current in producing, and the interior sense of current flows to negative electrode from anode.
(3) removal of organism and ammonia nitrogen: send sewage to cathode compartment from water-in, a part of organic substance in sewage provides carbon source for denitrifying bacterium, for denitrifying bacterium growth, make in sewage original nitric nitrogen be reduced to nitrogen and remove, remove simultaneously partial organic substances.The anolyte compartment is directly sent in the cathode compartment water outlet.The oxidized removal of organism, discharge proton in the anolyte compartment, and proton infiltrates cathode compartment by cationic exchange membrane.Ammonia nitrogen is oxidized to nitric nitrogen by nitrobacteria, and nitric nitrogen infiltrates cathode compartment by anion-exchange membrane, is reduced to nitrogen at cathode compartment by denitrifying bacterium, discharges reactor, and ammonia nitrogen is removed.
(4) extrinsic current produces: under the ultraviolet light irradiation, electronics is flowed to the negative electrode that scribbles titanium dioxide by the anode utmost point that scribbles silicon-dioxide, form extrinsic current.The extrinsic current direction is the cathode system anode.Simultaneously, organism and ammonia nitrogen are oxidized in the anolyte compartment, discharge electronics.Microorganism is passed to anode with electronics by conductive filler material, then is passed to negative electrode from external circuit.Nitric nitrogen is at the negative electrode trapped electron, and self is reduced to nitrogen.Photochemical catalysis and microbiological fuel cell are completed the generation of extrinsic current jointly, and the extrinsic current direction is from the cathode system anode.
The processing parameter of this device is as follows: the volume of anode of microbial fuel cell chamber and cathode compartment is 4.5L; Scribble the long-pending 300cm of being of conductive glass surface of photocatalyst
2When the organic waste water chemical oxygen demand (COD) is 500 mg/L; Ammonia-nitrogen content is 150 mg/L; The organic waste water flow is 20 mL/min; Ultraviolet lighting intensity is 0.5mW/cm
2The time, the product point ability of device is 0.32 W/m
2, organic waste water chemical oxygen demand (COD) degradation rate is 85.3%, ammonia nitrogen removal frank is 89.7%.
Claims (2)
1. the device that microbiological fuel cell technical finesse sewage generates electricity is simultaneously worked in coordination with in a photochemical catalysis, it is characterized in that: described device comprises anolyte compartment and cathode compartment, separated by ion-exchange membrane between anolyte compartment and cathode compartment, ion-exchange membrane respectively accounts for half area by anionic membrane and cationic membrane and jointly forms a film, and ion-exchange membrane makes proton and the nitric nitrogen that in the anolyte compartment, nitration reaction produces transfer to cathode compartment;
The outer side wall of anolyte compartment take the conductive glass that scribbles p-type semiconductor light-catalyst film as the anolyte compartment, place conductive filler material and nitrobacteria in the anolyte compartment, the conductive glass that scribbles p-type semiconductor light-catalyst film connects conductive filler material as the anode of microbiological fuel cell; Under ultra violet lamp, the electronics of p-type semi-conductor conductive glass is to cathodic migration, and enrichment makes anode be oxidisability from the hole that cathodic migration is come, the oxidation removal organism, and ammonia nitrogen is oxidized to nitric nitrogen;
The outer side wall of cathode compartment take the conductive glass that scribbles N-shaped semiconductor light-catalyst film as cathode compartment, place conductive filler material and denitrifying bacterium in cathode compartment, the conductive glass that scribbles N-shaped semiconductor light-catalyst film connects conductive filler material as the negative electrode of microbiological fuel cell; Under ultra violet lamp, the migration of the hole anode of N-shaped semi-conductor conductive glass, and the enrichment electronics of coming from the anode migration make negative electrode be reductibility, are nitrogen with nitrate-nitrogen reduction;
Conductive filler material in described cathode and anode chamber is connected by external circuit, and under UV-irradiation, electronics flows to the N-shaped semi-conductor by the p-type semi-conductor through external circuit, and extrinsic current flows to the anolyte compartment by cathode compartment;
Bottom at cathode compartment is provided with water intake, and the top arranges the cathode compartment water outlet, and anolyte compartment's water-in is arranged on the bottom, anolyte compartment, and the cathode compartment water outlet directly imports the anolyte compartment, at the top of anolyte compartment, anolyte compartment's water outlet is set.
2. the method for utilizing device claimed in claim 1 to carry out sewage disposal and generate electricity simultaneously is characterized in that: said method comprising the steps of:
(1) microorganism culturing: cultivate nitrobacteria in the anolyte compartment, cultivate denitrifying bacterium at cathode compartment;
(2) interior electric current produces: in the anolyte compartment, the proton that organic matter degradation produces changes cathode compartment over to by cationic exchange membrane, carries out anti-nitration reaction for denitrifying bacterium in cathode compartment; Proton turns to cathode compartment by the anolyte compartment, electric current in producing, and the interior sense of current is for to flow to negative electrode from anode;
(3) removal of organism and ammonia nitrogen: send sewage to cathode compartment from the cathode compartment water-in, a part of organic substance in sewage provides carbon source for denitrifying bacterium, for denitrifying bacterium growth, make in sewage original nitric nitrogen be reduced to nitrogen and remove, remove simultaneously partial organic substances; The cathode compartment water outlet is directly sent into the anolyte compartment by anolyte compartment's water-in, and the oxidized removal of organism, discharge proton in the anolyte compartment, and proton infiltrates cathode compartment by cationic exchange membrane; Ammonia nitrogen is oxidized to nitric nitrogen in the anolyte compartment by nitrobacteria, and nitric nitrogen infiltrates cathode compartment by anion-exchange membrane, is reduced to nitrogen at cathode compartment by denitrifying bacterium, discharges reactor, and ammonia nitrogen is removed;
(4) extrinsic current produces: under the ultraviolet light irradiation, electronics scribbles the semi-conductive negative electrode of N-shaped by being coated with the semi-conductive anode utmost point flow direction of p-type, forms extrinsic current, and the extrinsic current direction is the cathode system anode; Simultaneously, organism and ammonia nitrogen are oxidized in the anolyte compartment, discharge electronics;
Microorganism is passed to anode with electronics by conductive filler material, then is passed to negative electrode from external circuit;
Nitric nitrogen is at the negative electrode trapped electron, and self is reduced to nitrogen; Like this, photochemical catalysis and microbiological fuel cell are completed the generation of extrinsic current jointly, and the extrinsic current direction is from the cathode system anode.
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