CN103820811A - Method for recovering elementary copper from copper-containing wastewater by using microbiological fuel cell - Google Patents

Method for recovering elementary copper from copper-containing wastewater by using microbiological fuel cell Download PDF

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CN103820811A
CN103820811A CN201410017732.1A CN201410017732A CN103820811A CN 103820811 A CN103820811 A CN 103820811A CN 201410017732 A CN201410017732 A CN 201410017732A CN 103820811 A CN103820811 A CN 103820811A
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copper
anode
mfc
containing wastewater
fuel cell
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CN103820811B (en
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刘维平
印霞棐
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Jiangsu University of Technology
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Jiangsu University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
    • 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
    • C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention discloses a method for recovering elementary copper from copper-containing wastewater by using a microbiological fuel cell. The method comprises the following steps: (1): a double-chamber MFC reactor is built, MFC anode strains are domesticated and cultured, and anode substrates are led into the anode chamber, wherein the double-chamber MFC reactor comprises a cathode chamber, an anode chamber and a data collection system, and the cathode chamber and the anode chamber are separated by a proton exchange membrane; (2): in the domesticated and cultured anode strains and calcium phosphate buffer solutions, the COD value of the anode substrates is larger than 850mg/L, and the volume ratio of the anode strains and the anode substrates is 1:(8-14); copper-containing wastewater solutions are led into the cathode chamber to be used as catholyte. When the density of electric current produced by the MFC is 0.1-4.5mA.m<-2>, bronzed substances are separated out from a cathode, after the operation is performed for 190 hours to 400 hours, the cathode is taken out, bronzed sediments on the cathode are scraped into a product collector by a brush, and products are detected as the elementary copper via an X-ray diffractometer.

Description

From copper-containing wastewater, reclaim the method for elemental copper with microbiological fuel cell
Technical field
The present invention relates to the recovery method of copper in copper-containing wastewater, be specifically related to a kind of method that reclaims elemental copper with microbiological fuel cell from copper-containing wastewater.
Background technology
Along with the high speed development of modern industry, in the industries such as Metal smelting, plating and printed circuit board (PCB), produce a large amount of copper-containing wastewaters.Take a medium scale plastic electroplating factory as example, conventionally every day waste discharge approximately 1500 t, wherein copper-containing wastewater approximately 840 t, if calculate with copper content 50mg/L, the copper amount that discharge every day reaches 42 kg.Copper-containing wastewater enters in environment will cause huge harm to environment.
The traditional treatment method of copper-containing wastewater comprises chemical precipitation method, ion exchange method etc., and these methods are difficult to realize the recovery of copper, also may produce secondary pollution.Electrolytic process flow process is simple, easy to operate, do not need to add other chemical agents, do not produce the secondary pollutions such as mud, efficiently quick, can directly reclaim metallic copper, but the main drawback of electrolytic process is the heavy metal wastewater thereby that is difficult to process dilute concentration; And the contained waste liquid of high density is after electrolysis, copper content still may exceed emission standard.In addition, electrolytic process energy consumption is high, process high-concentration waste liquid fashion and can produce comparatively considerable economic benefit, but current efficiency reduces along with the reduction of copper concentration in contained waste liquid, be subject to economic benefit factors restriction, limited electrolytic process applying in low concentration wastewater is processed.
Microbiological fuel cell (Microbial fuel cell, MFC) is to utilize microorganism as reactive agent, the chemical energy of organic substance is converted into a kind of device of electric energy; It is a kind of new technology that has merged sewage disposal and biological electrogenesis in recent years developing rapidly.MFC is divided into positive column and cathodic area, and Zhe Liangge district is separated by proton exchange membrane.
In the positive column of MFC, microorganism is take organism as electron donor, using electrode as electron acceptor(EA) by oxidation operation, in the oxidized process of organism, produce electronics and proton, electronics is enrichment on anode, transfers to negative electrode by external circuit, and proton enters cathodic area by proton exchange membrane.In cathodic area, electronics and electron acceptor(EA) and remaining proton can react, and the process that is accompanied by anode organic substance decomposing is exactly the process of transfer transport.
If with Cu 2+as the cathode electronics acceptor of MFC, can utilize the electric current that MFC produces to replace the conventional power source in electrolytic process Treatment of Copper waste water technology.
About the technology of microbiological fuel cell Treatment of Copper waste water, China document " the microbiological fuel cell Treatment of Copper waste water that excess sludge is substrate " (Liang Min, Tao Huchun etc., environmental science, Vol.32, No.1, Jan., 2011) adopt two chamber MFC, be placed between two Room that volume is 1L through pretreated proton exchange membrane.In its M3 reactor, outer meeting resistance is 0 Ω, and anolyte compartment adds thickened sludge 1000mL, in the starting period, using phosphate buffer solution as cathode solution, exposes to the sun into air, after the starting period finishes, stops aeration, and negative electrode buffered soln is replaced by 1000mL[Cu 2+the copper-bath of]=1000mg/L, carries out Cu 2+reduction experiment.Cu in cathode solution after reaction beginning 192h 2+concentration is down to 68.8mg/L, and clearance reaches 93.3%, and the highest clearance reaches 10.7 mg/h.After 192h, speed of reaction reduces, and average removal rate is 0.5mg/h, and the final clearance that 288h experiment finishes is 97.8%.After experiment finishes, scrape sorrel settling on negative plate and carry out X-ray diffraction analysis, M3 cathodic reduction product is mainly elemental copper, is Red copper oxide on a small quantity.
Chinese patent literature CN 101710625 B disclose a kind of fuel cell system and sewage disposal electrogenesis and reducing heavy metal.Fuel cell system carries out sewage disposal, electrogenesis and reducing heavy metal and comprises the following steps: sewage is imported in anolyte compartment; Buffered soln is imported in cathode compartment, move and after 24 hours to 72 hours, heavy metal ion solution is imported in described cathode compartment; By the microorganism active thing in anolyte compartment, the sewage of the anolyte compartment that flows through is processed; Heavy metal ion solution is accepted electronics and is reduced in cathode compartment, and the proton of anolyte compartment migrates to cathode compartment by proton exchange membrane, makes chamber, the two poles of the earth in inside reactor electrical communication, produces electric energy.MFC in embodiment is directly take copper-bath as cathode solution, and building two chambers take waste water as anode substrate has film MFC.In operational process, the Cu in MFC cathode solution 2+under the pressure of concentration difference, can be penetrated into anolyte compartment by proton exchange membrane, postpone to add copper sulfate can effectively suppress Cu 2+infiltration.In embodiment 2, MFC is to Cu in 0.1mol/L copper-bath 2+clearance higher, can reach 18.59%; XRD analysis proves Cu(II) in negative electrode surface reduction process, can form a large amount of Cu 4(OH) 6sO 4, reduzate comprises Cu and Cu 2o, and be deposited on respectively (0057 section, the specification sheets of CN 101710625 B) in electrode and proton exchange membrane.
Chinese patent literature CN 103397195 A(application number 201310345115.X) retrieving arrangement and the recovery method of metallic copper in a kind of discarded printed circuit boards are disclosed, by after discarded printed circuit boards fragmentation, use Fe 3+metallic copper oxidation in discarded printed circuit boards is generated to Cu 2+; After microbiological fuel cell maximum output voltage is stable, microorganism fuel cell cathode chamber phosphate buffered saline buffer is changed in discarded printed circuit boards in metallic copper Leaching reaction device containing Cu 2+solution, operation is taken out negative electrode after for some time, can obtain elemental copper.
Above-mentioned three kinds of methods are all first to add phosphate buffer soln at cathode compartment, after operation for some time, then the solution of cathode compartment are changed into containing Cu 2+solution; Be 24h～72h the start time of front two pieces of documents, negative electrode Cu 2+reduzate except elemental copper, also comprise Cu 4(OH) 6sO 4and Cu 2o.The startup of CN 103397195 A needs 4 weeks (0036 section, the specification sheets of CN 103397195 A), and start time is long, and the organic efficiency of copper is low.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method that reclaims elemental copper with microbiological fuel cell from copper-containing wastewater that start time is short, organic efficiency is high.
The technical scheme that realizes the object of the invention is a kind of method that reclaims elemental copper with microbiological fuel cell from copper-containing wastewater, comprises the following steps:
1. build two chambers MFC reactor, comprise cathode compartment and anolyte compartment, the two poles of the earth are isolated by proton exchange membrane between chamber, and two chambers MFC reactor also comprises data collecting system.
2. the domestication of MFC anode bacterial classification is cultivated.
3. the recovery of copper, 2. indoor anode substrate, the step of passing into of anode tame anode bacterial classification and the phosphate buffer soln after cultivation, and the COD value of anode substrate is greater than 850mg/L, and the volume ratio of anode bacterial classification and anode substrate is 1: 8～14; Pass into copper-containing wastewater solution as catholyte to cathode compartment.
The current density producing as MFC is 0.1～4.5 mAm -2time, there is copper-colored material to separate out at negative electrode, after operation 190h～400h, take out negative electrode, with hairbrush, the copper-colored settling on negative electrode to be scraped in product-collecting device, product detects it for elemental copper through X-ray diffractometer.
Above-mentioned steps 1. middle MFC negative electrode is graphite rod, and MFC anode is graphite rod.
Above-mentioned steps 2. MFC anode bacterial classification domestication cultivate time, take glucose solution as bacteria culture fluid, in every 1L solution, contain: 2～5 g glucose, 0.5～1 g NH 4cl, 0.1～0.5 g K 2hPO 4, 0.05～0.1 g MgSO 4, 0.05～0.1 g NaCl, 0.05～0.1 g CaCl 2; Using the anaerobic sludge of municipal sewage plant as inoculum, after the deoxidation of nutrient solution nitrogen aeration, tame under anaerobic state with inoculum 1: 1 by volume～2 to cultivate and within 18～24 hours, obtain anode bacterial classification; Domestication is cultivated the anode bacterial classification obtaining and is kept under anaerobic environment.
The above-mentioned steps 3. COD value of anode substrate is 850 mg/L～1000mg/L.
Above-mentioned steps is 3. in the removal process of copper, and the pH value in anolyte compartment is controlled at 6.5～7.2.
The present invention has positive effect:
(1) the present invention combines MFC with electrolysis tech, process the organic waste water of anolyte compartment and the copper-containing wastewater of cathode compartment simultaneously, the electric energy producing with MFC anode strain degradation organism replaces the required external power source of copper-containing wastewater electrolysis treatment, solve the high problem of electrolytic process energy consumption, also solved the electric energy problem of effectively utilizing MFC to produce simultaneously.
(2) when the startup of MFC of the present invention, anode chamber adds as the organic waste water of anode substrate, active sludge and phosphate buffer soln, and cathode compartment adds copper-containing wastewater, treats that current density is greater than 0.1mAm -2time, there is copper powder to separate out at negative electrode, collect cathodic reduction product after moving continuously 190h～400h; Prior art anode chamber adds organic waste water and active sludge, and cathode compartment adds phosphate buffer soln to start, and its starting period generally needs 3～7 days.Therefore the start time of the MFC that the inventive method is used is short, has improved the organic efficiency of copper.
(3) cathode product of the present invention is through XRD analysis, and settling is elemental copper; Do not detect Cu 2o and Cu 4(OH) 6sO 4.
(4) the present invention adds phosphate buffer soln in anolyte compartment, and the pH value indoor at MFC operational process Anodic is controlled at 6.5～7.2, is conducive to give full play to degraded and the electricity generation ability of bacterial classification; Phosphate buffer soln add raising ionic conductivity, the increase of conductive ions increases the ionic strength of whole solution system, has improved the electroconductibility of anolyte compartment's solution, has reduced the ohmic internal resistance of system, thereby improves the output rating of MFC.
If do not add phosphate buffer soln in anolyte compartment, in anolyte compartment, pH is along with operation can slowly be risen, and this is because the bacterial classification adopting is methanogen, after simple domestication, is directly used in electrogenesis.Because the domestication time is shorter, anode substrate abundance, there is competition in 2 kinds of production capacity modes of Production by Bacteria methane and electrogenesis, and only some is converted into electric energy to the chemical energy of storing in matrix; Methanogen has produced certain basicity in gas generation process, and in anolyte compartment, pH can slowly rise, and causes proton motive force to decline, and then reduces battery output rating.
Accompanying drawing explanation
Fig. 1 is the current density change curve of the MFC of embodiment 1;
Fig. 2 is the XRD figure spectrum of cathode product after the MFC end of run of embodiment 1;
Fig. 3 is the photo of cathode surface after the MFC end of run of embodiment 1;
Fig. 4 is the current density change curve of the MFC of embodiment 2;
Fig. 5 is the XRD figure spectrum of cathode product after the MFC end of run of embodiment 2.
Embodiment
(embodiment 1)
The method that reclaims elemental copper with microbiological fuel cell from copper-containing wastewater of the present embodiment comprises the following steps:
1. build two chambers MFC reactor.
The present embodiment MFC reactor used comprises cathode compartment and the anolyte compartment that volume is identical, material is polyethylene, the volume of chamber, the two poles of the earth is that in 500 mL～700mL(the present embodiment, useful volume is 700mL), wherein the useful volume of chamber, the two poles of the earth is that in 300 mL～500mL(the present embodiment, useful volume is 500mL); Between chamber, the two poles of the earth, isolate (Nafion by the pretreated proton exchange membrane of process tM212, E.I.Du Pont Company).In anolyte compartment and cathode compartment, be respectively equipped with anode and negative electrode, MFC anode is graphite rod, and effective surface area is 31cm 2; MFC negative electrode is graphite rod, and effective surface area is 31cm 2.Between chamber, the two poles of the earth, be connected with wire, and between chamber, the two poles of the earth, access the variable resistance box (it is 50 Ω that resistance is set in the present embodiment) of 10 Ω～100 Ω.Anolyte compartment's sealing, keeps anaerobic environment.
The pretreatment process of above-mentioned proton exchange membrane is: by proton exchange membrane in 80 ℃ of water-baths, each 1 h that soaks in the sulphuric acid soln of distilled water, 3% hydrogen peroxide solution and 0.5 mol/L successively, then use distilled water immersion 1 h, repeat abovementioned steps three times, be finally immersed in normal temperature in distilled water and save backup.
Pretreatment process before MFC graphite anode rod uses is identical with the pretreatment process of proton exchange membrane; Salpeter solution with 0.5mol/L before MFC negative electrode graphite rod uses cleans.
Also connection data acquisition and recording system of two chamber MFC, inserts saturated calomel electrode (SEC, 212 types, Shanghai Russell Science and Technology Ltd.) as reference electrode in anolyte compartment.Voltage acquisition register system is by data collecting card (capture card model ADAM4017, more generation science and technology (Beijing) company limited of brilliant wound) and PC composition, for gathering the voltage at variable resistance box two ends.
The cathode compartment of MFC is provided with opening for feed and discharge port, and opening for feed is arranged on the lower end of cathode compartment, and opening for feed is connected with the discharge end of peristaltic pump by pipeline, and the feed end of peristaltic pump is connected with organic waste water storage tank by pipeline.The discharge port of cathode compartment is arranged on upper end.
The anolyte compartment of MFC is provided with water-in and water outlet, and water-in is arranged on the lower end of anolyte compartment, and water outlet is arranged on the upper end of anolyte compartment; Water-in is connected with the water side of transferpump by pipeline, and the feed-water end of transferpump is connected with copper-containing wastewater storage tank by pipeline, and water outlet is connected with backwater tank by pipeline.
2. the domestication of MFC anode bacterial classification is cultivated.
Take glucose solution as bacteria culture fluid, in every 1L solution, contain: 2～5 g glucose, 0.5～1 g NH 4cl, 0.1～0.5 g K 2hPO 4, 0.05～0.1 g MgSO 4, 0.05～0.1 g NaCl, 0.05～0.1 g CaCl 2.
Using the anaerobic sludge of municipal sewage plant as inoculum, after the deoxidation of nutrient solution nitrogen aeration, cultivate and within 24 hours, obtain anode bacterial classification with inoculum 1: 1.5 by volume domestication under anaerobic state.Domestication is cultivated the anode bacterial classification obtaining and is kept under anaerobic environment.This anode bacterial classification is methanogen.
3. the recovery of copper.
Anode is indoor passes into anode substrate 400mL, 2. step tames anode bacterial classification 50mL and phosphate buffer soln 150mL after cultivation, and in the present embodiment, using glucose solution as anode substrate, the COD value of anode substrate is 1000mg/L.Pass into 500mL Cu to cathode compartment 2+concentration is 6400mgL -1copper-bath as catholyte.
See Fig. 1, data collecting system gathers the voltage at resistance two ends every 5s, be converted into after current density, observes current density over time.The MFC of the present embodiment is in the time of operation 150h, and current density reaches peak value, is 4.5mAm -2.
The current density producing as MFC is 0.1～4.5 mAm -2time, there is copper-colored material to separate out at negative electrode, operation is taken out negative electrode after 390h, the copper-colored settling (see figure 3) on negative electrode is scraped in product-collecting device with hairbrush.In operational process, the pH value in anolyte compartment is controlled at 6.5～7.2.
After MFC end of run, emit the material in cathode compartment and anolyte compartment, pass into fresh material and carry out the processing of next batch anode substrate and copper-containing wastewater.
On X-ray diffractometer with 0.02 ° Walk apart from from 10 ° of continuous sweeps to 80 °, obtain its XRD figure and compose as shown in Figure 2.X-ray diffractometer used is the APEX II DUO type X-ray diffractometer of Bruker company.
See Fig. 2, cathode deposit diffracting spectrum is 43.9 °, 50.4 ° and 73.6 ° of diffraction peaks that appearance is sharp-pointed at 2 θ, and machine examination rope is consistent with the characteristic peak of elemental copper as calculated; And there is not 36.4 °, 43.2 ° of characteristic peaks and 61.4 ° and the Cu of Red copper oxide 4(OH) 6sO 413.9 °, 16.6 °, 22.8 °, 33.5 ° and 35.7 ° of characteristic peaks.Prove that cathodic reduction product is elemental copper, divalence copper is directly reduced to elemental copper.
The present embodiment adds phosphate buffer soln in anolyte compartment, and the pH value indoor at MFC operational process Anodic is controlled at 6.5～7.2, is conducive to give full play to degraded and the electricity generation ability of bacterial classification; Adding of phosphate buffer soln also improved ionic conductivity, and the increase of conductive ions increases the ionic strength of whole solution system, has improved the electroconductibility of anolyte compartment's solution, has reduced the ohmic internal resistance of system, thereby improves the output rating of MFC.
If do not add phosphate buffer soln in anolyte compartment, in anolyte compartment, pH is along with operation can slowly be risen, and this is because the bacterial classification adopting is methanogen, after simple domestication, is directly used in electrogenesis.Because the domestication time is shorter, anode substrate abundance, there is competition in 2 kinds of production capacity modes of Production by Bacteria methane and electrogenesis, and only some is converted into electric energy to the chemical energy of storing in matrix; Methanogen has produced certain basicity in gas generation process, and in anolyte compartment, pH can slowly rise, and causes proton motive force to decline, and then reduces battery output rating.
(embodiment 2)
All the other are identical with embodiment 1 for the method that reclaims elemental copper with microbiological fuel cell from copper-containing wastewater of the present embodiment, and difference is:
The step 3. COD value of Anodic substrate is 850mg/L.
The electricity generation performance of the MFC of the present embodiment is shown in Fig. 4, and MFC maximum current density is 0.6 mAm -2.Operation is taken out negative electrode after 190h, the copper-colored settling on negative electrode is scraped in product-collecting device with hairbrush.
The XRD diffracting spectrum of the present embodiment cathode deposit is shown in Fig. 5, and according to the detection method of embodiment 1, cathode deposit diffracting spectrum is 43.9 °, 50.4 ° and 73.6 ° of diffraction peaks that appearance is sharp-pointed at 2 θ, and machine examination rope is consistent with the characteristic peak of elemental copper as calculated; And there is not 36.4 °, 43.2 ° of characteristic peaks and 61.4 ° and the Cu of Red copper oxide 4(OH) 6sO 413.9 °, 16.6 °, 22.8 °, 33.5 ° and 35.7 ° of characteristic peaks.Prove that cathodic reduction product is elemental copper, divalence copper is directly reduced to elemental copper.

Claims (5)

1. a method that reclaims elemental copper with microbiological fuel cell from copper-containing wastewater, is characterized in that comprising the following steps:
1. build two chambers MFC reactor, comprise cathode compartment and anolyte compartment, the two poles of the earth are isolated by proton exchange membrane between chamber, and two chambers MFC reactor also comprises data collecting system;
2. the domestication of MFC anode bacterial classification is cultivated;
3. the recovery of copper, 2. indoor anode substrate, the step of passing into of anode tame anode bacterial classification and the phosphate buffer soln after cultivation, and the COD value of anode substrate is greater than 850mg/L, and the volume ratio of anode bacterial classification and anode substrate is 1: 8～14;
Pass into copper-containing wastewater solution as catholyte to cathode compartment;
The current density producing as MFC is 0.1～4.5 mAm -2time, there is copper-colored material to separate out at negative electrode, after operation 190h～400h, take out negative electrode, with hairbrush, the copper-colored settling on negative electrode to be scraped in product-collecting device, product detects it for elemental copper through X-ray diffractometer.
2. the method that reclaims elemental copper with microbiological fuel cell from copper-containing wastewater according to claim 1, is characterized in that: step 1. middle MFC negative electrode is graphite rod, and MFC anode is graphite rod.
3. the method that reclaims elemental copper with microbiological fuel cell from copper-containing wastewater according to claim 1, it is characterized in that: step 2. MFC anode bacterial classification domestication cultivate time, take glucose solution as bacteria culture fluid, in every 1L solution, contain: 2～5 g glucose, 0.5～1 g NH 4cl, 0.1～0.5 g K 2hPO 4, 0.05～0.1 g MgSO 4, 0.05～0.1 g NaCl, 0.05～0.1 g CaCl 2; Using the anaerobic sludge of municipal sewage plant as inoculum, after the deoxidation of nutrient solution nitrogen aeration, tame under anaerobic state with inoculum 1: 1 by volume～2 to cultivate and within 18～24 hours, obtain anode bacterial classification; Domestication is cultivated the anode bacterial classification obtaining and is kept under anaerobic environment.
4. the method that reclaims elemental copper with microbiological fuel cell from copper-containing wastewater according to claim 1, is characterized in that: the step 3. COD value of anode substrate is 850 mg/L～1000mg/L.
5. the method that reclaims elemental copper with microbiological fuel cell from copper-containing wastewater according to claim 1, is characterized in that: step is 3. in the removal process of copper, and the pH value in anolyte compartment is controlled at 6.5～7.2.
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CN101710624B (en) * 2009-11-10 2011-10-05 四川大学 Continuous and efficient wastewater treatment microbial fuel cell
CN101719555B (en) * 2009-11-24 2011-12-07 哈尔滨工业大学 Double-chamber alga microbial fuel cell and method thereof for treating waste water and realizing zero carbon emission
CN102290590B (en) * 2011-07-28 2013-07-24 清华大学 Biocathode microbial fuel cell
CN102610843B (en) * 2012-03-29 2014-05-21 南京大学 Microbial fuel cell

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHENG SHAO-AN: "Increasing efficiencies of microbial fuel cells for collaborative treatment of copper and organic wastewater by designing reactor and selecting operating parameters", 《BIORESOURCE TECHNOLOGY》 *
CHENG SHAO-AN: "Increasing efficiencies of microbial fuel cells for collaborative treatment of copper and organic wastewater by designing reactor and selecting operating parameters", 《BIORESOURCE TECHNOLOGY》, 14 August 2013 (2013-08-14) *
梁敏: "剩余污泥为底物的微生物燃料电池处理含铜废水", 《环境科学》 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104499003A (en) * 2014-11-13 2015-04-08 黄石市英柯有色金属有限公司 Method for extracting metal in aqueous solution
CN106571498A (en) * 2016-11-11 2017-04-19 大连理工大学 Method used for separating and recycling molybdenum stannum from molybdenum stannate mixed solution using microbial fuel cells
CN106571498B (en) * 2016-11-11 2019-02-01 大连理工大学 Molybdenum tin method is separated and recovered from from molybdenum stannic acid mixed salt solution using microbiological fuel cell
CN107381776A (en) * 2017-06-07 2017-11-24 南昌航空大学 A kind of preparation method of microbiological fuel cell processing ion containing heavy metal copper
CN107946623A (en) * 2017-10-31 2018-04-20 江苏理工学院 A kind of method of the microbiological fuel cell for handling Copper-Containing Mine Acid Water and copper recycling
CN108977850A (en) * 2018-07-12 2018-12-11 江苏理工学院 A method of the Call Provision in cobalt-carrying solution
CN110078295A (en) * 2019-03-26 2019-08-02 杭州电子科技大学 A kind of synchronization process landfill leachate and the method produced electricity
CN110373544A (en) * 2019-07-25 2019-10-25 中国科学院过程工程研究所 A kind of Deep-Sea Microorganisms gradient handles the device and method of metal ion in heavy metal sewage sludge

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