CN103820811B - The method reclaiming elemental copper from copper-containing wastewater with microbiological fuel cell - Google Patents

The method reclaiming elemental copper from copper-containing wastewater with microbiological fuel cell Download PDF

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CN103820811B
CN103820811B CN201410017732.1A CN201410017732A CN103820811B CN 103820811 B CN103820811 B CN 103820811B CN 201410017732 A CN201410017732 A CN 201410017732A CN 103820811 B CN103820811 B CN 103820811B
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copper
anode
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containing wastewater
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CN103820811A (en
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刘维平
印霞棐
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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

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Abstract

The invention discloses a kind of method that microbiological fuel cell reclaims elemental copper from copper-containing wastewater, comprise the following steps: build dual chamber MFC reactor, including cathode chamber and anode chamber, the two poles of the earth are isolated by PEM between room, and dual chamber MFC reactor also includes data collecting system；MFC anode tamed strain is cultivated；Being passed through anode substrate, step to anode indoor and 2. tame the anode strain after cultivation and phosphate buffered solution, the COD value of anode substrate is more than 850mg/L, and anode strain is 1: 8～14 with the volume ratio of anode substrate；It is passed through copper-containing wastewater solution as catholyte to cathode chamber；The electric current density produced as MFC is 0.1～4.5 mA m-2Time, there is copper-colored material to separate out at negative electrode, take out negative electrode after running 190h～400h, with hairbrush, the copper-colored deposit on negative electrode is scraped in product catcher, product detects it for elemental copper through X-ray diffractometer.

Description

The method reclaiming elemental copper from copper-containing wastewater 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 microbiological fuel cell reclaims elemental copper from copper-containing wastewater.
Background technology
Along with the high speed development of modern industry, the industry such as metal smelt, plating and printed circuit board (PCB) produces substantial amounts of copper-containing wastewater.As a example by a medium scale plastic electroplating factory, usual every day waste discharge about 1500 T, wherein copper-containing wastewater about 840 t, if calculating with copper content 50mg/L, the copper amount that every day discharges reaches 42 kg.Copper-containing wastewater enters and environment will cause in environment huge harm.
The traditional treatment method of copper-containing wastewater includes chemical precipitation method, ion exchange etc., and these methods are difficulty with the recovery of copper, it is also possible to produce secondary pollution.Electrolysis flow process is simple and convenient to operate, need not to add other chemical agents, do not produce the secondary pollutions such as mud, efficiently quick, can directly reclaim metallic copper, but the major defect of electrolysis is the heavy metal wastewater thereby being difficult to process dilute concentration；And the contained waste liquid of high concentration is after electrolysis, copper content still can exceed that discharge standard.In addition, electrolysis energy consumption is high, processes high-concentration waste liquid fashion and can produce the most considerable economic benefit, but current efficiency along with in contained waste liquid the reduction of copper concentration and reduce, restricted by economic benefit factors, limit electrolysis popularization and application in low concentration wastewater processes.
Microbiological fuel cell (Microbial fuel cell, MFC) is to utilize microorganism as reactive agent, and the chemical energy of organic substance is converted into a kind of device of electric energy；It it is a kind of new technique having merged sewage disposal and bio electricity in recent years developed rapidly.MFC is divided into anode region and cathode chamber, the two district to be separated by PEM.
In the anode region of MFC, microorganism is with Organic substance as electron donor, using electrode as electron acceptor by oxidation operation, electronics and proton is produced during Organic substance is oxidized, electronics is enriched with on anode, transfers to negative electrode by external circuit, and proton enters cathode chamber by PEM.On cathode chamber, electronics and electron acceptor and remaining proton can react, and the process decomposed along with anode Organic substance is exactly the process of electron transfer.
If with Cu2+As the cathode electronics receptor of MFC, then the electric current that MFC can be utilized to produce replaces the conventional power source in electrolysis Treatment of Copper waste water technology.
Technology about microbiological fuel cell Treatment of Copper waste water, the China document microbiological fuel cell Treatment of Copper waste water of substrate " excess sludge be " (Liang Min, Tao Huchun etc., environmental science, Vol.32, No.1, Jan., 2011) using dual chamber MFC, the PEM through pretreatment is placed between two Room that volume is 1L.In its M3 reactor, outer meeting resistance is 0 Ω, and anode chamber adds thickened sludge 1000mL, using phosphate buffer solution as cathode solution in the starting period, exposes into air, the starting period terminate after stop aeration, negative electrode buffer solution is replaced by 1000mL [Cu2+The copper-bath of]=1000mg/L, carries out Cu2+Reduction experiment.Cu in cathode solution after reaction beginning 192h2+Concentration is down to 68.8mg/L, and clearance reaches 93.3%, and the highest clearance reaches 10.7 mg/h.After 192h reaction rate reduce, average removal rate be 0.5mg/h, 288h experiment terminate final clearance be 97.8%.Experiment scrapes bronzing deposit on minus plate after terminating and carries out X-ray diffraction analysis, and M3 cathode reduction products is mainly elemental copper, is Red copper oxide on a small quantity.
Chinese patent literature CN 101710625 B discloses a kind of fuel cell system and electricity and reducing heavy metal are produced in sewage disposal.Fuel cell system carries out sewage disposal, product electricity and reducing heavy metal and comprises the following steps: imported in anode chamber by sewage；Buffer solution is imported in cathode chamber, after running 24 hours to 72 hours, heavy metal ion solution is imported in described cathode chamber；By the microbial activity thing in anode chamber, the sewage flowing through anode chamber is processed；Heavy metal ion solution accepts electronics in cathode chamber and is reduced, and the proton of anode chamber migrates to cathode chamber by PEM, makes room, the two poles of the earth in inside reactor electrical communication, produces electric energy.MFC in embodiment is directly with copper-bath as cathode solution, and building dual chamber with waste water for anode substrate has film MFC.Cu in running, in MFC cathode solution2+Anode chamber can be penetrated into by PEM under the pressure of concentration difference, postpone to add copper sulfate and can effectively suppress Cu2+Infiltration.In embodiment 2, MFC is to Cu in 0.1mol/L copper-bath2+Clearance higher, up to 18.59%；XRD analysis proves Cu(II) substantial amounts of Cu can be formed in cathode electrode surface reduction process4(OH)6SO4, reduzate includes Cu and Cu2O, and it is respectively deposited on electrode and PEM (description of CN 101710625 B 0057 section).
Chinese patent literature CN 103397195 A(application number 201310345115.X) disclose retracting device and the recovery method of metallic copper in a kind of discarded printed circuit boards, after broken for discarded printed circuit boards, use Fe3+Metallic copper in discarded printed circuit boards is generated Cu2+；After microbiological fuel cell maximum output voltage is stable, microorganism fuel cell cathode room phosphate buffer is changed in discarded printed circuit boards contain in metallic copper leaching reactor Cu2+Solution, run and take out negative electrode after a period of time, elemental copper can be obtained.
Above-mentioned three kinds of methods are all first to add phosphate buffered solution at cathode chamber, after running a period of time, then change the solution of cathode chamber containing Cu into2+Solution；The startup time of front two documents is 24h～72h, negative electrode Cu2+Reduzate in addition to elemental copper, also include Cu4(OH)6SO4And Cu2O。CN The startup of 103397195 A needs 4 weeks (CN The description of 103397195 A 0036 section), start overlong time, the organic efficiency of copper is low.
Summary of the invention
The technical problem to be solved is to provide and a kind of starts the method reclaiming elemental copper from copper-containing wastewater with microbiological fuel cell that the time is short, organic efficiency is high.
The technical scheme realizing the object of the invention is a kind of method that microbiological fuel cell reclaims elemental copper from copper-containing wastewater, comprises the following steps:
1. building dual chamber MFC reactor, including cathode chamber and anode chamber, the two poles of the earth are isolated by PEM between room, and dual chamber MFC reactor also includes data collecting system.
2. MFC anode tamed strain is cultivated.
3. the recovery of copper, is passed through anode substrate, step and 2. tames the anode strain after cultivation and phosphate buffered solution to anode indoor, and the COD value of anode substrate is more than 850mg/L, and anode strain is 1: 8～14 with the volume ratio of anode substrate；It is passed through copper-containing wastewater solution as catholyte to cathode chamber.
The electric current density produced as MFC is 0.1～4.5 mA m-2Time, there is copper-colored material to separate out at negative electrode, take out negative electrode after running 190h～400h, with hairbrush, the copper-colored deposit on negative electrode is scraped in product catcher, 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.
When above-mentioned steps 2. MFC anode tamed strain is cultivated, with glucose solution as bacteria culture fluid, every 1L solution contains: 2～5 g glucoses, 0.5～1 g NH4Cl, 0.1～0.5 g K2HPO4, 0.05～0.1 g MgSO4, 0.05～0.1 g NaCl, 0.05～0.1 g CaCl2；Using the anaerobic sludge of municipal sewage plant as inoculum, after culture fluid nitrogen aeration deoxidation with inoculum by volume 1: 1～2 under anaerobic state domestication cultivate within 18～24 hours, obtain anode strain；Domestication cultivates the anode fungi preservation obtained under anaerobic environment.
The COD value of above-mentioned steps 3. anode substrate is 850 mg/L～1000mg/L.
In the removal process of above-mentioned steps 3. copper, the pH value in anode chamber controls 6.5～7.2.
The present invention has a positive effect:
(1) MFC is combined by the present invention with electrolysis tech, process the organic wastewater of anode chamber and the copper-containing wastewater of cathode chamber simultaneously, the electric energy produced with MFC anode strain degradation Organic substance replaces the external power source needed for copper-containing wastewater electrolysis process, solve the problem that electrolysis energy consumption is high, also solve the electric energy problem effectively utilizing MFC to produce simultaneously.
(2) during the startup of the MFC of the present invention, adding organic wastewater, activated sludge and phosphate buffered solution as anode substrate to anode chamber, cathode chamber adds copper-containing wastewater, treats that electric current density is more than 0.1mA m-2Time, there is copper powder to separate out at negative electrode, after running 190h～400h continuously, collect cathode reduction products；Prior art adds organic wastewater and activated sludge to anode chamber, and cathode chamber adds phosphate buffered solution and starts, and its starting period is it is generally required to 3～7 days.The startup time of the MFC that therefore the inventive method is used is short, improves the organic efficiency of copper.
(3) cathode product of the present invention is through XRD analysis, and deposit is elemental copper；Do not detect Cu2O and Cu4(OH)6SO4。
(4) phosphate buffered solution is added in anode chamber by the present invention, and the pH value indoor at MFC running Anodic controls, 6.5～7.2, to be conducive to giving full play to the degraded of strain and electricity generation ability；The addition of phosphate buffered solution improves ionic conductivity, and the increase of conductive ions makes the ionic strength of whole solution system increase, improves the electric conductivity of anode chamber's solution, reduces the ohmic internal resistance of system, thus improve the output of MFC.
If without phosphate buffered solution in anode chamber, in anode chamber, solution ph can slowly rise along with operation, this be the strain owing to using be methanogen, after simple domestication, be directly used in product electricity.Owing to the domestication time is shorter, anode substrate is sufficient, and Production by Bacteria methane exists competition with producing 2 kinds of production capacity modes of electricity, and in substrate, only some is converted into electric energy to the chemical energy of storage；Methanogen creates certain basicity in gas generation process, and in anode chamber, pH can slowly rise, and causes proton motive force to decline, and then reduces cell output.
Accompanying drawing explanation
Fig. 1 is the current density change curve of the MFC of embodiment 1；
Fig. 2 be embodiment 1 MFC end of run after cathode product XRD figure spectrum；
Fig. 3 be embodiment 1 MFC end of run after the photo of cathode surface；
Fig. 4 is the current density change curve of the MFC of embodiment 2；
Fig. 5 be embodiment 2 MFC end of run after cathode product XRD figure spectrum.
Detailed description of the invention
(embodiment 1)
The reclaiming the method for elemental copper from copper-containing wastewater with microbiological fuel cell and comprise the following steps of the present embodiment:
1. dual chamber MFC reactor is built.
MFC reactor used by the present embodiment includes cathode chamber and the anode chamber that volume is identical, and material is polyethylene, and the volume of room, the two poles of the earth is 500 In mL～700mL(the present embodiment, dischargeable capacity is 700mL), during wherein the dischargeable capacity of room, the two poles of the earth is 300 mL～500mL(the present embodiment, dischargeable capacity is 500mL)；(Nafion is isolated by the PEM through pretreatment between room, the two poles of the earthTM212, E.I.Du Pont Company).Being respectively equipped with anode and negative electrode in anode chamber and cathode chamber, MFC anode is graphite rod, and effective surface area is 31cm2；MFC negative electrode is graphite rod, and effective surface area is 31cm2.It is connected with wire between room, the two poles of the earth, and between room, the two poles of the earth, accesses the variable resistance box (arranging resistance in the present embodiment is 50 Ω) of 10 Ω～100 Ω.Anode chamber seals, and keeps anaerobic environment.
The preprocess method of above-mentioned PEM is: by PEM in 80 DEG C of water-baths, each immersion 1 h in the sulfuric acid solution of distilled water, the hydrogen peroxide solution of 3% and 0.5 mol/L successively, then with distilled water immersion 1 h, repeat abovementioned steps three times, be finally immersed in room temperature in distilled water and save backup.
Preprocess method before MFC graphite anode rod uses is identical with the preprocess method of PEM；MFC negative electrode graphite rod uses the salpeter solution of front 0.5mol/L to clean.
Dual chamber MFC is also connected with data acquisition logging system, inserts saturated calomel electrode (SEC, 212 types, Shanghai Russell Science and Technology Ltd.) as reference electrode in anode chamber.Voltage acquisition record system is by data collecting card (capture card model ADAM4017, brilliant wound more generation science and technology (Beijing) company limited) and PC composition, for gathering the voltage at variable resistance box two ends.
The cathode chamber of MFC is provided with charging aperture and discharging opening, and charging aperture is arranged on the lower end of cathode chamber, and charging aperture is connected with the discharge end of peristaltic pump by pipeline, and the feed end of peristaltic pump is connected with organic wastewater storage tank by pipeline.The discharging opening of cathode chamber is arranged on upper end.
The anode chamber of MFC is provided with water inlet and outlet, and water inlet is arranged on the lower end of anode chamber, and outlet is arranged on the upper end of anode chamber；Water inlet is connected with the water side of delivery pump by pipeline, and the water inlet end of delivery pump is connected with copper-containing wastewater storage tank by pipeline, and outlet is connected with backwater tank by pipeline.
2. MFC anode tamed strain is cultivated.
With glucose solution as bacteria culture fluid, every 1L solution contains: 2～5 g glucoses, 0.5～1 g NH4Cl, 0.1～0.5 g K2HPO4, 0.05～0.1 g MgSO4, 0.05～0.1 g NaCl, 0.05～0.1 g CaCl2。
Using the anaerobic sludge of municipal sewage plant as inoculum, after culture fluid nitrogen aeration deoxidation with inoculum by volume 1: 1.5 under anaerobic state domestication cultivate within 24 hours, obtain anode strain.Domestication cultivates the anode fungi preservation obtained under anaerobic environment.This anode strain is methanogen.
3. the recovery of copper.
Be passed through anode substrate 400mL to anode indoor, 2. step tames the anode strain 50mL after cultivation and phosphate buffered solution 150mL, and using glucose solution as anode substrate in the present embodiment, the COD value of anode substrate is 1000mg/L.It is passed through 500mL Cu to cathode chamber2+Concentration is 6400mg L-1Copper-bath as catholyte.
Seeing Fig. 1, data collecting system gathers the voltage at resistance two ends every 5s, after being converted into electric current density, observes electric current density over time.The MFC of the present embodiment is when running 150h, and electric current density reaches peak value, for 4.5mA m-2。
The electric current density produced as MFC is 0.1～4.5 mA m-2Time, there is copper-colored material to separate out at negative electrode, take out negative electrode after running 390h, with hairbrush, the copper-colored deposit (see figure 3) on negative electrode is scraped in product catcher.In running, the pH value in anode chamber controls 6.5～7.2.
Release cathode chamber and the material in anode chamber after MFC end of run, be passed through fresh material and carry out next group anode substrate and the process of copper-containing wastewater.
On X-ray diffractometer with 0.02 ° away from from 10 ° of continuous scannings to 80 °, obtain its XRD figure compose as shown in Figure 2.The used APEX II DUO type X-ray diffractometer that X-ray diffractometer is Bruker company.
Seeing Fig. 2, cathode deposition diffracting spectrum is that 43.9 °, 50.4 ° and 73.6 ° sharp-pointed diffraction maximum occur at 2 θ, is computed machine examination rope consistent with the characteristic peak of elemental copper；And characteristic peak 36.4 °, 43.2 ° and 61.4 ° and the Cu of Red copper oxide do not occur4(OH)6SO4Characteristic peak 13.9 °, 16.6 °, 22.8 °, 33.5 ° and 35.7 °.Proof cathode reduction products is elemental copper, and bivalence copper is directly reduced to elemental copper.
Phosphate buffered solution is added in anode chamber by the present embodiment, and the pH value indoor at MFC running Anodic controls, 6.5～7.2, to be conducive to giving full play to the degraded of strain and electricity generation ability；The addition of phosphate buffered solution also improves ionic conductivity, and the increase of conductive ions makes the ionic strength of whole solution system increase, and improves the electric conductivity of anode chamber's solution, reduces the ohmic internal resistance of system, thus improves the output of MFC.
If without phosphate buffered solution in anode chamber, in anode chamber, solution ph can slowly rise along with operation, this be the strain owing to using be methanogen, after simple domestication, be directly used in product electricity.Owing to the domestication time is shorter, anode substrate is sufficient, and Production by Bacteria methane exists competition with producing 2 kinds of production capacity modes of electricity, and in substrate, only some is converted into electric energy to the chemical energy of storage；Methanogen creates certain basicity in gas generation process, and in anode chamber, pH can slowly rise, and causes proton motive force to decline, and then reduces cell output.
(embodiment 2)
The present embodiment reclaim the method for elemental copper from copper-containing wastewater with microbiological fuel cell remaining is same as in Example 1, difference is:
The COD value of step 3. Anodic substrate is 850mg/L.
The electricity generation performance of the MFC of the present embodiment is shown in that Fig. 4, MFC maximum current density is 0.6 mA m-2.Take out negative electrode after running 190h, with hairbrush, the copper-colored deposit on negative electrode is scraped in product catcher.
The XRD diffracting spectrum of the present embodiment cathode deposition is shown in Fig. 5, and according to the detection method of embodiment 1, cathode deposition diffracting spectrum is that 43.9 °, 50.4 ° and 73.6 ° sharp-pointed diffraction maximum occur at 2 θ, is computed machine examination rope consistent with the characteristic peak of elemental copper；And characteristic peak 36.4 °, 43.2 ° and 61.4 ° and the Cu of Red copper oxide do not occur4(OH)6SO4Characteristic peak 13.9 °, 16.6 °, 22.8 °, 33.5 ° and 35.7 °.Proof cathode reduction products is elemental copper, and bivalence copper is directly reduced to elemental copper.

Claims (4)

1. the method reclaiming elemental copper from copper-containing wastewater with microbiological fuel cell, it is characterised in that comprise the following steps:
1. building dual chamber MFC reactor, including cathode chamber and anode chamber, the two poles of the earth are isolated by PEM between room, and dual chamber MFC reactor also includes data collecting system；
2. MFC anode tamed strain is cultivated；When MFC anode tamed strain is cultivated, with glucose solution as bacteria culture fluid, every 1L solution contains: 2 ~ 5 g glucoses, 0.5 ~ 1 g NH4Cl、0.1~0.5 g K2HPO4、0.05~0.1 g MgSO4、0.05~0.1 g NaCl、0.05~0.1 g CaCl2；Using the anaerobic sludge of municipal sewage plant as inoculum, after culture fluid nitrogen aeration deoxidation with inoculum by volume 1: 1～2 under anaerobic state domestication cultivate within 18～24 hours, obtain anode strain；Domestication cultivates the anode fungi preservation obtained under anaerobic environment；
3. the recovery of copper, is passed through anode substrate, step and 2. tames the anode strain after cultivation and phosphate buffered solution to anode indoor, and the COD value of anode substrate is more than 850mg/L, and anode strain is 1: 8～14 with the volume ratio of anode substrate；
It is passed through copper-containing wastewater solution as catholyte to cathode chamber；
The electric current density produced as MFC is 0.1～4.5 mA m-2Time, there is copper-colored material to separate out at negative electrode, take out negative electrode after running 190h～400h, with hairbrush, the copper-colored deposit on negative electrode is scraped in product catcher, product detects it for elemental copper through X-ray diffractometer.
Microbiological fuel cell the most according to claim 1 reclaims the method for elemental copper from copper-containing wastewater, it is characterised in that: step 1. middle MFC negative electrode is graphite rod, and MFC anode is graphite rod.
Microbiological fuel cell the most according to claim 1 reclaims the method for elemental copper from copper-containing wastewater, it is characterised in that: the COD value of step 3. anode substrate is 850 mg/L～1000mg/L.
Microbiological fuel cell the most according to claim 1 reclaims the method for elemental copper from copper-containing wastewater, it is characterised in that: in the removal process of step 3. copper, the pH value in anode chamber controls 6.5～7.2.
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