CN110143662A - Transition metal base Electrode-biofilm fuel cell electroplating waste processing equipment and method - Google Patents
Transition metal base Electrode-biofilm fuel cell electroplating waste processing equipment and method Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F3/00—Biological treatment of water, waste water, or sewage
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- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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Abstract
The present invention provides a kind of transition metal base Electrode-biofilm fuel cell electroplating waste processing equipment and method, including biological anode chamber, cathode chamber, further include be connected to the biological anode chamber and the cathode chamber be connected to bridge, the biology anode chamber and the cathode chamber use transition metal base electrode, and the anode transition metal base electrode of the biology anode chamber stores electric appliance by outside and connect to form closure electrical circuit with the cathode transition metal base electrode of the cathode chamber；The transition metal base electrode is metal nanoparticle composition-nanofiber electrode；The anode transition metal base electrode surface is covered with one layer of microorganism blanket, and the microorganism is anaerobe or amphimicrobe；Aerator is set in the cathode chamber.Device and method provided by the invention can handle the electroplating wastewater and electroplating sludge of plating industrial district simultaneously, and have efficient conductivity, removal of heavy metal ions rate, lower production costs.
Description
Technical field
The invention belongs to the biological fuel cell plating in electroplating wastewater processing field, in particular to transition metal base electrode is useless
Water treatment facilities and method.
Background technique
In the prior art electroplating effluent treatment method have chemical precipitation method, oxidation-reduction method, chemical neutralisation, gas floatation process,
Biosorption process, bio-flocculation process, electroosmose process, electric flocculation waste water treatment process, ion-exchange, membrane separation process, active carbon are inhaled
Attached method.These methods generally have to be handled for certain specific heavy metal, and other heavy metal ion can not be removed effectively, and
Technological parameter setting is complicated, and elimination efficiency is low, the high technological deficiency of production cost.
Global energy crisis and environmental pollution accelerate the research to sustainable clean energy resource, and biological fuel cell is a kind of
Chemical energy in organic matter is directly translated into the device of electric energy using microorganism, used in biocatalyst cleaning, can hold
It is continuous, it can produce electricl energy in a mild condition, compared with noble metal catalyst, battery cost can be greatly lowered.Meanwhile it is raw
Object fuel cell utilizes cheap, environmental-friendly, sustainable fuel, such as carbohydrate, waste water to generate electricity.All these features all make
The substitute of conventional batteries can be become by obtaining biological fuel cell, have very big development prospect.
Mostly use proton exchange membrane by anode chamber and cathode using the device that biological fuel cell carries out electroplating wastewater processing
Room separates, and to prevent oxygen from diffusing to anode from cathode, but proton is allowed to be transferred to cathode, such as Chinese patent from anode
Proton exchange membrane in 201310494795.1 is Nafion, and this film expensive price cannot repeat after a period of use
It uses, cost for wastewater treatment is high, biological fuel cell service life is short.Chinese patent 201710727172.2 discloses a kind of energy
Device and method that are enough while handling plating industrial district sludge and electroplating wastewater, but it is using biological-cathode room, sun
Pole room and chemical cathode room provide stable working environment for anode chamber using biological-cathode room, waste anode chamber's generation
Proton and electronics, and also use proton exchange membrane carry out proton transmitting, high production cost, although being adopted in technical solution
With graphite electrode, but still it is impossible to meet sewage and the demands rapidly and efficiently of Treatment of Sludge for conductivity.
Summary of the invention
In view of the above technical problems, the present invention provides a kind of transition metal base Electrode-biofilm fuel cell electroplating wastewater processing
Device and method, such device and method can handle the electroplating wastewater and electroplating sludge of plating industrial district simultaneously, and
With efficient conductivity, removal of heavy metal ions rate, lower production costs, nano material can also provide sufficient microenvironment,
The stability of catalyst is kept, activity and service life are improved.
The invention adopts the following technical scheme: transition metal base Electrode-biofilm fuel cell electroplating waste processing equipment, packet
Include biological anode chamber 1, cathode chamber 2, which is characterized in that further include being connected to being connected to for the biological anode chamber 1 and the cathode chamber 2
Bridge 3, the biology anode chamber 1 and the cathode chamber 2 use transition metal base electrode, the anode transition of the biology anode chamber 1
Electrode metal substrate 11 connect formation closure electricity with the cathode transition metal base electrode 21 of the cathode chamber 2 by external electric appliance 4 of storing
Circuit；The transition metal base electrode is to receive using metal ion nitrate and nanofiber, using metal made of CVD method
Rice grain composition 5- nanofiber electrode 6, the metal nanoparticle composition is by the first metal nanoparticle 51 and second
Metal nanoparticle 52 forms, and the nanofiber electrode is made of the first nanofiber 61 and the second nanofiber 62；It is described
First metal nanoparticle 51 is attached on the first nanofiber 61, and second metal nano 52 is attached to second nanometer
On fiber 62；11 surface of anode transition metal base electrode is covered with one layer of microorganism blanket 12, and the microorganism is anaerobism
Microorganism or amphimicrobe；Aerator 22 is set in the cathode chamber 2.
More preferably, it is filled with salt matter agar gel in the connection bridge 3, the salt matter agar gel is by mass fraction
The KCl solution or NaCl solution of 0.5-0.9% is mixed with containing the agar gel that agar mass fraction is 4.5-4.8%.
More preferably, the microorganism is any one of the pale bacterium of wheat, Escherichia coli, enterobacter cloacae, bacillus
Or it is several.
More preferably, first metal nanoparticle 51 is copper, zinc, aluminium or magnesium nano particle, second metal nano
Particle 62 is iron, cobalt, nickel or cadmium nano particle, then the metal nanoparticle composition 5 can be copper-iron nano-particle, copper-
Cobalt nano-particle, copper-nano nickel particles, copper-cadmium nano particle, zinc-iron nano-particle, zinc-cobalt nano-particle, zinc-nickel nanometer
Particle, zinc-cadmium nano particle, aluminium-iron nano-particle, aluminium-cobalt nano-particle, aluminium-nano nickel particles, aluminium-cadmium nano particle,
Any one of magnesium-iron nano-particle, magnesium-cobalt nano-particle, magnesium-nano nickel particles, magnesium-cadmium nano particle.
More preferably, first nanofiber 61 is activated carbon fibre, silicon carbide fibre or carbon nanotube, and described second receives
Rice fiber 62 be graphene nano fiber, carbon nano-fiber or boron carbide nanofiber, then the nanofiber electrode 6 can be
Active carbon-graphene nano fiber electrode, active carbon-carbon nano-fiber, active carbon-boron carbide nano particle, carbide-graphite
Alkene nanofiber, silicon carbide-carbon nanofiber, silicon carbide-carbon boron nano particle, carbon nanotube-graphene nano fiber, carbon
Any one of nanotube-carbon nano-fiber, carbon nanotube-boron carbide nanofiber.
Transition metal base Electrode-biofilm fuel cell electroplating wastewater described in claim 1 is utilized the present invention also provides a kind of
The method of processing unit processing electroplating wastewater, which is characterized in that the method follows the steps below:
One, 1.5L anode working electrolyte and LB broth bouillon are added in the biological anode chamber 1, it is continuous logical
N230min provides anaerobic environment for biological anode chamber；By the microbial inoculant in the biological anode chamber 1,18 are tamed
It, replaced the primary anode working electrolyte every 6 days during domestication；
Two, the K for being 100mM by 2L concentration3Fe(CN)6Solution is added in cathode chamber 2, is opened aerator 22, is connected
Continuous aeration 48h, until biological fuel cell has a stable 250mV Voltage Feedback；
Three, it is added to electroplating wastewater sludge as anode substrate in the biological anode chamber 1；Using electroplating wastewater as yin
Pole substrate is added in the cathode chamber 2, is adjusted initial pH to 1.5-2 with 0.5M HCl, is continuously led to N230min mentions for cathode chamber
For anaerobic environment；
Four, power switch is opened, the electroplating waste processing equipment is started, carries out electroplating wastewater and electroplating wastewater sludge
It handles simultaneously, the biological anode chamber 1 and cathode chamber 2 is kept to work between 25 DEG C -35 DEG C, every the 3-4 days primary institutes of replacement
State the electroplating wastewater of cathode chamber 2, the electroplating wastewater sludge and microelement of the primary biological anode chamber 1 of replacement in every 5-10 days
Liquid.
More preferably, the anode working electrolyte composition of the biological anode chamber are as follows: the NaCl of 12.00mM-14.00mM,
2.00mM-3.00mM KCl, 1.00mM-2.00mM Na2HPO4, 17.00mM-18.00mM KH2PO4、2.00mM-
3.00Mm NH4The CaCl of Cl, 0.01mM-0.02mM2, 1.00mM-1.50mM NaHCO3, 3.00mM-5.00mM
CH3COONa；The pH of the anode working electrolyte is 7.
More preferably, 10 μM of -100 μM of anthraquinone -2,6- sodium disulfonates, anthraquinone-2-sulfonic acids are additionally added in the biological anode chamber 1
Any one or more of sodium or Nucin, anthraquinone -2,6- sodium disulfonate, anthraquinone-2-sodium and 5- hydroxyl
Base -1,4-naphthoquinone is electron transfer mediators, and the electronics that can speed up in biological anode chamber 1 is shifted, and then accelerates cathode chamber 2
The reduction reaction of interior heavy metal ion accelerates the removal rate of heavy metal ion.
More preferably, the Cr in the processing method removal electroplating wastewater6+、Ag+、Cu2+、Ni2+、Zn2+。
More preferably, the Cr in electroplating wastewater6+Concentration is 50-1800mg/L.
Compared with prior art, the application has the beneficial effect that
1) biological fuel cell of transition metal base electrode is used, transition metal base electrode uses nano material, and then makes
There is electrode very high middle porosity to be conducive to grow biomembrane in anode surface, and the anaerobism improved in anode biotron is micro-
Biology or amphimicrobe decompose electronics transfer caused by the substance in electroplating wastewater to anode surface；It is received by metal
The use of rice grain composition reduces the obstruction to contact with each other between anode surface and electrolyte, and then improves electronics
The efficiency of transfer；Pass through Cu nano particle, the Zn nano particle, Mg nanometers in the good metal nanoparticle composition of electrical conductance
Any one of particle, Al nano particle are received with the graphene nano fiber in nanofiber electrode, carbon nano-fiber, boron carbide
The conductivity that can be improved electrode is applied in combination in any one of rice fiber；Fe nano particle, Co in metal nano composition
Nano particle, Ni nano particle, Cd nano particle can carry out reduction reaction as electron acceptor in the heavy metal ion of cathode
Play the role of catalyst in the process, and then improves the removal efficiency of heavy metal out of electroplating wastewater ion.
2) cathode does not need additionally to add microorganism, therefore can bear the heavy metal in electroplating wastewater ion of higher concentration,
And cathode does not need buffer medium during biological fuel cell works heavy-metal ion removal, reduces P, Ca, Na and exists
Electroplating wastewater is handled in the process in the formation of cathode, and then improves reduction process of the heavy metal ion as electron acceptor, this
The easy operating procedure of biological fuel cell processing electroplating wastewater of sample, and improve high concentration heavy metal ion electroplating wastewater
Treatment effeciency, reduce cost.Aerator is set in cathode chamber, constantly can provide the air of purification for cathode chamber,
To promote the generation of peroxide reducing agent, and then accelerate the reduction removal of heavy metal ion in cathode chamber.
3) anode surface can speed up anode electricity using anaerobe or amphimicrobe as biocatalyst
Organic substance or inorganic substances in waste electroplating are converted into electronics, and then the process of cathode is transferred to by resistance.Utilize transition
Sludge and heavy metal ion method in the biological fuel cell electroplating waste processing equipment processing electroplating wastewater of electrode metal substrate
In the process, it is added in anthraquinone -2,6- sodium disulfonate, anthraquinone-2-sodium or Nucin in biological anode chamber
Any one or several electronics that can effectively improve in biological anode chamber 1 are shifted, and heavy metal out of electroplating wastewater ion is improved
Removal efficiency.
4) it is connected to bridge using connect biological anode chamber and cathode chamber, instead of the utilization of proton exchange membrane, reduces benefit
The cost of electroplating wastewater is handled with biological fuel cell, and can increase the removal rate of heavy metal ion；And pass through salt bridge
By H+It is transported to cathode, the Cr being plated in waste water6+Reduction reaction is utilized, and the H in cathode chamber is thereby reduced+Concentration, i.e.,
The OH- concentration of cathode chamber is increased, and then is conducive to the Cr that reduction generates3+And other heavy metal ion react and generate hydrogen
Oxide precipitation, and then reached the removal together of the heavy metal ion in electroplating wastewater.
Detailed description of the invention
Fig. 1 is transition metal base biological fuel cell electroplating waste processing equipment schematic diagram of the invention；
Fig. 2 is transition metal base electrode surface structures schematic diagram of the invention.
Specific embodiment
In the following with reference to the drawings and specific embodiments, the present invention is furture elucidated, it should be understood that embodiment is merely to illustrate this hair
Bright rather than limit the scope of the invention, after the present invention has been read, those skilled in the art are to of the invention various etc.
The modification of valence form falls within the application range as defined in the appended claims.
Embodiment 1
The transition metal base Electrode-biofilm fuel cell electroplating waste processing equipment of the present embodiment, including biological anode chamber 1,
Cathode chamber 2, the connection biological anode chamber 1 and the cathode chamber 2 are connected to bridge 3, and interior be filled with by mass fraction of connection bridge 3 is
The KCl salt matter agar gel that 0.75% KCl solution is mixed with the agar gel for being 4.60% containing agar mass fraction,
Proton to generate anode is transferred to cathode from anode, and proton participates in going back for heavy metal in electroplating wastewater ion in cathode chamber
Original reaction, while preventing oxygen from diffusing to anode from cathode.Biological anode chamber 1 uses anode transition metal base electrode 11, cathode
Room 2 uses cathode transition metal base electrode 21, anode transition metal base electrode 11 be using have the nitrate of copper ion, iron from
The nitrate of son, active carbon nanofibers and graphene nano fiber, using (copper-iron nano-particle)-made of CVD method
(active carbon-graphene nano fiber) electrode, copper nano particles are attached on active carbon nanofibers, and iron nano-particle is attached to
In graphene nano fiber.Cathode transition metal base electrode 21 is using (zinc-cobalt nano-particle)-made of CVD method (carbonization
Silico-carbo nanofiber) electrode, zinc nanoparticles are attached on SiC nano fiber, and cobalt nano-particle is attached to carbon Nanowire
In dimension.
The anode transition metal base electrode 11 of biological anode chamber 1 passes through the external cathode mistake for storing electric appliance 4 and the cathode chamber 2
It crosses the connection of electrode metal substrate 21 and forms closure electrical circuit, outside storage electric appliance 4 is to store biological fuel cell processing electroplating wastewater
Generated electric energy, and the electronics for allowing biological anolyte reaction chamber to generate is transferred to cathode chamber by external electric appliance 4 of storing, to electricity
The reduction reaction of waste electroplating heavy metal ion.Anode transition metal base electrode surface adheres to one layer by the pale bacterium of wheat and large intestine bar
The microorganism blanket 12 that bacterium mixes sets aerator 22 in cathode chamber 2, continuous exposure when for pre-processing in cathode chamber
Gas is that cathode chamber constantly provides the air of purification, peroxide reducing agent is formed, to accelerate the hair of heavy metal ion reduction reaction
It is raw, and then accelerate the removal rate of heavy metal ion.
Embodiment 2
The transition metal base Electrode-biofilm fuel cell electroplating waste processing equipment of the present embodiment, including biological anode chamber 1,
Cathode chamber 2, be connected to the biological anode chamber 1 and the cathode chamber 2 is connected to bridge 3, to the proton that generates anode from anode
It is transferred to cathode, proton participates in the reduction reaction of heavy metal in electroplating wastewater ion in cathode chamber, while preventing oxygen from cathode
Diffuse to anode.
Biological anode chamber 1 uses anode transition metal base electrode 11, and cathode chamber 2 uses cathode transition metal base electrode 21,
Anode transition metal base electrode 11 and cathode transition metal base electrode 21 be using with aluminum ions nitrate, with nickel from
Nitrate, carbon nanotube and the boron carbide nanofiber of son, using (aluminium-nano nickel particles)-(carbon nanometer made of CVD method
Pipe-boron carbide nanofiber) electrode, aluminum nanoparticles are attached on carbon nano tube nano fiber, and nano nickel particles are attached to carbon
Change on boron nanofiber.
The anode transition metal base electrode 11 of biological anode chamber 1 passes through the external cathode mistake for storing electric appliance 4 and the cathode chamber 2
It crosses the connection of electrode metal substrate 21 and forms closure electrical circuit.Anode transition metal base electrode surface have by enterobacter cloacae attachment and
The microorganism blanket 12 of formation sets aerator 22 in cathode chamber 2, and continuous aeration when for pre-processing in cathode chamber is yin
Pole room constantly provides the air of purification, forms peroxide reducing agent, to accelerate the generation of heavy metal ion reduction reaction, in turn
Accelerate the removal rate of heavy metal ion.
Embodiment 3
It is a kind of to be handled using any transition metal base Electrode-biofilm fuel cell electroplating waste processing equipment of embodiment 1-2
The method of electroplating wastewater, comprising the following steps:
One, the anthraquinone -2,6- for being 10 μM by 1.5L anode working electrolyte, the LB broth bouillon of 0.45L and concentration
Sodium disulfonate and 50 μM of anthraquinone-2-sodium are added in biological anode chamber 1, continuously lead to N230min is biological anode chamber
1 provides anaerobic environment, anthraquinone -2,6- sodium disulfonate and the total 0.05L of anthraquinone-2-sodium；By the pale bacterium of wheat and Escherichia coli
Mixed Microbes or enterobacter cloacae be inoculated in the biological anode chamber 1, tame 18 days, it is primary every replacement in 6 days during domestication
Anode working electrolyte；The anode working electrolyte composition of biological anode chamber are as follows: the KCl of NaCl, 2.48mM of 13.00mM,
1.39mM Na2HPO4, 17.50mM KH2PO4, 2.56Mm NH4The CaCl of Cl, 0.01mM2, 1.5mM NaHCO3、
4.00mM CH3COONa；The pH of anode working electrolyte is 7；In LB broth bouillon comprising 26.78mg/L peptone with
And the yeast extract of 26.78mg/L；
Two, the K for being 100mM by 2L concentration3Fe(CN)6Solution is added in cathode chamber 2, is opened aerator 22, is connected
Continuous aeration 48h, until biological fuel cell has a stable 250mV Voltage Feedback；
Three, it is added to electroplating wastewater sludge as anode substrate in the biological anode chamber 1；Using electroplating wastewater as yin
Pole substrate is added in the cathode chamber 2, is adjusted initial pH to 1.5 with 0.5M HCl, is continuously led to N230min provides for cathode chamber
Anaerobic environment；
Four, power switch is opened, electroplating waste processing equipment is started, while carrying out electroplating wastewater and electroplating wastewater sludge
It handles, the Cr in electroplating wastewater6+Concentration is 1000mg/L, keeps biological anode chamber 1 and cathode chamber 2 to work at 30 DEG C, every 3 days
Replace the electroplating wastewater of the primary cathode chamber 2, the electroplating wastewater sludge of the primary biological anode chamber 1 of replacement in every 8 days and
Liquid microelement.
The Cr in electroplating wastewater can be removed using this processing method6+、Ag+、Cu2+、Ni2+、Zn2+。
Using the Cr in diphenyl carbazide spectrophotometry measurement cathode chamber6+Concentration, using atomic absorption spectrphotometry
Meter method measures the Ag in cathode chamber+、Cu2+、Ni2+、Zn2+Concentration and removal rate, used standard are GB 7475-87 and GB
11912-89；Sludge TCOD concentration and its removal rate in biological anode chamber 1 are measured using potassium bichromate method, and use gravimetric method
Measure the sludge total suspended matter TSS concentration of biological anode chamber 1, the removal rate that sludge volatile suspended matter VSS concentration is distinguished with it,
Measuring standard used by sludge TCOD concentration is GB 11914-89.Using voltage digital capture card two input ports and
The two poles of the earth of biological fuel cell are connected, and collect and record the voltage of biological fuel cell generation, calculate the sun of biological fuel cell
Pole coulombic efficiency CE；Linear sweep voltammetry, electrochemical impedance using voltage-stablizer progress to measure real-time open voltage OCP
Spectrum measurement and other electrochemical measurements calculate the maximum energy-density of biological fuel cell, real-time current density and in real time
Open voltage；Using full-automatic specific surface and pore-size distribution analysis-e/or determining biology anode chamber and the indoor transition metal base of cathode
Hole specific surface area, total pore size volume and the pore-size distribution percentage of electrode.As shown in Table 1, Cr6+Degradation peak velocity reaches
It is interior for 24 hours to contain Cr to 106.5mg/L-h6+The degradation of concentration 1000mg/L is to 6mg/L, Cr6+Removal rate be 99.40%, it is raw
Object fuel cell maximum energy-density is 790mW/m2, real-time current density is 2304mA/m2, real-time open voltage OCP is
445mV；The Cr of 48h6+Concentration is down to 3.3mg/L, Cr6+Removal rate be 99.67%, biological fuel cell maximum energy-density
For 822mW/m2, real-time current density is 2500mA/m2, real-time open voltage OCP is 467mV；The Cr of 72h6+Concentration is down to
1.21mg/L Cr6+Removal rate be 99.88%, biological fuel cell maximum energy-density be 834mW/m2, real-time current density
For 2640mA/m2, real-time open voltage OCP is 475mV.
Cr after the 3 different disposal time of one embodiment of table in cathode chamber6+Concentration and electrochemistry index measurement
As shown in Table 2, the Ag before processing+Concentration is 10.29mg/L, and the concentration after handling 72h is 0.28mg/L, removal
Rate is 97.27%；Cu before processing2+Concentration is 105.48mg/L, and the concentration after handling 72h is 0.31mg/L, and removal rate is
99.71%；Ni before processing2+Concentration is 6.17mg/L, and the concentration after handling 72h is 0.25mg/L, removal rate 95.95%；
Zn before processing2+Concentration is 11.34mg/L, and the concentration after handling 72h is 0.35mg/L, removal rate 96.91%.
In two embodiment of table, 3 cathode chamber heavy metal ion initial concentration and processing 72h after concentration
| Ion | Initial concentration | Concentration after processing 72h |
| Ag+ | 10.29mg/L | 0.28mg/L |
| Cu2+ | 105.48mg/L | 0.31mg/L |
| Ni2+ | 6.17mg/L | 0.25mg/L |
| Zn2+ | 11.34mg/L | 0.35mg/L |
As shown in Table 3, anode chamber's sludge TCOD initial concentration was 20650.00mg/L, by 8 days biological fuel cells
Degradation, anode chamber's sludge TCOD concentration are down to 3350.00mg/L, and sludge TCOD degradation rate is 83.78%.Coulombic efficiency (CE) is
50%, this shows that the organic matter that the biological fuel cell of the present embodiment can efficiently use in electroplating wastewater is produced electricity.Sludge
Total suspended matter TSS initial concentration is 11200.00mg/L, and TSS concentration is down to 2724.96mg/L after handling 72h, and TSS removal rate is
75.67%, sludge volatile suspended matter VSS initial concentration is 7384.00mg/L, and VSS concentration is down to after handling 72h
The removal rate of 1346.10mg/L, VSS are 81.77%.
Three embodiment of table 3 anode chamber sludge TCOD, TSS and VSS concentration before and after the processing
| Sludge index | Initial concentration | Concentration after processing 8 days |
| TCOD | 20650.00mg/L | 3350.00mg/L |
| TSS | 11200.00mg/L | 2724.96mg/L |
| VSS | 7384.00mg/L | 1346.10mg/L |
Embodiment 4
The difference of the present embodiment and embodiment 3 is only that does not add 10 μM of two sulphur of anthraquinone -2,6- in biological anode chamber
Sour sodium and 50 μM of anthraquinone-2-sodium only add the anode working electrolyte of 1.5L and the LB broth bouillon of 0.5L,
And using method measurement electroplating wastewater sludge, heavy metal ion, voltage, electrochemistry index and dual chamber similarly to Example 3
Electrode pore structure index.
As shown in Table 4, Cr6+Degradation peak velocity reaches 101.8mg/L-h, interior for 24 hours to contain Cr6+Concentration 1000mg/L's
It degrades to 7.5mg/L, Cr6+Removal rate be 99.25%, biological fuel cell maximum energy-density be 756mW/m2, electric in real time
Current density is 2286mA/m2, real-time open voltage OCP is 437mV；The Cr of 48h6+Concentration is down to 3.8mg/L, Cr6+Removal rate
It is 99.62%, biological fuel cell maximum energy-density is 798mW/m2, real-time current density is 2482mA/m2, open a way in real time
Power OCP is 459mV；The Cr of 72h6+Concentration is down to 1.34mg/L, Cr6+Removal rate be 99.87%, biological fuel cell is most
Big energy density is 812mW/m2, real-time current density is 2596mA/m2, real-time open voltage OCP is 463mV.
Cr after the four different disposal time of table in cathode chamber6+Concentration and electrochemistry index measurement
As shown in Table 5, the Ag before processing+Concentration is 10.29mg/L, and the concentration after handling 72h is 0.35mg/L, removal
Rate is 96.60%；Cu before processing2+Concentration is 105.48mg/L, and the concentration after handling 72h is 0.59mg/L, and removal rate is
99.44%；Ni before processing2+Concentration is 6.17mg/L, and the concentration after handling 72h is 0.37mg/L, removal rate 94.00%；
Zn before processing2+Concentration is 11.34mg/L, and the concentration after handling 72h is 0.42mg/L, removal rate 96.30%.
In five cathode chamber of table heavy metal ion initial concentration and processing 72h after concentration
| Ion | Initial concentration | Concentration after processing 72h |
| Ag+ | 10.29mg/L | 0.35mg/L |
| Cu2+ | 105.48mg/L | 0.59mg/L |
| Ni2+ | 6.17mg/L | 0.37mg/L |
| Zn2+ | 11.34mg/L | 0.42mg/L |
As shown in Table 6, anode chamber's sludge TCOD initial concentration was 20650.00mg/L, by 8 days biological fuel cells
Degradation, anode chamber's sludge TCOD concentration are down to 3169.74mg/L, and sludge TCOD degradation rate is 83.19%.Coulombic efficiency (CE) is
47%, this shows that the organic matter that the biological fuel cell of the present embodiment can efficiently use in electroplating wastewater is produced electricity.Sludge
Total suspended matter TSS initial concentration is 11200.00mg/L, and TSS concentration is down to 2874.32mg/L after handling 72h, and TSS removal rate is
74.34%, sludge volatile suspended matter VSS initial concentration is 7384.00mg/L, and VSS concentration is down to after handling 72h
The removal rate of 1346.10mg/L, VSS are 80.96%.
Table six anode chamber sludge TCOD, TSS and VSS concentration before and after the processing
| Sludge index | Initial concentration | Concentration after processing 8 days |
| TCOD | 20650.00mg/L | 3469.74mg/L |
| TSS | 11200.00mg/L | 2874.32mg/L |
| VSS | 7384.00mg/L | 1405.64mg/L |
Comparative example 1
A kind of method of biological fuel cell electroplating waste processing equipment processing electroplating wastewater of the present embodiment, this comparison
The difference of embodiment and embodiment 3 is only that: biological anode chamber 1 and cathode chamber 2 are all made of the copper nanometer made of CVD method
Copper nano particles described in grain-(active carbon-graphene nano fiber) electrode are attached to active carbon nanofiber surface, and graphene is received
Rice fiber surface adheres to without metal nanoparticle, the described method comprises the following steps:
One, by 1.5L anode working electrolyte, the LB broth bouillon of 0.45L, 0.05L10 μM of two sulphur of anthraquinone -2,6-
Sour sodium and 50 μM of anthraquinone-2-sodium are added in biological anode chamber 1, continuously lead to N230min is that biological anode chamber 1 mentions
For anaerobic environment；The Mixed Microbes or enterobacter cloacae of the pale bacterium of wheat and Escherichia coli are inoculated in the biological anode chamber 1,
Domestication 18 days, every the anode working electrolyte of replacement in 6 days during domestication；The anode working electrolyte composition of biological anode chamber
Are as follows: the Na of KCl, 1.39mM of NaCl, 2.48mM of 13.00mM2HPO4, 17.50mM KH2PO4, 2.56Mm NH4Cl、
The CaCl of 0.01mM2, 1.5mM NaHCO3, 4.00mM CH3COONa；The pH of anode working electrolyte is 7；LB meat soup culture
The yeast extract of peptone and 26.78mg/L in base comprising 26.78mg/L；
Two, the K for being 100mM by 2L concentration3Fe(CN)6Solution is added in cathode chamber 2, is opened aerator 22, is connected
Continuous aeration 48h, until biological fuel cell has a stable 250mV Voltage Feedback；
Three, it is added to electroplating wastewater sludge as anode substrate in the biological anode chamber 1；Using electroplating wastewater as yin
Pole substrate is added in the cathode chamber 2, is adjusted initial pH to 1.5 with 0.5M HCl, is continuously led to N230min provides for cathode chamber
Anaerobic environment；
Four, power switch is opened, electroplating waste processing equipment is started, while carrying out electroplating wastewater and electroplating wastewater sludge
It handles, the Cr in electroplating wastewater6+Concentration is 1000mg/L, keeps biological anode chamber 1 and cathode chamber 2 to work at 30 DEG C, every 3 days
Replace the electroplating wastewater of the primary cathode chamber 2, the electroplating wastewater sludge of the primary biological anode chamber 1 of replacement in every 8 days and
Liquid microelement.
Using embodiment 3 same procedure measurement electroplating wastewater sludge, heavy metal ion, voltage, electrochemistry index and
Dual chamber electrode pore structure index.
Comparative example 2
A kind of anode chamber and cathode chamber are all made of the biological fuel cell electroplating waste processing equipment processing electricity of graphite electrode
The method of waste electroplating, method of this embodiment using the specification embodiment 3 of Chinese patent CN104386826A, operation dual chamber life
Object fuel cell, the environment of operation and the sludge initial concentration of electroplating wastewater are identical with concentration of heavy metal ion, can to have
Electroplating wastewater sludge, heavy metal ion, voltage, electrochemistry index are measured than property, and using the same procedure of the embodiment of the present application 3
And dual chamber electrode pore structure index.
By table seven as it can be seen that the embodiment of the present application 3 is for embodiment 4, due to being added to anthracene in biological anode chamber 1
Any one or more of quinone -2,6- sodium disulfonate, anthraquinone-2-sodium or Nucin electron transfer mediators, energy
It is enough effective to improve electron transfer rate, and then sludge and heavy metal ion in electroplating wastewater are improved compared to embodiment 4
Removal rate, and the electrochemistry index such as improve maximum energy-density；Embodiment 3 and embodiment 4 be not relative to using
It crosses for the comparative example 1 and comparative example 2 of electrode metal substrate in the TCOD removal rate of sludge, TSS removal rate and VSS
Removal rate, heavy metal ion Cr6+、Ag+、Cu2+、Ni2+、Zn2+Removal rate, have in the electrochemistry index after 72h and significantly mention
It rises；Embodiment 3 and embodiment 4 are due to using the transition metal base electrode using CVD method production, such transition metal base electricity
Pole is attached with second nanometer due to being attached with the first nano-metal particle on the first nanofiber on the second nanofiber electrode
Metallic particles, and then there is higher middle porosity and macroporosity, energy relative to comparative example 1 and comparative example 2
The electron transfer rate of transition metal base electrode is enough significantly improved, and then plays and improves going for the indoor heavy metal ion of cathode
Except rate, on the other hand, embodiment 3 and embodiment 4 are only in anode indoor inoculation anaerobism or amphimicrobe, cathode chamber
The high price configuration state of heavy metal ion is made full use of to also play the behaviour of such simplicity biological fuel cell processing electroplating wastewater
Make step, and significantly improves the effect of the removal rate of heavy metal；Embodiment 3 and embodiment 4 are relative to comparative example 2
It says, embodiment 3 and embodiment 4 can be played equally using the biological fuel cell structure with connection bridge 3 and transmit proton simultaneously
It prevents the indoor oxygen of cathode from entering the indoor effect of anode, has given up the use of expensive proton exchange membrane, reduced use
Biological fuel cell handles the production cost of electroplating wastewater and sludge.
The electroplating wastewater processing index of seven embodiment 3-4 of table and comparative example 1-2 compares
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. transition metal base Electrode-biofilm fuel cell electroplating waste processing equipment, including biological anode chamber (1), cathode chamber (2),
It is characterized in that, further including being connected to being connected to bridge (3) for the biological anode chamber (1) and the cathode chamber (2), the biological anode
Room (1) and the cathode chamber (2) use transition metal base electrode (11；21), the anode transition metal of the biological anode chamber (1)
Base electrode (11) connect formation with the cathode transition metal base electrode (21) of the cathode chamber (2) by external storage electric appliance (4) and closes
Close electrical circuit；The transition metal base electrode (11；It 21) is metal nanoparticle composition (5)-nanofiber electrode (6), institute
Metal nanoparticle composition (5) is stated to be made of the first metal nanoparticle (51) and the second metal nanoparticle (52), it is described
Nanofiber electrode (6) is made of the first nanofiber (61) and the second nanofiber (62)；First metal nanoparticle
(51) it is attached on the first nanofiber (61), second metal nanoparticle (52) is attached to the second nanofiber (62)
On；Anode transition metal base electrode (11) surface is covered with one layer of microorganism blanket (12), and the microorganism is that anaerobism is micro-
Biology or amphimicrobe；Aerator (22) are set in the cathode chamber (2).
2. transition metal base Electrode-biofilm fuel cell electroplating waste processing equipment according to claim 1, feature exist
In filled with salt matter agar gel in the connection bridge (3), the salt matter agar gel is 0.5-0.9%'s by mass fraction
KCl solution or NaCl solution are mixed with containing the agar gel that agar mass fraction is 4.5-4.8%.
3. transition metal base Electrode-biofilm fuel cell electroplating waste processing equipment according to claim 1, feature exist
In the microorganism is any one or more of the pale bacterium of wheat, Escherichia coli, enterobacter cloacae, bacillus.
4. transition metal base Electrode-biofilm fuel cell electroplating waste processing equipment according to claim 2 or 3, described
One metal nanoparticle (51) is copper, zinc, aluminium or magnesium, and second metal nanoparticle (52) is iron, cobalt, nickel or cadmium.
5. transition metal base Electrode-biofilm fuel cell electroplating waste processing equipment according to claim 2 or 3, described
One nanofiber (61) is activated carbon fibre, silicon carbide fibre or carbon nanotube, and second nanofiber (62) is graphene
Nanofiber, carbon nano-fiber or boron carbide nanofiber.
6. useless using transition metal base Electrode-biofilm fuel cell electroplating waste processing equipment processing plating described in claim 1
The method of water, which is characterized in that the method follows the steps below:
One, 1.5L anode working electrolyte and LB broth bouillon are added in the biological anode chamber (1), continuously lead to N2
30min provides anaerobic environment for biological anode chamber；By the microbial inoculant in the biological anode chamber (1), tame 18 days,
The primary anode working electrolyte was replaced during domestication every 6 days；
Two, the K for being 100mM by 2L concentration3Fe(CN)6Described interior to cathode chamber (2), unlatching aerator (22) is added in solution, into
Row continuous aeration 48h, until biological fuel cell has a stable 250mV Voltage Feedback；
Three, it is added to electroplating wastewater sludge as anode substrate in the biological anode chamber (1)；Using electroplating wastewater as cathode
Substrate is added in the cathode chamber (2), is adjusted initial pH to 1.5-2 with 0.5M HCl, is continuously led to N230min is cathode chamber
Anaerobic environment is provided；
Four, power switch is opened, the electroplating waste processing equipment is started, while carrying out electroplating wastewater and electroplating wastewater sludge
Processing kept the biological anode chamber (1) and cathode chamber (2) to work between 25 DEG C -35 DEG C, every the 3-4 days primary institutes of replacement
State the electroplating wastewater of cathode chamber (2), the electroplating wastewater sludge of the primary biological anode chamber (1) of replacement in every 5-10 days and micro
Element liquid.
7. the plating according to claim 6 using transition metal base Electrode-biofilm fuel cell electroplating waste processing equipment
Waste water and method for sludge treatment, which is characterized in that the anode working electrolyte composition of the biology anode chamber are as follows: 12.00mM-
The Na of KCl, 1.00mM-2.00mM of NaCl, 2.00mM-3.00mM of 14.00mM2HPO4, 17.00mM-18.00mM
KH2PO4, 2.00mM-3.00Mm NH4The CaCl of Cl, 0.01mM-0.02mM2, 1.00mM-1.50mM NaHCO3、3.00mM-
5.00mM CH3COONa；The pH of the anode working electrolyte is 7.
8. the plating according to claim 6 using transition metal base Electrode-biofilm fuel cell electroplating waste processing equipment
Waste water and method for sludge treatment, which is characterized in that 10 μM -100 μM of anthraquinone -2,6- is additionally added in the biology anode chamber (1)
Sodium disulfonate, anthraquinone-2-sodium or 5- hydroxyl -1,4- naphthoquinones.
9. the plating according to claim 6 using transition metal base Electrode-biofilm fuel cell electroplating waste processing equipment
Waste water and method for sludge treatment, which is characterized in that the Cr in the processing method removal electroplating wastewater6+、Ag+、Cu2+、Ni2+、Zn2 +。
10. the electricity according to claim 9 using transition metal base Electrode-biofilm fuel cell electroplating waste processing equipment
Waste electroplating and method for sludge treatment, which is characterized in that the Cr in the electroplating wastewater6+Concentration is 50-1800mg/L.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113398523A (en) * | 2021-05-12 | 2021-09-17 | 华南理工大学 | FeSxElectrode, preparation method and FeSxDevice and method for fixing Cr (VI) through synergistic microbial mineralization |
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| CN113816501A (en) * | 2021-08-25 | 2021-12-21 | 福建农林大学 | Bio-photoelectrochemical reagent for synchronously realizing plastic degradation and heavy metal reduction and preparation method thereof |
| CN113816501B (en) * | 2021-08-25 | 2022-08-12 | 福建农林大学 | Bio-photoelectrochemical reagent for synchronously realizing plastic degradation and heavy metal reduction and preparation method thereof |
| CN114837877A (en) * | 2022-05-05 | 2022-08-02 | 杭州传一科技有限公司 | Tidal wave monitoring buoy capable of generating power and power generation method |
| CN114890637A (en) * | 2022-05-24 | 2022-08-12 | 龙岩学院 | Method for treating sludge and method for preparing environment-friendly bricks from obtained solid waste sludge |
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