CN108275777A - A kind of cathode catalysis film coupling membraneless microbiological fuel cell is used for coking wastewater processing system - Google Patents
A kind of cathode catalysis film coupling membraneless microbiological fuel cell is used for coking wastewater processing system Download PDFInfo
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- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 51
- 238000004939 coking Methods 0.000 title claims abstract description 42
- 239000002351 wastewater Substances 0.000 title claims abstract description 36
- 239000000446 fuel Substances 0.000 title claims abstract description 30
- 230000002906 microbiologic effect Effects 0.000 title claims abstract description 29
- 230000008878 coupling Effects 0.000 title claims abstract description 20
- 238000010168 coupling process Methods 0.000 title claims abstract description 20
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 20
- 238000012545 processing Methods 0.000 title claims abstract description 13
- 239000012528 membrane Substances 0.000 claims abstract description 44
- 230000003197 catalytic effect Effects 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 244000005700 microbiome Species 0.000 claims abstract description 12
- 230000005611 electricity Effects 0.000 claims abstract description 10
- 238000011049 filling Methods 0.000 claims abstract description 9
- 239000006004 Quartz sand Substances 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000005374 membrane filtration Methods 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical group O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 239000004065 semiconductor Substances 0.000 claims description 6
- 239000002134 carbon nanofiber Substances 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 229910002518 CoFe2O4 Inorganic materials 0.000 claims description 4
- 229910002588 FeOOH Inorganic materials 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000010411 electrocatalyst Substances 0.000 claims description 4
- 230000002572 peristaltic effect Effects 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- 238000005273 aeration Methods 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 229920002301 cellulose acetate Polymers 0.000 claims description 3
- 239000004020 conductor Substances 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 3
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 238000005276 aerator Methods 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- 230000009977 dual effect Effects 0.000 claims description 2
- 239000006260 foam Substances 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000003918 potentiometric titration Methods 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims 1
- 239000005441 aurora Substances 0.000 claims 1
- JRKICGRDRMAZLK-UHFFFAOYSA-N peroxydisulfuric acid Chemical compound OS(=O)(=O)OOS(O)(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-N 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 9
- 238000007254 oxidation reaction Methods 0.000 abstract description 9
- 239000010865 sewage Substances 0.000 abstract description 6
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000000356 contaminant Substances 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000003321 amplification Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000013461 design Methods 0.000 abstract description 2
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 2
- 230000003287 optical effect Effects 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 7
- 238000001914 filtration Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 239000000571 coke Substances 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- 239000003245 coal Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000011112 process operation Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 208000005735 Water intoxication Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000011712 cell development Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
Classifications
-
- 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
- C02F3/005—Combined electrochemical biological processes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46152—Electrodes characterised by the shape or form
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/46115—Electrolytic cell with membranes or diaphragms
-
- 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
- C02F3/28—Anaerobic digestion processes
-
- 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
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Biodiversity & Conservation Biology (AREA)
- Environmental & Geological Engineering (AREA)
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- Health & Medical Sciences (AREA)
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- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Materials Engineering (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention belongs to sewage purification and utilization of wastewater resource technical field, discloses a kind of cathode catalysis film coupling membraneless microbiological fuel cell and be used for coking wastewater processing system.More particularly to anode chamber's electricity-producing microorganism anaerobic oxidation, the effect of cathode catalysis film optical electrical catalytic degradation and membrane filtration is cooperateed with to act on degradation of contaminant, interval and continuous operation mode obtain higher degradation rate, reach the purpose of design of sewage disposal and biology electricity production.The invention has the advantages that improving the effluent quality of tradition MFC；Proton exchange membrane is substituted using quartz sand filling middle layer, reduces cost；Coupled system electric microfield promotes oxidation catalyst filter film service life, catalytic oxidation treatment object difficult to degrade；Reaction system takes up little area, flow is short, high treating effect and energy conservation and environmental protection, is conducive to carry out amplification test and industrialization.
Description
Technical field
The invention belongs to sewage disposals and refractory wastewater and application technology as the second resource field, are related to a kind of new coupling
Close cathode catalysis film, the microbiological fuel cell reactor without amberplex is shown when handling coking wastewater difficult to degrade
Good result.
Background technology
Coking wastewater is a kind of typical hard-degrading high concentrated organic wastewater, is that coal chemical industry is produced in the coke making process stage
Raw waste water, source are more concentrated.China is currently the first in the world coke production state and exported country, and the pollution of coking wastewater is asked
Topic is particularly acute.Coking wastewater complicated component, organic concentration is high, and coloration is high, and toxicity is big, difficult to degrade, to the place of coking wastewater
Reason has become a great problem of water treatment field.It is general to use in order to reach sewage drainage standard of the country to coal chemical industry
Pretreatment, biological treatment and advanced treating tertiary treatment method, traditional coking waste water treatment process flow complexity, treatment effect
It is poor, therefore, it is necessary to design a kind of energy saving, efficient sewage treatment process, realize coking wastewater high-efficiency removal.
Microbiological fuel cell (Microbial Fuel Cell, abbreviation MFC) technology is a kind of collection rapidly developed this year
Biological wastewater treatment and production capacity can not only realize the purified treatment of waste water, moreover it is possible to convert chemical energy in integrated new technology
Electric energy.Under the action of anode microorganism, oxidative degradation pollutant generates proton and electronics simultaneously, and proton passes through proton exchange membrane
Cathode is reached, the electron reduction O of cathode is transmitted to external circuit2Form H2O or H2O2.However, only handled through single MFC
Effluent quality is poor, and it is the bottleneck problem of restriction micro-organisms fuel cell development that the efficiency of processing is low.And membrane separation technique is a kind of
Energy-efficient water technology, due to having the characteristics that under room temperature operation, without phase-state change, without chemical change, adaptable
Be widely used every field.But general micro-filtration or ultrafiltration cannot retain small molecule contaminants, cannot solve water intoxication hardly possible
The removal problem of degradation of contaminant, thus will catalysis, high-level oxidation technology (photocatalysis, electro-catalysis, photoelectrocatalysis, ozone oxidation,
Potentiometric titrations oxidation etc.) it is combined with membrane separation technique, membrane filtration and catalysed oxidn can be cooperateed with to remove pollutant, to
Improve effluent quality.And overcoming membrane pollution problem existing for membrane separation technique, fouling membrane causes in processing procedure under separating effect
The high energy consumption of drop, common film surface cleaning method and aeration method.By combining electric microfield and catalytic action can in this system
Achieve effective control membrane pollution problem.Microbiological fuel cell technology is coupled to actual sewage processing with catalytic membrane, on the one hand,
It solves the problems, such as that microbiological fuel cell effluent quality is poor, fuel cell is on the other hand utilized to generate electric microfield and Membrane catalysis work
With mitigation fouling membrane.The application of microbiological fuel cell technology is limited by the cost of wherein amberplex and electrode, does not use
Amberplex will reduce cost.And electrode and filter membrane are coupled in one, electrode film filtering function is assigned, also reduces
Additional materials and cost.Further supported catalyst helps while producing electricity filtering, to realize urging for Recalcitrant chemicals
Change oxidation, promote treatment effeciency and reduces cost.
A kind of novel cathode catalytic membrane coupling of present invention structure is without amberplex microbiological fuel cell reactor and coke
Change waste water treatment system, handles waste water using anode microbiological anaerobic, (light) electro-catalysis of cathode catalysis film and filtering promote water outlet
Water quality；Respective advantage is made full use of, realizes continuous high-efficient processing；Proton exchange membrane, drop are substituted using quartz sand filling middle layer
Low process operation cost promotes oxidation catalyst filter film service life；And applied to the processing of practical coking wastewater difficult to degrade, reach
Efficient process and energy-efficient purpose.
Invention content
The object of the present invention is to provide a kind of coupling of novel cathode catalytic membrane is anti-without amberplex microbiological fuel cell
It answers device and coking wastewater processing system, solves microbiological fuel cell effluent quality difference and coking wastewater is difficult, technological process
Complicated problem.
Technical scheme of the present invention：
A kind of cathode catalysis film coupling membraneless microbiological fuel cell is used for coking wastewater processing system, including reactor,
Aerator and computer data acquisition system；The reactor is dual chamber, and cathode chamber is arranged aeration head and exposes air, and cathode is to urge
Change membrane electrode；Medial compartment between two Room for quartz sand filling replaces proton exchange membrane；Load is placed in anode chamber has electricity production micro-
The active carbon particle of biology, compactedness 75-85%, carbon-point are that conductive anode is inserted into active carbon particle, and top is closed, has into water
Mouthful；Connect external resistance between anode and cathode, resistance value is 1-1200 Ω, and external resistance connects data collecting system, and record generates voltage；Cathode
Water pump is connected outside catalysis membrane electrode, by being discharged after cathode catalysis membrane filtration.
The preparation method of the cathode catalysis film, steps are as follows：
The cathode catalysis film is electro-catalysis membrane or photoelectrocatalysis film, and the catalysis material in cathode catalysis film is and anode
There are the semi-conducting material of fermi level difference or with the material of electro catalytic activity；It need to select conductive substrates or conductive by adding
Material increases the electric conductivity of electrode, realizes electron transmission；Catalysis material is flat in being prepared in substrate with filmogen mixing knifing
Plate film, directly by catalysis material growth in situ in substrate, or addition adhesive coated obtains cathode and urges in the first-class mode of substrate
Change film.
The cathode catalysis film conductive substrates are stainless (steel) wire, carbon cloth, nickel foam or carbon felt；Add conductive material
For carbon nano-fiber, carbon nanotube, graphene or iron powder etc., filmogen is Kynoar, cellulose acetate etc.；
Elctro-catalyst in the cathode electrocatalyst film is MnO2、CoFe2O4Or FeOOH.
Semiconductor catalyst in the cathode luminous catalytic membrane is TiO2、g-C3N4, SiC or WO3, cathode chamber external demand
Add ultraviolet or visible light source.
The cathode chamber can add persulfate or peroxydisulfate is a concentration of (10-200mg/L), promote sulfate radical certainly
It is generated by base, auxiliary cathode (light) electrocatalysis.
Above-mentioned reactor assembly is used for actual treatment coking wastewater：The system handles practical coking wastewater COD ranging from
200-2500mg/L, the laggard water process of anode microorganism is tamed before starting reactor by diluting coking wastewater, and cathodic coating is logical
Peristaltic pump driving filtering is crossed, operational mode is intermittent or continous way, continuous hydraulic residence time 6h-48h.
Beneficial effects of the present invention：The membraneless microbiological fuel cell system handles waste water using anode microbiological anaerobic,
It cooperates with cathode catalysis film (light) electrocatalysis and circulating filtration to handle coking wastewater difficult to degrade, makes full use of respective advantage,
It solves the problems, such as that traditional MFC organic matters decomposition efficiency is low, promotes the effluent quality of MFC；It is replaced using quartz sand filling middle layer
For proton exchange membrane, process operation cost is reduced；Coupled system electric microfield promotes oxidation catalyst filter film service life；The reaction system
Take up little area, flow is short, high treating effect and energy conservation and environmental protection, be conducive to carry out amplification and pilot experiment, to promote the industry of achievement
Change
Description of the drawings
A kind of membraneless microbiological fuel cells of Fig. 1 couple cathode catalysis membranous system figure.
Fig. 2 low concentrations coking wastewater TiO under the different disposal time2/ pvdf membrane is discharged COD removal rates, abscissa in figure
For time (unit：Hour), ordinate is COD removal rates.
Fig. 3 high concentration cokings TiO under the different disposal time2/ pvdf membrane is discharged COD removal rates, abscissa in figure
For time (unit：Hour), ordinate is COD removal rates.
Fig. 4 high concentration cokings TiO under the different disposal time2/ pvdf membrane makees cathod system potential energy diagram, horizontal seat in figure
It is designated as time (unit：Minute), ordinate is potential.
Specific implementation mode
Below in conjunction with attached drawing and technical solution, the specific implementation mode that further illustrates the present invention.
Embodiment 1
(1) cathode TiO2The preparation of/PVDF catalytic membranes：By TiO2The addition of (15wt%) and carbon nano-fiber (25wt%) exists
In PVDF (10wt%) DMF casting solutions, after 6h is stirred, ultrasonic deaeration 30min, using carbon nano-fiber cloth as substrate, coating
Thickness is 300 μm, and TiO is obtained after inversion of phases 12h2/ PVDF catalytic membrane cathodes.
(2) membraneless microbiological fuel cell coupling cathode catalysis membranous system processing low concentration coking wastewater operation：Anode chamber
It is that conductive anode is inserted into active carbon particle that middle filling load, which has the active carbon particle (compactedness 85%) of electricity-producing microorganism, carbon-point,
In, the closed low concentration coking wastewater in top (COD about 200mg/L)；Medial compartment between two Room for quartz sand filling replaces proton
Exchange membrane；By above-mentioned catalytic membrane loaded on (two-sided) in rectangle membrane module, cathode chamber bottom is exposed into air, provides oxygen for electronics
Activating oxygen generates free radicals；By pumping cathode membrane module top-end water-outlet, connected by 1000 Ω external resistances between anode and cathode
It connects.Dilution ratio is 100%, 50% to practical coking wastewater successively, 0% domestication anode microorganism.When anode microorganism electricity generation is steady
After fixed, low concentration coking wastewater, hydraulic detention time 48h are continuously pumped by peristaltic pump.At interval of 12h respectively by pumping from
Water sample is taken out above cathode membrane module, and water outlet COD removal rates are measured using potassium dichromate method.As shown in Fig. 2, low concentration wastewater is straight
It connects and couples cathodic coating electrocatalysis by anode microbial action, operation 12h reaches 90% removal rate, and cathode chamber water outlet is final
COD removal rates are up to 99%.
Embodiment 2
(1) cathode TiO2The preparation of/PVDF catalytic membranes：Described in case study on implementation 1.
(2) membraneless microbiological fuel cell coupling cathode catalysis membranous system processing high concentration coking operation：Anode chamber
It is that conductive anode is inserted into active carbon particle that middle filling load, which has the active carbon particle (compactedness 85%) of electricity-producing microorganism, carbon-point,
In, the closed low concentration coking wastewater in top (COD about 2000mg/L)；Medial compartment between two Room for quartz sand filling replaces proton
Exchange membrane；By above-mentioned catalytic cathode film loaded on (two-sided) in rectangle membrane module, cathode chamber bottom exposes into air, provides oxygen and be used for
Electronic activation oxygen generates free radicals；By pumping cathode membrane module top-end water-outlet, pass through 1000 Ω dispatches from foreign news agency between anode and cathode
Resistance connection.Dilution ratio is 100%, 50% to practical coking wastewater successively, 0% domestication anode microorganism.When anode microorganism produces
After electricity is stablized, low concentration coking wastewater, hydraulic detention time 48h are continuously pumped by peristaltic pump.Pass through pump respectively at interval of 12h
It inhales and takes out water above cathode membrane module, water outlet COD removal rates are measured using potassium dichromate method.As shown in figure 3, cathode chamber is discharged
COD removal rates are about 75% up to removal rate after 80%, 80h after 48h.System electricity production situation is as shown in figure 4, rise under this condition
The preceding 5h cell voltage potentials of beginning cell voltage potential about 0.45v, system operation are steady after reduction with the raising of cathode chamber contaminant degradation rate
It is fixed.
Claims (10)
1. a kind of cathode catalysis film coupling membraneless microbiological fuel cell is used for coking wastewater processing system, which is characterized in that institute
The cathode catalysis film coupling membraneless microbiological fuel cell and coking wastewater processing system stated include reactor, aerator and meter
Calculation machine data collecting system；The reactor is dual chamber, and cathode chamber is arranged aeration head and exposes air, and cathode is catalysis membrane electrode；Two
Medial compartment between room for quartz sand filling replaces proton exchange membrane；Load is placed in anode chamber the activated carbon of electricity-producing microorganism
Particle, compactedness 75-85%, carbon-point are that conductive anode is inserted into active carbon particle, and top is closed, there is water inlet；Anode and cathode it
Between connect external resistance, resistance value is 1-1200 Ω, and external resistance connects data collecting system, and record generates voltage；Cathode catalysis membrane electrode
Water pump is connected outside, by being discharged after cathode catalysis membrane filtration.
2. cathode catalysis film coupling membraneless microbiological fuel cell according to claim 1 is used for Treatment of Coking Effluent system
System, which is characterized in that the preparation method of the cathode catalysis film, steps are as follows：
The cathode catalysis film is electro-catalysis membrane or photoelectrocatalysis film, and the catalysis material in cathode catalysis film is existed with anode
The semi-conducting material of fermi level difference or the material with electro catalytic activity；By selecting conductive substrates or by adding conduction material
Material increases the electric conductivity of electrode, realizes electron transmission；By catalysis material and filmogen mixing knifing in preparing tablet in substrate
Film, directly by catalysis material growth in situ in substrate, or addition adhesive coated is in substrate, obtaining cathode catalysis film.
3. cathode catalysis film coupling membraneless microbiological fuel cell according to claim 1 or 2 is used for Treatment of Coking Effluent
System, which is characterized in that the cathode catalysis film conductive substrates are stainless (steel) wire, carbon cloth, nickel foam or carbon felt.
4. cathode catalysis film coupling membraneless microbiological fuel cell according to claim 1 or 2 is used for Treatment of Coking Effluent
System, which is characterized in that the conductive material be carbon nano-fiber, carbon nanotube, graphene or iron powder, it is described at membrane material
Material is Kynoar or cellulose acetate.
5. cathode catalysis film coupling membraneless microbiological fuel cell according to claim 3 is used for Treatment of Coking Effluent system
System, which is characterized in that the conductive material is carbon nano-fiber, carbon nanotube, graphene or iron powder, the filmogen
For Kynoar or cellulose acetate.
6. the cathode catalysis film coupling membraneless microbiological fuel cell according to claim 1,2 or 5 is at coking wastewater
Reason system, which is characterized in that the elctro-catalyst in the cathode electrocatalyst film is MnO2、CoFe2O4Or FeOOH；Described the moon
Semiconductor catalyst in aurora electro-catalysis membrane is TiO2、g-C3N4, SiC or WO3, ultraviolet or visible light light is added outside cathode chamber
Source.
7. cathode catalysis film coupling membraneless microbiological fuel cell according to claim 3 is used for Treatment of Coking Effluent system
System, which is characterized in that the elctro-catalyst in the cathode electrocatalyst film is MnO2、CoFe2O4Or FeOOH；The cathode light
Semiconductor catalyst in electro-catalysis membrane is TiO2、g-C3N4, SiC or WO3, ultraviolet or visible light source is added outside cathode chamber.
8. cathode catalysis film coupling membraneless microbiological fuel cell according to claim 4 is used for Treatment of Coking Effluent system
System, which is characterized in that the elctro-catalyst in the cathode electrocatalyst film is MnO2、CoFe2O4Or FeOOH；The cathode light
Semiconductor catalyst in electro-catalysis membrane is TiO2、g-C3N4, SiC or WO3, ultraviolet or visible light source is added outside cathode chamber.
9. the cathode catalysis film coupling membraneless microbiological fuel cell according to claim 1,2,5,7 or 8 is useless for coking
Water treatment system, which is characterized in that the persulfate or peroxy-disulfuric acid of a concentration of 10-200mg/L are added in the cathode chamber
Salt promotes potentiometric titrations to generate, auxiliary cathode catalytic action.
10. cathode catalysis film coupling membraneless microbiological fuel cell according to claim 9 is used for Treatment of Coking Effluent system
System, which is characterized in that the COD of the coking wastewater is 200-2500mg/L, useless by diluting coking before starting reactor
Water tames the laggard water process of anode microorganism, and cathodic coating is driven by peristaltic pump and filtered, and operational mode is intermittent or continous way,
Continuous hydraulic residence time 6h-48h.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
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| CN201810211965.3A CN108275777A (en) | 2018-03-06 | 2018-03-06 | A kind of cathode catalysis film coupling membraneless microbiological fuel cell is used for coking wastewater processing system |
| PCT/CN2018/091909 WO2019169785A1 (en) | 2018-03-06 | 2018-06-20 | Use of membrane-free microbial fuel cell coupled with cathode catalytic membrane in coking wastewater treatment system |
| ZA2020/05265A ZA202005265B (en) | 2018-03-06 | 2020-08-24 | Membrane-free microbial fuel cell combined catalytic membrane cathode system for coking wastewater treatment |
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| CN201810211965.3A CN108275777A (en) | 2018-03-06 | 2018-03-06 | A kind of cathode catalysis film coupling membraneless microbiological fuel cell is used for coking wastewater processing system |
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| ZA202005265B (en) | 2020-10-28 |
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