CN106745676A - A kind of ecological many negative electrode urine processing devices and method - Google Patents

A kind of ecological many negative electrode urine processing devices and method Download PDF

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Publication number
CN106745676A
CN106745676A CN201611057812.5A CN201611057812A CN106745676A CN 106745676 A CN106745676 A CN 106745676A CN 201611057812 A CN201611057812 A CN 201611057812A CN 106745676 A CN106745676 A CN 106745676A
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electrode
urine
sludge
cathode
pericarp
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CN106745676B (en
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应贤斌
冯华军
顾源
程坤
沈东升
周广澜
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Zhejiang Gongshang University
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Zhejiang Gongshang University
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/005Combined electrochemical biological processes
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/02Hydrogen or oxygen
    • C25B1/04Hydrogen or oxygen by electrolysis of water
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/50Processes
    • C25B1/55Photoelectrolysis
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/16Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/005Black water originating from toilets
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00Apparatus for treatment of water, waste water or sewage
    • C02F2201/009Apparatus with independent power supply, e.g. solar cells, windpower, fuel cells
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00Controlling or monitoring parameters in water treatment
    • C02F2209/08Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00Controlling or monitoring parameters in water treatment
    • C02F2209/14NH3-N
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00Specific treatment goals
    • C02F2303/10Energy recovery
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/36Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00Technologies for wastewater treatment
    • Y02W10/30Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37Wastewater or sewage treatment systems using renewable energies using solar energy

Abstract

The invention discloses the ecological many negative electrode urine processing devices of one kind and method, device includes three Room reactors, storage urine pot, ammonia tourie and hydrogen container, pericarp electrode is set in anode chamber, sludge electrode is set in cathode chamber, it is connected with pericarp electrode after two sludge electrode parallel connections, the branch road of each sludge electrode is provided with a photovoltaic battery panel connected with sludge electrode;Air cathode is covered with the side that cathode chamber is not connected with anode chamber, is connected with pericarp electrode after all air cathode parallel connections.The present invention can not only efficiently remove the COD in the middle of urine, moreover it is possible to reclaim the resources such as ammonia nitrogen, hydrogen, and the processing method puts into without external energy, non-secondary pollution, be a kind of concept type urine processing device and method for meeting environment-friendly and sustainable development.

Description

A kind of ecological many negative electrode urine processing devices and method
Technical field
The present invention relates to urine process reactor development and water-treatment technology field, a kind of ecological many negative electrode urine are specifically referred to Liquid processing device and method.
Background technology
Environmental protection and energy shortage are two hang-ups that the world faces now.China is in and will be chronically at industry In change, the urbanization process fast-developing stage, the development of its rough type and the random construction of drainage system are caused at waste water Bottleneck problem of the reason as China's environmental improvement.
In conventional waste water processing procedure, waste water treatment plant puts into substantial amounts of energy to remove and reclaim nutrient (nitrogen And phosphorus).Wherein, nitrogen-containing compound is removed by changing into inert nitrogen;And phosphorus then it is many with precipitation forms such as phosphate from being Body weight spins off.However, about 80% nitrogen, 50% phosphorus and 10% COD are derived from the mankind's in sanitary sewage Urine, and these urines only account for the 1% of sanitary sewage cumulative volume.If by organic matter (COD), nitrogen, phosphorus in sanitary sewage Etc. poor energy and resource recycling, wastewater treatment load can not only be greatly reduced, reduce processing cost, moreover it is possible to recover energy And resource, environmental protection and energy sustainable development are all significant
Microbiological fuel cell (Microbial fuel cells, MFCs) and microorganism electrolysis cell (Microbial Electrolysis cells, MECs) it is emerging bioelectrochemistry technology, clean energy resource can be reclaimed while waste water is processed And resource.Such technology by be carried on anode surface electricity production bacterium (Exoelectrogen) degradation of organic substances or electronics, and By electron medium or nm-class conducting wire by electron transmission to anode, electronics is by external circuitses generation electric energy, and wherein MECs Then negative electrode can be made to produce hydrogen under additional power source effect.Such technology has the dirty efficiency high of drop, consume energy small, non-secondary pollution and The features such as reclaiming clean energy resource, meets environment-friendly and sustainable development theory.
Patent CN201110029516.5 provides a kind of urine and is processed above by nitrifying microorganisms for 10 times in dilution, then The removal of nitrogen is realized in the presence of microorganism in denitrification reactor.The method is a kind of power consumption purification method, after Macrodilution The total amount of pollutant entered in sewage be increased and No Assets are reclaimed.
Patent CN201210128854.9 provides a kind of by adding by the limonite of specially treated, in externally-applied magnetic field In the presence of obtain magnetic organic composite nanometer denitrogenation material, the method only only accounts for how avoiding the secondary pollution of ammonia nitrogen, There is no good Resource recovery.In existing urine wastewater processing technology, without more ripe technical scheme.
Patent CN201210131068.4 discloses a kind of membrane bioreactor and sewage-treatment plant group combined system.Should The high electric field processing cost that the technique that system solves existing utilization additional electric field control fouling membrane is present is high, suppresses microorganism and lives Property, the problem of Treatment of Sludge.However, the system has used the metal building materials such as titanium silk, stainless steel as electrode material, there is cost Height, cathode consumption agent increases cost input the shortcomings of perishable, and needed for such reactor.
Therefore, using advanced bioelectrochemistry technology, a kind of low energy consumption, high efficiency are developed and the money such as ammonia nitrogen can be reclaimed The apparatus and method in source are necessary.
The content of the invention
The invention provides the ecological many negative electrode urine processing devices of one kind and method, the device can not only efficiently remove urine Central COD, moreover it is possible to reclaim the resources such as ammonia nitrogen, hydrogen, and the processing method puts into without external energy, non-secondary pollution is A kind of concept type urine processing device and method for meeting environment-friendly and sustainable development.
A kind of ecological many negative electrode urine processing devices, including three Room reactors, storage urine pot, ammonia tourie and hydrogen container, Three Room reactor includes being located at middle anode chamber and the cathode chamber positioned at anode chamber both sides, anode chamber and two cathode chambers Between separated by cation-exchange membrane, the anode chamber is provided with urine import and export, and the gas vent of the cathode chamber is sequentially connected Ammonia tourie and hydrogen container;
Set in the anode chamber and sludge electrode is set in pericarp electrode, the cathode chamber, after two sludge electrode parallel connections Connected with pericarp electrode, the branch road of each sludge electrode is provided with a photovoltaic battery panel connected with sludge electrode;
Air cathode is covered with all sides that the cathode chamber is not connected with anode chamber, the air cathode inner side is negative Carry anion-exchange membrane to be spaced with solution, connected with pericarp electrode after all air cathode parallel connections.
All air cathodes are in parallel with sludge negative electrode, i.e., an anode, all of the moon are set in device of the invention Extremely separate and whole parallel connection, and be connected with anode after company.
By wired in series photovoltaic battery panel between carbonization pericarp anode and sludge negative electrode, additional electric is provided for negative electrode produces hydrogen Pressure.
Reactor of the invention is followed successively by left room, medial compartment and right ventricle along its length, between left and right room and medial compartment by Cationic membrane separates, and is connected by conductor in parallel between all air cathodes and sludge electrode, is connected with pericarp electrode after parallel connection Under night non-illuminated conditions, anode produces electricity bacterium and produces electronics by the COD that degrades and lift NH4 +Concentration, oxygen is cloudy by air What pole received that anode passes over is electronically generated OH-, OH-Diffuse to cathode chamber and NH4 +Reaction generation NH3Gas overflowing, by dilute Acid solution reclaims NH3, urine tentatively pre-processed;Connected and gone here and there by wire between carbonization pericarp anode and activated sludge negative electrode Connection one piece of photovoltaic battery panel of connection, in the case where having illumination condition daytime, photovoltaic battery panel is produced when producing voltage accumulation urine process Voltage, urine electrolysis liberation of hydrogen after processing cathode chamber, hydrogen reclaims by hydrogen storage gas tank, while through tentatively pretreated urine Liquid is strengthened treatment.The method reaches not only efficient process urine on the basis of without additional energy consumption but also reclaims clean energy resource hydrogen The purpose of gas and ammonia nitrogen resource.
Preferably, air cathode is covered with all sides not being connected with anode chamber of the cathode chamber, each air Lateral load anion-exchange membrane in negative electrode.It is further preferred that the cathode chamber has 6 faces, wherein not being connected with anode chamber Five faces on be respectively provided with air cathode.
It is preferred that, the pericarp electrode is prepared by the following method:
(1) by discarded pericarp excision forming, 20~30h is air-dried under natural conditions;
(2) 60~90 DEG C of 0.5~2h of drying under nitrogen atmosphere of the pericarp after air-drying are cut;
(3) under nitrogen atmosphere, 800~1000 DEG C of temperature is controlled, pericarp is carbonized, be carbonized after finishing under nitrogen atmosphere Room temperature is naturally cooled to, it is standby.
It is further preferred that preparing by the following method:
(1) by discarded pericarp excision forming, 24h is air-dried under natural conditions;
(2) cut pericarp after air-drying and dry 1h for 80 DEG C under nitrogen atmosphere;
(3) under nitrogen atmosphere, 900 DEG C of temperature is controlled, pericarp is carbonized, carbonization is naturally cold under nitrogen atmosphere after finishing But it is standby to room temperature.
Preferably, the discarded pericarp is including watermelon peel, pomelo peel, stalk etc. and not within the above range possibly as sun The pericarp and agricultural wastes of pole.Further preferably, the pericarp anode is carbonization pomelo peel, and material quantity is big, in sea after carbonization Continuous shape, hole is more, with good electric conductivity, is derived beneficial to microorganism colonization and electronics.
Preferably, the sludge electrode is carbonization sludge electrode, is prepared by the following method:
(1) sludge in an oven 40~60 DEG C drying 1~3h after carry out Mechanical Crushing;
(2) sludge after crushing crosses 80~120 eye mesh screens, the bulky grain thing in removal sludge;
(3) sludge after filtering is mixed with the hydrogen peroxide hydrogen peroxide for accounting for sludge quality 5~20%, prepares initial electrode;
(4) initial electrode is sintered under nitrogen atmosphere, controls 800~1200 DEG C of temperature, continues 1~3h, after heating is finished Room temperature is naturally cooled under nitrogen atmosphere.
It is further preferred that the sludge electrode is prepared by the following method:
(1) sludge in an oven 50 DEG C drying 2h after carry out Mechanical Crushing;
(2) sludge uses 100 mesh sieve net filtrations, the bulky grain thing in removal sludge after crushing;
(3) sludge mixes with hydrogen peroxide after filtering, and prepares initial electrode;
(4) sinter under nitrogen atmosphere, control 1000 DEG C of temperature, continue 2h, heating is natural under nitrogen atmosphere after finishing It is cooled to room temperature.
Preferably, the sludge may be made within the above range including excess sludge, municipal sludge, agriculture waste etc. and not Sludge, excrement for anode.More preferably sewage plant excess sludge electrode, raw material is huge, and sludge components are complicated, after carbonization With good electric conductivity and catalytic performance, stable, non-secondary pollution.
In the present invention preferably, pericarp electrode used and sludge electrode are original electrode of the invention, and pericarp electrode has High-specific surface area and good conductance can improve electricity generation performance, while heavy metal, active function groups in sludge electrode etc. is urged Change effect promoting cathodic reduction performance, pericarp electrode and the collaboration of sludge electrode are used, and combination among the strong ones is reached at low-energy-consumption high-efficiency Manage the purpose of urine waste water.
Preferably, air cathode material is platinum-carrying carbon cloth, carbon paper or prepares electrode certainly.It is more preferably electric from preparing Pole, the electrode is formed and is fabricated to compared to platinum-carrying carbon cloth or carbon paper by the ventilative tunica albuginea of waterproof, catalysis black film, stainless (steel) wire compacting This is low, while three-dimensional structure can provide a large amount of oxygen reduction interfaces, reduces loss of the water by negative electrode.
Preferably, air cathode preparation method is as follows:
(1) activated carbon, acetylene black and polytetrafluoroethylene (PTFE) (PTFE) press 3:(3~4):(3~4) mass ratio mixes after stainless The film that thickness is 0.2~0.3mm is pressed on steel mesh;
(2) catalyst such as Ag are carried on reducing process the film surface obtained by step (1);
(3) sodium sulphate and PTFE press (3~4):Suppressed on the electrode obtained by step (2) after the mixing of (6~7) mass ratio;
(4) anion-exchange membrane processes 3min under the conditions of 140 DEG C and 1780kPa, is directly hot-pressed onto step (3) obtained Obtained final product on negative electrode.
The catalyst is Ag etc., and the reducing process is:In 0.1M AgNO3In solution, with silver electrode as anode, step (1) the wherein one side of gained negative electrode is negative electrode, the reduction of 5~6V potential electrolysis.
The application of air cathode can solve the problem that because increasing the technical finesse cost using cathode consumption agent;But specially in the past Many of the device air cathode in face of use one in profit so that negative electrode turns into system rate-limiting step.Device in the present invention, uses Two-way multiaspect air cathode parallel combination, solve it turns into the rate-limiting step of wastewater treatment and energy recovery because area is limited Problem, Method And Principle is simple but significant.
The anode chamber and cathode chamber (single) volume ratio are 1:0.2~1:2.
The cathode chamber carries gas vent, and gas vent is sequentially connected ammonia tourie and hydrogen container, and mixed gas are led to When crossing ammonia tourie, the absorbing liquid in tourie absorbs ammonia, and hydrogen goes successively to be stored in hydrogen container.
The present invention also provides a kind of method for processing urine using ecological many negative electrode urine processing devices, including as follows Step:
(1) anode chamber's inoculation bacterium solution, normal temperature anaerobic fermentation is continuously introduced into 8~12 days (preferably after success biofilm to anode chamber 10 days) urine, electrolyte is contained in cathode chamber;
(2) under non-illuminated conditions, anode produces electricity bacterium and produces electronics by the COD that degrades and lift NH4 +Concentration, oxygen passes through What air cathode received that anode passes over is electronically generated OH-, OH-Diffuse to cathode chamber and NH4 +Reaction generation NH3Gas overflowing, NH is reclaimed by dilute acid soln3;Urine in anode chamber after preliminary treatment is kept in after deriving;
(3) optical condition starts photovoltaic battery panel, there is provided the voltage of stabilization, through the urine after step (2) preliminary treatment It is continuously introduced into anode chamber again, anode produces electricity bacterium and obtains electronics by organic matter of degrading, and gives sludge negative electrode by electron transmission, Voltage, H in cathode chamber electrolyte are provided+Obtain electron reduction into H2, derived into hydrogen container from cathode chamber;
(4) urine after thoroughly being purified through anode chamber is derived by drainpipe, and a portion is used as the electrolyte of cathode chamber.
Directly using the urine after being purified through the inventive method as catholyte in the present invention, after treatment terminates, Urine in cathode chamber as electrolyte is discharged by drainpipe.
Preferably, the voltage that photovoltaic battery panel is provided is 0.7~1.0V.
Preferably, reactor is started under normal temperature condition (20~40 DEG C) after unlatching photovoltaic battery panel.
Preferably, the bacterium solution by organic wastewater that COD concentration is 4000~6000mg/L with electricity production bacterium solution with volume ratio (3~5):1 composition.
Further, the bacterium solution is 5000mg/L organic wastewaters by COD concentration and produces electricity bacterium solution with volume ratio 1:4 groups Into.
Electricity production bacterium used of the invention is conventional electricity production bacterium, such as Geobacteraceae species and Shewanella Species etc.
Preferably, anode chamber enters uroflow amount and goes out uroflow amount for 0.1~0.5m3/(m3D), it is considered to COD removal efficiency and Removal effect, more preferably 0.3m3/(m3·d)。
It is further preferred that increasing device startup stage before step (1):Negative electrode adds M9 electrolyte, and anode chamber connects Bacterium solution is planted, bacterium solution is by the waste water mixed liquor containing 5000mg/L organic matters and electricity production bacterium solution 1:4 (volume ratios) are constituted, and open photovoltaic Cell panel, starts reactor under the conditions of 30 DEG C, start about 1~7 day time;
Startup stage makees the electrolyte of cathode chamber with M9 electrolyte, after thoroughly being purified in the process of the present invention in normal operation Urine is used as cathode chamber electrolyte.
After plant running stabilization, by urine with 0.3m3/(m3D) flow is continuously introduced into twice in period day and night two Anode chamber, microorganism obtains sufficient carbon source on anode electrode, and COD is effectively degraded;Cathode chamber regularly replaces electricity according to pH value Solution liquid (urine after processing).Anode electrode of the present invention, using carbonization pericarp electrode, is raw material using pericarp in house refuse, The anode of high-specific surface area, high conductivity, bio-compatibility high is obtained through a series for the treatment of;Cathode electrode is remaining using Sewage Plant Sludge, activated sludge negative electrode is obtained through a series for the treatment of, is turned waste into wealth.
The present invention produces electronics, night using the COD being carried in the electroactive microbial degradation organic wastewater of anode surface Under late non-illuminated conditions, urine is continuously introduced into anode chamber, and the urine after processing completely sends into cathode chamber, anode as electrolyte Electricity production bacterium produces electronics and lifts NH by the COD that degrades4 +Concentration, oxygen receives the electronics that anode is passed over by air cathode Generation OH-, OH-Diffuse to cathode chamber and NH4 +Reaction generation NH3Gas overflowing, urine is tentatively pre-processed;In daylight Under the conditions of, preliminary treatment urine is continuously introduced into anode chamber again, and air cathode persistently plays a role, and electronics is derived through external circuit and produced The voltage of raw 0.3~0.6V, photovoltaic battery panel is additionally provided 0.7~1.0V voltages under illumination condition, and electrolysis catholyte chamber is complete Urine after treatment obtains H2, further lifted and improve cathode chamber basicity, more NH3Gas overflowing, is washed by dilute acid soln Reclaim NH3, H2Reclaimed by hydrogen container, urine has been fully processed.Urine after processing completely can make as catholyte With.
The present invention combines both emerging bioelectrochemistry technologies of MFCs and MECs, using principles such as ion diffusions, at place Clean energy resource and precious resources are obtained while reason urine, meets environment-friendly and sustainable development theory;More meaning It is that package unit low in input cost turns waste into wealth the solid waste such as pericarp, excess sludge, reaches the work(of pollution treatment of having given up Effect, has much novelty.
The present invention uses solid waste on electrode material, and anode material and cathode material are respectively by waste and old pericarp, surplus Prepared by remaining sludge, reach with the purpose of pollution treatment of giving up.In handling process, present invention coupling MECs and MFCs systems are in three Room reactors Integration is realized, Resource recovery NH while treatment urine3With clean energy resource H2
Compared with prior art, the present invention has the effect that:
(1) negative electrode locular wall uses air cathode, realizes the O in air2It is direct electron acceptor, without cathode consumption agent, Greatly reduce cost input;
(2) be carbonized a photovoltaic battery panel of being connected between pericarp anode and carbonization sludge negative electrode, under sunlight conditions, processes urine H is obtained simultaneously2
(3) anode chamber's inner anode material, cathode chamber inner cathode material are respectively adopted carbonization pericarp and excess sludge, mitigate rubbish Rubbish processes load, while solve surplus sludge volume greatly, the environmental problem such as difficult;
(4) device coupling MECs and MFCs systems, the COD in the middle of efficient process urine, and reclaim ammonia nitrogen and H2
Brief description of the drawings
Fig. 1 is the structural representation of reactor of the present invention.
Fig. 2 is the structural representation of cathode chamber of the present invention.
Fig. 3 is the connection diagram between electrode of the present invention.
1- hydrogen container 2- ammonia tourie 3- cathode chambers
4- air cathode 5- sludge electrode 6- cation-exchange membranes
7- pericarp electrode 8- photovoltaic battery panel 9- anode chambers
10- anode compartment outlet 11- Anode chamber inlets 12- storage urine pots
13- anion-exchange membrane 14- light sources.
Specific embodiment
As depicted in figs. 1 and 2, a kind of ecological many negative electrode urine processing devices, including three Room reactors, storage urine pot 12, ammonia Aspiration closed cans 2 and hydrogen container 1, three Room reactors are rectangular reactor according, internal along its length by 6 points of cation-exchange membrane Three Room are divided into, medial compartment is anode chamber 9, and anode chamber both sides are cathode chamber 3.
Anode chamber carries urine import 11 and urine outlet 10, and urine import connection storage urine pot 12, storage urine pot is used to store Crude urine liquid, the cathode chamber of both sides carries gas vent, and gas vent is sequentially connected ammonia tourie 2 and hydrogen container 1.
Pericarp electrode 7 is set in anode chamber;Cathode chamber carries and sludge is set in electrolyte inlet and waste liquid outlet, cathode chamber Electrode 5, on 5 sides that cathode chamber is not connected with anode chamber respectively set one piece of air cathode of circle 4, air cathode outside with Air contact, interior lateral load anion-exchange membrane 13 separates with negative electrode indoor liquid, and the exploded view of cathode chamber is as shown in Figure 2.
Connected mode between pericarp electrode and sludge electrode and air cathode is as shown in Figure 3 (for accompanying drawing in wherein Fig. 1 Clear not drawn according to actual connected mode, connected mode is defined in Fig. 3), with pericarp electricity after two sludge electrode parallel connections Pole is connected, 8,10 pieces of air cathodes of photovoltaic battery panel of being connected on the branch road of each sludge electrode it is in parallel and with sludge electrode it Between also connect with pericarp electrode after parallel connection, i.e., pericarp electrode is anode, mutual between two sludge electrodes and ten pieces of air cathodes All connect independently and with pericarp electrode, constitute loop.
Light source 14 provides illumination for photovoltaic battery panel, and light source 14 can also be able to be the equipment such as illumination lamp for natural light.
Wherein, pericarp electrode used is prepared by the following method:
(1) by discarded pericarp excision forming, 20~30h is air-dried under natural conditions;
(2) 60~90 DEG C of 0.5~2h of drying under nitrogen atmosphere of the pericarp after air-drying are cut;
(3) under nitrogen atmosphere, 800~1000 DEG C of temperature is controlled, pericarp is carbonized, be carbonized after finishing under nitrogen atmosphere Room temperature is naturally cooled to, it is standby.
Present embodiment can preferably be prepared by the following method:
(1) by discarded pericarp excision forming, 24h is air-dried under natural conditions;
(2) cut pericarp after air-drying and dry 1h for 80 DEG C under nitrogen atmosphere;
(3) under nitrogen atmosphere, 900 DEG C of temperature is controlled, pericarp is carbonized, carbonization is naturally cold under nitrogen atmosphere after finishing But it is standby to room temperature.
Sludge electrode is prepared by the following method for carbonization sludge electrode:
(1) sludge in an oven 40~60 DEG C drying 1~3h after carry out Mechanical Crushing;
(2) sludge after crushing crosses 80~120 eye mesh screens, the bulky grain thing in removal sludge;
(3) sludge after filtering is mixed with the hydrogen peroxide hydrogen peroxide for accounting for sludge quality 5~20%, prepares initial electrode;
(4) initial electrode is sintered under nitrogen atmosphere, controls 800~1200 DEG C of temperature, continues 1~3h, after heating is finished Room temperature is naturally cooled under nitrogen atmosphere.
In present embodiment preferably, prepare by the following method:
(1) sludge in an oven 50 DEG C drying 2h after carry out Mechanical Crushing;
(2) sludge uses 100 mesh sieve net filtrations, the bulky grain thing in removal sludge after crushing;
(3) sludge mixes with hydrogen peroxide after filtering, and prepares initial electrode;
(4) sinter under nitrogen atmosphere, control 1000 DEG C of temperature, continue 2h, heating is natural under nitrogen atmosphere after finishing It is cooled to room temperature.
Air cathode preparation method is as follows:
(1) activated carbon, acetylene black and polytetrafluoroethylene (PTFE) (PTFE) press 3:(3~4):(3~4) mass ratio mixes after stainless The film that thickness is 0.2~0.3mm is pressed on steel mesh;
(2) catalyst such as Ag are carried on reducing process the film surface obtained by step (1);
(3) sodium sulphate and PTFE press (3~4):Suppressed on the electrode obtained by step (2) after the mixing of (6~7) mass ratio;
(4) anion-exchange membrane processes 3min under the conditions of 140 DEG C and 1780kPa, is directly hot-pressed onto step (3) obtained Obtained final product on negative electrode.
The catalyst is Ag etc., and the reducing process is:In 0.1M AgNO3In solution, with silver electrode as anode, step (1) the wherein one side of gained negative electrode is negative electrode, the reduction of 5~6V potential electrolysis.
Processing procedure and principle are as follows:
Anode chamber biofilm microorganism is electricity production bacterium, and under night non-illuminated conditions, urine is continuously introduced into anode chamber, will locate completely Urine after reason sends into cathode chamber as electrolyte, and anode produces electricity bacterium and produces electronics by the COD that degrades and lift NH4 +Concentration, oxygen Gas is electronically generated OH by what air cathode received that anode passes over-, OH-Diffuse to cathode chamber and NH4 +Reaction generation NH3Gas Body is overflowed and is absorbed by olefin(e) acid, and urine obtains preliminary treatment;Under the conditions of daylight, preliminary treatment urine is continuously introduced into again Anode chamber, air cathode persistently plays a role, and electronics derives the voltage for producing 0.3~0.6V through external circuit, and photovoltaic battery panel exists It is additionally provided 0.7~1.0V voltages under illumination condition, the urine after electrolysis catholyte chamber is processed completely obtains H2, further lifting Improve cathode chamber basicity, more NH3Gas overflowing, washs and reclaims NH by dilute acid soln3, H2Reclaimed by hydrogen container, urine Have been fully processed.Urine after processing completely can be used as catholyte.
Embodiment 1
Anodic degradation room is with 0.3m3/(m3D) flow enters water COD concentration for 12000mg/L, ammonia-nitrogen content 4500mg/L's Urine, cathode chamber water inlet is the urine for having processed.It is 5 days timing acquiring water of 0.7V stable operations by above-mentioned method control voltage Sample analyzes COD degradation situation, collects hydrogen and calculates hydrogen output, runs 5 batches altogether in the same way.
As a result:Waste water COD water outlet drops to 450~600mg/L, and ammonia-nitrogen content is down to 60~75mg/L, every liter of urine hydrogen Gas yield is 8.20L-9.56L, and more than 2g NH are reclaimed per L urines4 +-N。
Embodiment 2
Anodic degradation room is with 0.3m3/(m3D) flow enters water COD concentration for 11000mg/L, and ammonia-nitrogen content is 5000mg/L Urine, cathode chamber enters the complete urine of water process.It is 5 days timing acquiring water of 1.0V stable operations by above-mentioned method control voltage Sample analyzes COD degradation situation, collects hydrogen and calculates hydrogen output, runs 5 batches altogether in the same way.
As a result:Waste water COD water outlet drops to 300~500mg/L, and ammonia-nitrogen content is down to 45~55mg/L, and every liter of life is dirty Water process hydrogen output is 10.11L-10.46L, and more than 3g NH are reclaimed per L urines4 +-N。
The specific implementation case of patent of the present invention is the foregoing is only, but the technical characteristic of patent of the present invention is not limited to This, any those skilled in the relevant art in the field of the invention, all cover of the invention special by the change or modification made Among sharp scope.

Claims (8)

1. a kind of ecological many negative electrode urine processing devices, including three Room reactors, storage urine pot, ammonia tourie and hydrogen container, institute Stating three Room reactors includes being located at middle anode chamber and the cathode chamber positioned at anode chamber both sides, anode chamber and two cathode chambers it Between separated by cation-exchange membrane, the anode chamber is provided with urine import and export, and the gas vent of the cathode chamber is sequentially connected ammonia Aspiration closed cans and hydrogen container;Characterized in that,
Set in the anode chamber and sludge electrode is set in pericarp electrode, the cathode chamber, with fruit after two sludge electrode parallel connections Skin electrode is connected, and the branch road of each sludge electrode is provided with a photovoltaic battery panel connected with sludge electrode;
Air cathode is covered with all sides that the cathode chamber is not connected with anode chamber, lateral load is cloudy in the air cathode Amberplex is spaced with solution, is connected with pericarp electrode after all air cathode parallel connections.
2. ecological many negative electrode urine processing devices according to claim 1, it is characterised in that the pericarp electrode is by such as lower section It is prepared by method:
(1) by discarded pericarp excision forming, 20~30h is air-dried under natural conditions;
(2) 60~90 DEG C of 0.5~2h of drying under nitrogen atmosphere of the pericarp after air-drying are cut;
(3) under nitrogen atmosphere, 800~1000 DEG C of temperature is controlled, pericarp is carbonized, carbonization is natural under nitrogen atmosphere after finishing Room temperature is cooled to, it is standby.
3. ecological many negative electrode urine processing devices according to claim 1, it is characterised in that the sludge electrode is by such as lower section It is prepared by method:
(1) sludge in an oven 40~60 DEG C drying 1~3h after carry out Mechanical Crushing;
(2) sludge after crushing crosses 80~120 eye mesh screens, the bulky grain thing in removal sludge;
(3) sludge after filtering is mixed with hydrogen peroxide, prepares initial electrode;
(4) initial electrode is sintered under nitrogen atmosphere, controls 800~1200 DEG C of temperature, continues 1~3h, is heated after finishing in nitrogen Atmosphere naturally cools to room temperature under enclosing.
4. the method that ecological many negative electrode urine processing devices described in a kind of utilization claim 1 process urine, it is characterised in that bag Include following steps:
(1) anode chamber's inoculation bacterium solution, the normal temperature anaerobic fermentation urine of 8~12 days is continuously introduced into after success biofilm to anode chamber, cloudy Electrolyte is contained in pole room;
(2) under non-illuminated conditions, anode produces electricity bacterium and produces electronics by the COD that degrades and lift NH4 +Concentration, oxygen passes through air What negative electrode received that anode passes over is electronically generated OH-, OH-Diffuse to cathode chamber and NH4 +Reaction generation NH3Gas overflowing, passes through Dilute acid soln reclaims NH3;Urine in anode chamber after preliminary treatment is kept in after deriving;
(3) optical condition starts photovoltaic battery panel, there is provided the voltage of stabilization, through the urine after step (2) preliminary treatment again It is continuously introduced into anode chamber, anode produces electricity bacterium and obtains electronics by organic matter of degrading, and gives sludge negative electrode by electron transmission, there is provided Voltage, H in cathode chamber electrolyte+Obtain electron reduction into H2, derived into hydrogen container from cathode chamber;
(4) urine after thoroughly being purified through anode chamber is derived by drainpipe, and a portion is used as the electrolyte of cathode chamber.
5. method according to claim 4, it is characterised in that the voltage that photovoltaic battery panel is provided is 0.7~1.0V.
6. method according to claim 4, it is characterised in that crude urine liquid import, derive anode chamber speed be 0.1~ 0.5m3/(m3·d)。
7. method according to claim 4, it is characterised in that the electricity production bacterium bacterium solution is with COD concentration by electricity production bacterium solution The organic wastewater of 4000~6000mg/L is with volume ratio 1:(3~5) constitute.
8. method according to claim 4, it is characterised in that increase device startup stage between step (1):Negative electrode is added M9 electrolyte, anode chamber's inoculation bacterium solution, opens photovoltaic battery panel, and reactor is started under the conditions of 30 DEG C, and the time that starts is 1~7 day.
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