CN101607781A - A kind of microbiological cell device and municipal sludge disposal method - Google Patents
A kind of microbiological cell device and municipal sludge disposal method Download PDFInfo
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- CN101607781A CN101607781A CNA2009100412354A CN200910041235A CN101607781A CN 101607781 A CN101607781 A CN 101607781A CN A2009100412354 A CNA2009100412354 A CN A2009100412354A CN 200910041235 A CN200910041235 A CN 200910041235A CN 101607781 A CN101607781 A CN 101607781A
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Abstract
The invention discloses a kind of microbiological cell device and municipal sludge disposal method.Described microbiological fuel cell comprises anolyte compartment, cathode compartment, anode, negative electrode and lead, and described anolyte compartment and cathode compartment adopt isolated material to isolate, and the anolyte compartment is provided with mud and imports and exports injection and discharge mud; Anode is located at the bottom, anolyte compartment and is buried by mud; The supernatant liquor that produces behind the sludge settling enters cathode compartment, and the negative electrode lower surface is close to the supernatant liquor liquid level, and the upper surface that negative electrode is coated with catalyzer contacts with air; Connect yin, yang the two poles of the earth with lead and form the loop.Microbiological fuel cell method for disposing sludge under the present invention provides simultaneously and utilized.As the new way of sludge disposal, the present invention can solve the deficiency that present Sludge Disposal Techniques exists, and the Application Areas of efficient extn microbiological fuel cell, has adapted to the needs of current environmental protection situation.
Description
Technical field
The invention belongs to environment and technical field of new energies, be specifically related to a kind of microbiological cell device and adopt described device to dispose the method for municipal sludge.
Background technology
Municipal sludge is the throw out that certainly leads in the municipal sewage treatment process.At present, China's municipal sludge year generation has reached 8,000,000 tons of dry weights, and with annual 10～15% speed increase.These mud are most to be filled out or arbitrarily throws aside by simple heap, has offset the effect of sewage work's environment purification greatly, has seriously restricted the sound development of sewage disposal cause.The disposal lack of standardization of mud has become the new hidden danger of current urban environment, how to dispose properly that these quantity are huge day by day, the organic solid castoff of high concentration, is one of sewage work's problem of having a headache most.In general, sludge treatment and disposal costs account for 30～40% of sewage disposal total expenses.
Existing sludge disposal mode mainly contains: 1) landfill; 2) burn; 3) composting; 4) soil utilization.Wherein, landfill is disposed mud fully as waste, does not bring into play its resource utilization and is worth; There are the secondary pollution risk in burning method equipment requirements height, investment and running cost height; The composting floor space is big, added value of product is lower; And there are secondary pollution problems such as heavy metal or pathogenic agent in the direct agricultural use of mud.Therefore, all there is the defective that self is difficult to overcome in existing sludge disposal mode, nor can satisfy current actual needs, along with the raising of sewage load, presses for and seeks new recycling sludge disposal outlet.
Under the situation that world today's fossil oil is exhausted and the global warming problem is increasingly serious, the energy technology of abandoned biomass (as municipal sludge, fowl and animal excrement, crop stalk, high concentrated organic wastewater) will have bright prospects.Microbiological fuel cell (MFC) is the power generation assembly that the chemical energy in the organism is converted into electric energy, has generating and waste treatment double effects.Compare with traditional anaerobic methane production gas technology, MFC directly extracts electric energy sustainably from waste, the needs of energy twice transformation and gas storage have been avoided, and in electrogenesis, can effectively remove organism, therefore be an advanced biomass energy utilization technologies that development potentiality is huge, be expected to become the pillar technology that following organic waste are handled.
The ultimate principle of MFC is: organism acts as a fuel in the anaerobism anolyte compartment by microbiological oxidation, the electronics that produces is caught and passes to galvanic anode by microorganism, electronics arrives negative electrode by external circuit, thereby form the loop and produce electric current, and proton arrives negative electrode by exchange membrane, with the oxygen water generation reaction.The general structure of existing microbiological fuel cell is: cathode and anode two Room, and the centre is separated by barrier film, and the anolyte compartment keeps anaerobic state, and cathode compartment adopts the ventilating mode oxygen supply.
Organic content height in the municipal sludge (generally can reach 40～50%) is containing huge biomass energy, if can realize mud is carried out electricity generation by microorganism as the fuel of MFC, can effectively carry out sludge disposal in the acquisition electric energy.By prior art report and disclosed patent retrieval are found, so far, yet there are no the technology report that MFC is used to handle municipal sludge.
Exist very big technical barrier and bottleneck if existing traditional MFC battery is directly applied to the actual cities sludge disposal: 1) proton exchange membrane that generally adopts of traditional MFC battery costs an arm and a leg, and cost is too high; 2) suspended particle organic content height in the mud easily stops up traditional MFC battery diaphragm space; 3) the cathodic oxygen reduction reaction needed continues ventilation oxygen-supplying, makes the oxygen supply power consumption surpass the output electric energy, and MFC can't realize that the oneself keeps operation; 4) traditional MFC battery structure is complicated, is unfavorable for practical application; 5) output voltage or the electric current of existing MFC battery cell can not satisfy practical application far away, the having little significance of popularization.Above-mentioned technical bottleneck has hindered application and the popularization of this advanced biomass energy utilization technologies of MFC aspect the municipal sludge processing.
Therefore, realize utilizing MFC to carry out the application of municipal sludge production by biological electrical treating, must solve following technical bottleneck: 1) seek suitable low-cost diaphragm material solution, thereby reduce the MFC cost significantly; 2) change design concept and prior art scheme, seek succinctly and be applicable to the MFC structure of mud; 3) promote MFC voltage.Through disclosed technical literature and patent retrieval, do not find technology report that municipal sludge is acted as a fuel and disposes as yet, be not the correlation technique report of the novel low-cost MFC battery of fuel with the municipal sludge yet.
Summary of the invention
One object of the present invention is to overcome existing microbiological fuel cell textural defect and operation scheme is unfavorable for utilizing mud to act as a fuel and cost is high shortcoming, and providing a kind of can municipal sludge be the novel low-cost microbial fuel cell unit of fuel.
Another object of the present invention is to further improve on the basis of said apparatus and expand, a kind of microbiological fuel cell pile device promptly is provided, described battery pile acts as a fuel with mud, have advantages such as compact construction, output power density height, easy expansion amplification, remedy the not high enough deficiency of microbiological fuel cell said apparatus output voltage of the present invention, effectively promote MFC voltage.
Of the present invention also have a purpose to provide a kind of new municipal sludge disposal method, promptly utilizes microbiological fuel cell technology disposing sludge to produce the cleaning electric energy simultaneously.
Purpose of the present invention is achieved by the following technical programs:
A kind of microbiological cell device is provided, comprises anolyte compartment, cathode compartment, anode, negative electrode and lead, described anolyte compartment and cathode compartment adopt isolated material to isolate, and the anolyte compartment is provided with mud and imports and exports injection and discharge mud; Anode is located at the bottom, anolyte compartment and is buried by mud; The supernatant liquor that produces behind the sludge settling enters cathode compartment, and the negative electrode lower surface is close to the supernatant liquor liquid level, and the upper surface that negative electrode is coated with catalyzer contacts with air; Connect yin, yang the two poles of the earth with lead and form the loop.
If described mud and supernatant liquor are to place among the container, can adopt isolated material isolation mud and supernatant liquor to form anolyte compartment and cathode compartment simultaneously.The supernatant liquor infiltrate isolated material that produces behind the sludge settling enters cathode compartment.
Described isolated material is a Web materials, and the aperture of grid material is 100～300 orders, preferred 200 orders, similar nylon cloth be difficult to biodegradable Web materials all can, preferred filter screen, filter cloth, purpose is to stop heavy mud, does not allow its come-up.The present invention does not use proton exchange membrane, negatively charged ion or cationic exchange membrane, nanofiltration membrane etc. than accurate, expensive mould material, preferably adopts low-cost grid cloth material common in the industry, prevents the come-up that sludge bulking causes, and reduces cost greatly.
Microbiological fuel cell structure optimization scheme of the present invention: establish an open container, be divided into upper and lower two portions space by isolated material, the lower part space is the anolyte compartment, is provided with mud and imports and exports, and injects municipal sludge; The upper section space is a cathode compartment, and the supernatant liquor infiltrate isolated material that produces after the municipal sludge natural subsidence enters cathode compartment; Anode is embedded among the municipal sludge; Negative electrode simultaneously is close to the supernatant liquor liquid level, and the negative electrode another side scribbles catalyzer, contacts with air; Connect yin, yang the two poles of the earth with lead and form the loop.
Described isolated material preferably is parallel to the bottom surface, anolyte compartment.
Described anode is selected the bigger serface electro-conductive material for use, can select for use with reference to prior art, for example carbon felt, graphite granule, carbon fiber brush etc.The preferred carbon felt of the present invention.Described cathode material can be selected carbon cloth, carbon paper or carbon felt etc. for use, preferred carbon felt, appendix catalyzer on it, catalyzer is selected for use according to existing routine techniques, for example platinum, pyrolysis ferrous phthalocyanine (pyr-FePc), tetramethoxy phenyl cobalt porphyrin (CoTMPP) or Manganse Dioxide.
The preparation method of described negative electrode, can be with reference to existing routine techniques, for example, taking by weighing carbon carries platinum powder end, pyr-FePc or CoTMPP and adds an amount of Virahol dispersion agent, add an amount of Nafion solution then and stir into pasty state, evenly be coated on the carbon felt behind the ultra-sonic dispersion ultra-sonic dispersion, vacuum-drying promptly gets the carried catalyst negative electrode; Perhaps, took by weighing carbon dust, manganese dioxide powder and binding agent PVDF respectively by 65: 20: 15, add an amount of dispersion agent N-methyl pyrrolidone, evenly be coated on the dried carbon felt behind the ultra-sonic dispersion, vacuum-drying obtains the carried catalyst negative electrode.Can be preparation method related in the patent application of CN101355170 also with reference to publication number.
Add pending mud in the anolyte compartment, connect external circuit, carry out the electrogenesis microbial acclimation; Treat that the anode microbial acclimation finishes, when forming ripe, stable microbial film, can carry out the operation of multiple sludge disposal and electrogenesis.Interim weekly, treat that voltage reduces to 50mV and change mud by container below import and export when following, enter next cycle.Mud is after the MFC electrogenesis consumes, and COD is effectively removed.
As a kind of monomer, the present invention also provides a kind of monomeric applied in any combination scheme with above-mentioned battery, can be applicable to municipal sludge and handles, and effectively promote MFC voltage.The technical scheme of described combination is to be banked up by at least two described battery cells to form, and each monomeric cathode and anode is drawn respectively by lead, end to end being connected in series or parallel; Do not communicate the independent input and output material of each monomer between monomer; The lead that first monomer male or female and end monomer negative electrode or anode are drawn connects extrernal resistance and constitutes external circuit.
As a kind of typical technical scheme, the present invention is divided into some vertical parallel cells with a container with dividing plate, and the structure of each cell comprises anolyte compartment, anode, isolated material, negative electrode and lead, and the anolyte compartment is provided with mud and imports and exports; Municipal sludge injects the anolyte compartment, and the supernatant liquor that produces after the municipal sludge sedimentation enters cathode compartment; Anode is embedded among the municipal sludge; Negative electrode is close to supernatant liquor water surface place, and its lower surface contacts with water, and upper surface is coated with catalyzer, contacts with air; The cathode and anode of each cell is drawn respectively by lead, end to end being connected in series or parallel; Do not communicate between each cell, separately input and output material; The lead that first cell male or female and end cell negative electrode or anode are drawn connects extrernal resistance and forms loop formation external circuit.Described battery pile has advantages such as compact construction, output power density height, easy expansion amplification, overcomes the affiliated not high enough deficiency of microbial battery output voltage of the present invention, effectively promotes MFC voltage.
The present invention provides municipal sludge disposal method simultaneously, adopt described microbiological fuel cell disposing sludge, mud injects the fuel of anolyte compartment as microbiological fuel cell, draw from the anode of anolyte compartment and the negative electrode of cathode compartment respectively with lead and to be connected external resistance and to constitute the loop, consume the mud organic substance chemical energy and produce cleaning electric energy and the final COD value that reduces mud.
Perhaps adopt described microbiological fuel cell pile disposing sludge, the anolyte compartment that mud injects each cell apparatus respectively acts as a fuel, and the microbial battery heap consumes mud organic substance and produces electric energy.
Described municipal sludge disposal method specifically may further comprise the steps:
(1) pending mud natural subsidence produces supernatant liquor;
(2) anode is embedded in the mud; Negative electrode is installed on the supernatant liquor liquid level, and the lower surface of negative electrode and supernatant liquor liquid level are close to, and the upper surface that negative electrode is coated with catalyzer contacts with air;
(3) with the anode and the negative electrode of lead connection microbiological fuel cell, connect external circuit, constitute the microbiological fuel cell monomer, carry out the electrogenesis microbial acclimation; After finishing, microbial acclimation carries out the operation of multiple sludge disposal and electrogenesis.
The invention has the beneficial effects as follows:
(1) the present invention overcomes the deficiency of traditional sludge method of disposal, comprise technical barriers such as the wasting of resources, running cost height, secondary pollution, a kind of new mud is provided, act as a fuel with mud, mud COD is effectively reduced, produce the cleaning electric energy in the time of disposing sludge; Microbiological fuel cell provided by the invention can make full use of useful component in the mud, and disposal of wastes produces electric energy simultaneously, and floor space is little, and environmental friendliness meets the requirement of clean energy development.
(2) the present invention separates anolyte compartment and cathode compartment with grid cloth cheap and easy to get, and negative electrode adopts by the pneumatic aeration oxygen supply, and the more traditional MFC of microbiological fuel cell cost of structure significantly reduces, the application of suitable sludge treatment aspect.The present invention need not ventilation power consumption, easy maintenance; Simple for structure, compact, easily floor space is amplified and is not increased in expansion; Cost is lower, and output power density height, COD removal effect are good, and suitable industry is applied, and helps expanding the Application Areas of MFC.
In sum, the invention provides a kind of new mud, when being acted as a fuel generation cleaning electric energy, mud reaches the effect of disposing sludge, providing a kind of simultaneously can municipal sludge be the novel low-cost microbial fuel cell unit of fuel, as the new technical scheme of sludge disposal, can solve the deficiency that present sludge disposal and microbiological fuel cell technology exist, have broad prospect of application, adapt to the needs of current environmental protection situation.
Description of drawings
Fig. 1 disposes the microbiological fuel cell monomer structure synoptic diagram of municipal sludge
Fig. 2 disposes the microbiological fuel cell electrogenesis principle schematic of municipal sludge
Fig. 3 disposes the microbiological fuel cell pile structural representation of municipal sludge
Fig. 4 embodiment 2 disposes the electrogenesis design sketch of the microbiological fuel cell of municipal sludge
Fig. 5 embodiment 3 disposes the electrogenesis design sketch of the microbiological fuel cell pile of municipal sludge
Fig. 6 embodiment 5 disposes the electrogenesis design sketch of the microbiological fuel cell pile of municipal sludge
Embodiment
The present invention makes up a kind of new microbiological fuel cell, described microbiological fuel cell adopts isolated material to be divided into anolyte compartment and cathode compartment, municipal sludge injects the fuel of anolyte compartment as microbiological fuel cell, the supernatant liquor infiltrate isolated material that the municipal sludge sedimentation produces enters cathode compartment, and negative electrode is by the pneumatic aeration oxygen supply; Draw from the anode of anolyte compartment and the negative electrode of cathode compartment respectively with lead and to be connected external resistance and to constitute the loop.When mud produced the cleaning electric energy as microbiological fuel cell by battery, mud was also effectively disposed, and its COD reduces greatly.Further describe the present invention below in conjunction with the drawings and specific embodiments, the present invention has changed the essential structure thinking of microbiological fuel cell, makes to utilize mud to act as a fuel to have practical feasibility.In following embodiment, only provide a kind of typical structure in order to explanation the present invention, therefore do not limit the scope of the invention.
Embodiment 1 utilizes microbiological fuel cell to dispose municipal sludge
The invention provides a kind of municipal sludge disposal method, may further comprise the steps:
(1) establishes an open container, the anode of microbiological fuel cell is installed on container bottom; Place the microbiological fuel cell container to carry out natural subsidence municipal sludge and produce supernatant liquor, isolated material is set mud and supernatant liquor are isolated;
The negative electrode of microbiological fuel cell is installed on the supernatant liquor, and the one side of negative electrode contacts with the supernatant liquor surface, and the one side that negative electrode is coated with catalyzer contacts with air;
(2) with the anode and the negative electrode of lead connection microbiological fuel cell, connect external circuit, carry out the electrogenesis microbial acclimation; After finishing, the anode microbial acclimation carries out the operation of multiple sludge disposal and electrogenesis.
Actually operating and operational standardization from now on the invention provides the disposal that a kind of microbial fuel cell unit is finished above-mentioned municipal sludge for convenience.The structure of described microbiological fuel cell as shown in Figure 1, the electrogenesis principle is as shown in Figure 2.Described microbiological fuel cell is simple in structure, only is made up of anolyte compartment, anode, isolated material, cathode compartment and negative electrode, compares with existing microbiological fuel cell, has omitted membrane module.The open container that can adopt polyethylene (or other insulating material) material to make, container is provided with opening for feed and discharge port according to routine techniques; Isolated material 3 is divided into superjacent air space 4 and following side space 1 with container, following side space 1 is the anolyte compartment, the size of placing isolated material 3 in the anolyte compartment is with anolyte compartment's cross section is suitable and can prevent effectively that sludge bulking from floating, if the surface-area of isolated material 3 one sides equates that with anolyte compartment's cross-sectional area effect is relatively good, can adopt grid cloth, filter screen or filter cloth as isolated material 3, the grid aperture of material is 100～300 orders, preferred 200 orders, described isolated material is parallel to the bottom surface, anolyte compartment as far as possible.
From the opening for feed of container municipal sludge is injected in the anolyte compartment 1, the supernatant liquor that the mud natural subsidence produces enters container headspace 4 by isolated material 3.The time of municipal sludge natural subsidence does not have particular requirement, and common container headspace 4 is gathered the certain volume supernatant liquor and got final product.It is thick that the preferred supernatant liquor of the present invention reaches the depth of water 2～4cm, keeps certain depth of water, is the anaerobic state for mud in the side space 1 under floating cathode electrode and the maintenance.Anode 2 is embedded in the mud, and anode 2 is generally rectangle, and anode 2 area size of the present invention preferably are slightly less than anolyte compartment's cross section.Distance between anode 2 and the isolated material 3 is preferably 1～3cm; Cathode size and anolyte compartment's cross section are suitable, negative electrode two sides 5 and 6, and cathode plane 5 is close to the supernatant liquor water surface, and the cathode plane 6 that scribbles catalyzer exposes to the sun in air towards air, the preferred 2～4cm of the distance between negative electrode and the isolated material; Anode and negative electrode all have lead to draw, and pull-up resistor 7 is connected external circuit.
Described anode is selected the bigger serface electro-conductive material for use, as graphite granule, carbon felt, carbon fiber brush etc.
Industrial filter screen, filter cloth that described isolated material can be selected for use is cheap, the space is moderate, materials such as gauze, nylon cloth.
Described negative electrode is selected for use in the form of sheets, the bigger serface electro-conductive material, as carbon felt, carbon cloth, carbon paper etc.
Catalyzer can adopt platinum, pyrolysis ferrous phthalocyanine (pyr-FePc), tetramethoxy phenyl cobalt porphyrin (CoTMPP) or Manganse Dioxide.
Cathodic reaction:
2O
2+8H
++8e
-→4H
2O
Anodic reaction:
C
2H
4O
2+2H
2O→2CO
2+8H
++8e
-
(1) municipal sludge sample
For examination mud is the thickened sludge of Gaobeidian City, Beijing sewage work, adopts back to place 4 ℃ of refrigerators to preserve.The mud physico-chemical property is as follows: pH is 6.86; Volatile organic content is about 49.5%; Total carbon, 279.4 gram/kilograms; Total nitrogen, 27.6 gram/kilograms.
(2) structure of microbiological fuel cell
As shown in Figure 1, adopting the cross section length of side is the polythene material cuboid container of 6cm, container height overall 10cm.Container below opening for feed (routine techniques does not do marking among the figure) injects 144mL mud, and Sludge Surface is about 4cm apart from the battery floor height, and shadow area is that (5 * 5cm) carbon felt places apart from the mud of Sludge Surface 1cm below as anode 25cm.It is the nylon cloth of 6cm that Sludge Surface covers the length of side, and the cloth aperture is 100 orders.Sludge settling produces supernatant liquor infiltrate nylon cloth and enters container headspace 4, is close to the supernatant liquid level and places the size carbon felt identical with anolyte compartment's cross-sectional area as negative electrode, and the surface that negative electrode contacts with air is coated with manganese dioxide-catalyst.The anode carbon felt is connected lead respectively with negative electrode, and when treating that the about 3cm of the supernatant liquor depth of water is high, load 1000 Ω resistance are connected external circuit.
Catalyzer prepares according to existing routine techniques, method is as follows: clip carbon felt (6 * 6cm), respectively take by weighing carbon dust, manganese dioxide powder and binding agent PVDF mixing in small beaker in right amount at 65: 20: 15 by mass ratio, adding an amount of dispersion agent N-methyl pyrrolidone solution makes it become pasty state, behind the ultra-sonic dispersion 20min, with brush pasty mixture evenly is coated on dried carbon felt surface, 100 ℃ of vacuum-drying 2h.Taking by weighing carbon felt weight before and after being coated with catalyzer, calculate catalyst loading, can be the disclosed technical scheme of patent application of CN101355170 with reference to publication number perhaps.
(3) start battery operation and continuous electrogenesis of municipal sludge and treatment effect
The above-mentioned battery of the present invention can start operation in 15～35 ℃ of environment of room temperature.When starting battery, will inject in the container for examination mud (water ratio is 96.3%, and COD is 31230mg/L), and connect cell circuit, the load extrernal resistance is 1000 Ω.Treat that input voltage rises to 0.3V when above, show the start battery success.Reduce to 50mV when following when output voltage, change mud, carry out the electrogenesis test.The operation result in 1 year shows by a definite date, described battery when handling mud, electrogenesis stably.Handling back mud COD is 9150mg/L, and the COD clearance is 70.7%.The electricity generation performance of battery is seen shown in the accompanying drawing 4, is 0.72V by accompanying drawing 4 visible battery open circuit voltages, and peak power output density is 29.5mW/m
2Microbiological fuel cell of the present invention can guarantee to realize the disposal of municipal sludge, and produces electric energy simultaneously.
(1) mud sample
For examination mud is the thickened sludge that moral sewage work is hunted in Guangzhou, adopts back to place 4 ℃ of refrigerators to preserve.Physico-chemical property is as follows: pH is 6.69; Volatile organic content is 45.2%; Total carbon 232.3 gram/kilograms; Total nitrogen 28.2 gram/kilograms.For the examination moisture percentage in sewage sludge is 96.7%, and COD is 29050mg/L.
(2) structure of battery
Adopting the cross section length of side is the polyethylene cuboid container of 6cm, container height overall 10cm.144mL mud is injected by import in the below, Sludge Surface is 4cm apart from the battery floor height, and shadow area is that (5 * 5cm) carbon felt places apart from the mud of Sludge Surface 2cm below as anode 25cm, fill graphite granule on every side for replenishing anode, to increase anode surface area.It is the nylon cloth of 6cm that Sludge Surface covers the length of side, and the cloth aperture is 200 orders.Sludge settling produces supernatant liquor infiltrate nylon cloth and enters container headspace 4, be close to the supernatant liquid level and place the size carbon felt identical as negative electrode with anolyte compartment's cross-sectional area, the surface that negative electrode contacts with air is coated with platinum catalyst layers, the anode carbon felt is connected lead respectively with negative electrode, when treating that the about 2cm of the supernatant liquor depth of water is high, load 1000 Ω resistance are connected external circuit.
Wherein, it is as follows to carry platinum carbon felt negative electrode preparation process:
1) clip carbon felt (size 6 * 6cm);
2) take by weighing 20% carbon and carry platinum powder end 0.12g in weighing bottle, add 12mL Virahol dispersion agent again, add 5% (massfraction) Nafion solution 0.46mL then and stir into pasty state, ultra-sonic dispersion 30 minutes;
3) with brush pasty mixture is coated on the exsiccant carbon felt equably, promptly made in 3 hours in 100 ℃ of vacuum-dryings and carry the platinum carbon cloth.
4) be coated with the catalyzer front and back and take by weighing carbon felt weight, calculate catalyst loading.
(3) start battery operation and continuous electrogenesis of municipal sludge and treatment effect
The present embodiment battery starts operation in 15～35 ℃ of environment of room temperature.When starting battery, will inject in the container for examination mud, and connect cell circuit, the load extrernal resistance is 1000 Ω.Treat that input voltage rises to 0.3V when above, show the start battery success.Reduce to 50mV when following when output voltage, change mud, carry out the electrogenesis test.The operation result in 1 year shows by a definite date, described battery when handling mud, electrogenesis stably.Handling back mud COD is 7810mg/L, and the COD clearance is 73.1%.The electricity generation performance of battery is seen shown in the accompanying drawing 5, is 0.70V by accompanying drawing 5 visible battery open circuit voltages, and peak power output density is 34.8mW/m
2
Microbiological fuel cell of the present invention can successfully be applicable to the disposal of various municipal sludges, and produces electric energy simultaneously.The size of container described in the embodiment 1～2 only is used for convenient the explanation visually and the present invention does not therefore limit scope of the present invention.
Present embodiment provides a kind of cell stack device synoptic diagram as shown in Figure 3.One container is divided into 6 vertical parallel cells by dividing plate, and each cell is a microbial battery monomer, does not communicate between monomer.Unibody construction is described with reference to embodiment 1 or 2, lead is drawn respectively by cathode and anode, the cathode wire 11 of first monomer 8 is connected with second monomer, 9 positive wires 12, the cathode wire of second monomer 9 is connected with the 3rd monomer positive wire, the rest may be inferred, and first monomer 8 positive wires 13 connect extrernal resistance 7 formation external circuit with the lead 14 that last monomer 10 negative electrode is drawn; Perhaps first monomeric positive wire is connected with second cathode wire, second monomeric positive wire is connected with the 3rd monomer cathode wire, the rest may be inferred, and the lead that first monomer cathode wire and last monomer anode are drawn connects extrernal resistance and constitutes external circuit.The independent input and output material of each monomer, the startup of each monomeric mud sample introduction, battery pile, operation method are identical with embodiment 1～2 described battery.
(1) mud sample
For examination mud is the thickened sludge that moral sewage work is hunted in Guangzhou, adopts back to place 4 ℃ of refrigerators to preserve.Physico-chemical property is as follows: pH is 6.69; Volatile organic content is 45.2%; Total carbon 232.3 gram/kilograms; Total nitrogen 28.2 gram/kilograms.For the examination moisture percentage in sewage sludge is 96.7%, and COD is 29050mg/L.
(2) structure of battery pile
Present embodiment provides another kind of battery pile, and a container is divided into 18 vertical parallel cells by dividing plate, constitutes 18 independently microbial battery monomers.The structure of each battery cell is with embodiment 4.Anode adopts the carbon felt material, and negative electrode adopts carbon felt appendix MnO
2Catalyzer, the method for attachment of lead constitute series connection with 4,18 cells of embodiment and get final product, and how cell is specifically arranged is not done particular requirement.
Catalyzer prepares according to existing routine techniques, method is as follows: clip carbon felt (6 * 6cm), respectively take by weighing carbon dust, manganese dioxide powder and binding agent PVDF mixing in small beaker in right amount at 65: 20: 15 by mass ratio, adding an amount of dispersion agent N-methyl pyrrolidone solution makes it become pasty state, behind the ultra-sonic dispersion 20min, with brush pasty mixture evenly is coated on dried carbon felt surface, 100 ℃ of vacuum-drying 2h.Taking by weighing carbon felt weight before and after being coated with catalyzer, calculate catalyst loading, can be the disclosed technical scheme of patent application of CN101355170 with reference to publication number perhaps.
(3) start battery operation and continuous electrogenesis of municipal sludge and treatment effect
Battery pile starts operation in the present embodiment in 15～35 ℃ of environment of room temperature.When starting battery pile, will be in examination mud (water ratio is 96.7%, and COD the is 29050mg/L) injecting reactor, with battery pile series connection energising loop, pond, the load extrernal resistance is 10000 Ω with lead.Treat that input voltage rises to 3V when above, show the start battery success.Reduce to 0.5V when following when output voltage, change mud, carry out the electrogenesis test.The operation result in 1 year shows by a definite date, described battery when handling mud, electrogenesis stably.Handling back mud COD is 9376mg/L, and the COD clearance is 67.7%.The electricity generation performance of battery is seen shown in the accompanying drawing 6, is 10.5V by accompanying drawing 6 visible battery open circuit voltages, and peak power output density is 21.1mW/m
2
As seen, microbiological fuel cell pile of the present invention is applicable to the disposal of municipal sludge, And produce simultaneously electric energy, described battery pile has compact conformation, output power density height, easily expands Unfold the advantages such as big, effectively promote MFC voltage.
Claims (10)
1, a kind of municipal sludge disposal method, it is characterized in that adopting microbiological fuel cell technology disposing sludge, described microbiological fuel cell adopts isolated material to be divided into anolyte compartment and cathode compartment, municipal sludge injects the fuel of anolyte compartment as microbiological fuel cell, the supernatant liquor infiltrate isolated material that the municipal sludge sedimentation produces enters cathode compartment, and negative electrode is by the pneumatic aeration oxygen supply; Draw from the anode of anolyte compartment and the negative electrode of cathode compartment respectively with lead and to be connected external resistance and to constitute the loop and consume mud organic substance and produce electric energy.
2, according to the described municipal sludge disposal method of claim 1, it is characterized in that may further comprise the steps:
(1) pending mud natural subsidence produces supernatant liquor;
(2) anode is embedded in the mud; Negative electrode is installed on the supernatant liquor liquid level, and the lower surface of negative electrode and supernatant liquor liquid level are close to, and the upper surface that negative electrode is coated with catalyzer contacts with air;
(3) with the anode and the negative electrode of lead connection microbiological fuel cell, connect external circuit, constitute the microbiological fuel cell monomer, carry out the electrogenesis microbial acclimation; After finishing, microbial acclimation carries out the operation of multiple sludge disposal and electrogenesis.
3, according to the described municipal sludge disposal method of claim 2, it is characterized in that further comprising the steps of: at least two described microbiological fuel cell monomers are banked up carried out the electrogenesis microbial acclimation again after forming microbiological fuel cell pile; After finishing, microbial acclimation carries out the operation of multiple sludge disposal and electrogenesis.
4,, it is characterized in that adopting between described mud of step (1) and the supernatant liquor isolated material to isolate according to the described municipal sludge disposal method of claim 2.
5, a kind of microbiological cell device of realizing claim 1 or 2 described methods is characterized in that comprising anolyte compartment, anode, isolated material, negative electrode and lead, and the anolyte compartment is provided with mud and imports and exports; Inject pending mud in the described anolyte compartment, anode is embedded in the mud; Negative electrode simultaneously is close to the supernatant liquor liquid level that produces behind the sludge settling, and the another side that negative electrode is coated with catalyzer contacts with air; Connect yin, yang the two poles of the earth with lead and form the loop.
6, microbiological cell device according to claim 5 is characterized in that described isolated material is parallel to the bottom surface, anolyte compartment.
7, microbiological cell device according to claim 5 is characterized in that described isolated material is filter screen, gauze, grid cloth or nylon cloth, and the grid aperture of described isolated material is 100～300 orders.
8, microbiological cell device according to claim 5 is characterized in that described anode material is carbon felt, graphite granule or carbon fiber brush; Described negative electrode is carbon cloth, carbon paper or the carbon felt of appendix catalyzer; Described catalyzer is platinum, pyrolysis ferrous phthalocyanine, tetramethoxy phenyl cobalt porphyrin or Manganse Dioxide.
9, a kind of microbiological cell device of realizing the described method of claim 3, it is characterized in that being banked up by at least two microbiological fuel cell monomers forms, and does not communicate the independent input and output material of each monomer between monomer; Each monomeric cathode and anode is drawn respectively by lead, end to end being connected in series or parallel; The lead that first monomer male or female and end monomer negative electrode or anode are drawn connects extrernal resistance and constitutes external circuit.
10, microbiological cell device according to claim 9 is characterized in that it being that a container is divided into some vertical parallel cells with dividing plate, and each cell constitutes a microbiological fuel cell monomer.
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