CN105689387A - Method for restoring combined pollution soil through electrodynamic force-fuel cell coupling device - Google Patents
Method for restoring combined pollution soil through electrodynamic force-fuel cell coupling device Download PDFInfo
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- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
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- B09C1/00—Reclamation of contaminated soil
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Abstract
The invention relates to a method for restoring combined pollution soil through an electrodynamic force-fuel cell coupling device. The method includes the following steps that (S1) a testing soil sample is manufactured; (S2) initial restoring through electrodynamic force is carried out; (S3) the coupling device is manufactured; and (S4) coupling restoring is carried out. When the method is adopted for restoring the combined pollution soil, the obvious removal rate of heavy metal and organic pollutant is achieved, and the method has a good prospect and the good industrial production potential in practical application.
Description
Technical field
The present invention relates to the purifier of a kind of pollutant and processing method, the method that particularly a kind of electric power-microorganism battery coupling device repairs combined contamination soil, belong to environmental conservation and prevention and cure of pollution and improvement field。
Background technology
At present, along with the fast development of China's industry and agricultural, people's living standard, while day by day improving, also result in extremely serious soil pollution。And agricultural product, subsoil water, ecological environment and health etc. are created very big threat by soil pollution in turn。
Therefore, strengthen the improvement of contaminated soil is very urgent, find a kind of quick, low energy consumption, the restorative procedure of contaminated soil that efficiency is high is of great practical significance。
At present, the recovery technique of tradition contaminated soil mainly has chemical method, Physical and biological restoration etc.。Wherein chemically and physically method is relatively costly, and easily the physicochemical property of soil is caused serious adverse effect。The advantages such as biological restoration has less costly, simple to operate, non-secondary pollution, therefore have extraordinary application prospect。
And for deep layer or the contaminated soil of waterflooding, mud or deposit, owing to lacking the oxygen of abundance, anoxia or anaerobic degradation are important approach of soil organic matter degraded。But under anoxia or anaerobic condition, microbial degradation organic pollution needs the electron acceptor such as nitrate, sulfate, therefore the shortage of electron acceptor can cause that microbial degradation rate reduction even stops。Add exogenous electron receptor and can promote that microbiological anaerobic is degraded, but these electron acceptors are not lasting。At the negative electrode of microorganism battery, oxygen is conveniently easy to get in the environment because of it and the clean environmental protection of product, is a kind of desirably cathode electronics receptor。If but provide oxygen as electron acceptor by the method for aeration, there is energy consumption height, the shortcoming that the dissolubility of oxygen is low。Oxygen will soon be consumed simultaneously。Therefore, the method needs lasting human and material resources and the energy to soil or deposit aeration, is greatly increased rehabilitation cost。
Microorganism battery system is the popular technology that compares nearly ten years, and it mainly utilizes electro-chemical activity microorganism as catalyst, and organic chemical energy is converted into electric energy。Microorganism battery under anaerobic can provide final electron acceptor at negative electrode place for microorganism continuously, thus promoting that pollutant are degraded when lacking the electron acceptors such as oxygen, nitrate, sulfate。Nature is widely present to be had the electron transmission that produces to the electrochemistry microorganism of electrode by metabolic function。
Therefore, microbiological fuel cell can utilize in the multiple environment such as soil, mud, deposit, sewage, human and animal excreta。
In recent years, microorganism battery, especially deposit microorganism battery increasingly obtained the concern of people because of its good electricity generation performance and contaminant removal efficiency。It has been carried out research extensively and profoundly by scientist, have developed multiple-microorganism battery restorative procedure and related device。
CN102386431A discloses a kind of soil microorganism fuel cell and the method repairing petroleum hydrocarbon contaminated soil。Described soil microorganism fuel cell is made up of U-tube and the membrane electrode being wrapped in its outer surface, U-tube is hollow pipe and tube wall uniformly distributed round, membrane electrode includes diffusion layer, carbon based layer, negative electrode, Catalytic Layer, glass fibre membrane and anode from inside to outside and is wound around composition layer structure, the anode of U-tube both sides and negative electrode are connected by wire self, battery is connected and composed by wire and outer meeting resistance between anode and negative electrode, adhering and sealing between U-tube and membrane electrode, the straight-tube portion height in U-tube embedment contaminated soil is identical with Polluted Soil layer thickness。
CN102368559A discloses a kind of alkaline microbial fuel cell。Described microbiological fuel cell includes container-like battery container, anode and air cathode；Described anode is NACF brush, carbon cloth or carbon paper, and air cathode is the carbon cloth collector body that two sides is respectively coated with politef diffusion layer and granular active carbon Catalytic Layer, and air cathode is placed in container both sides towards air, Catalytic Layer towards solution with diffusion layer；Electrolyte when electrolyte when the electrolyte of this fuel cell is divided into startup and electrogenesis run, electrolyte when wherein electrogenesis runs is divided into again Organic substance substrate and two kinds of main components of organic wastewater。Cathode catalysis material of the present invention is to adopt activated carbon, without any metallic catalyst, is substantially reduced cost。Running in the basic conditions, cathodic oxygen reduction performance is improved, and can improve organic energy conversion efficiency。When high-enriched organics, battery energy stable operation, and organism utilization rate is high。
CN202025824U discloses the soil microorganism fuel-cell device of a kind of organic material contaminated soil in-situ immobilization。Described utility model device includes film negative electrode and anode, is connected by wire between film negative electrode and anode。Film negative electrode outward flange is provided with water-stop sheet, so can form a cavity, enough buoyancy is provided, making film negative electrode floatability on the water surface, its two sides fully contacts with air and aqueous phase respectively, and its anode is embedded in soil, it is easily installed in flooded soils, organic pollution in local use flooded soils is fuel, carries out oxidative degradation, generates CO2With innocuous substances such as water, it is achieved the in-situ immobilization of soil。
CN102500610A disclose a kind of with low cost, practicability and effectiveness, environmental protection utilize electrogenesis microorganism and the plant-soil microbial fuel cell system of photosynthesis of plant coupling。It includes the external circuit of anode electrode, cathode electrode and jointed anode electrode and cathode electrode, also includes plant, and described anode electrode is placed in the soil of surrounding plant roots, and described cathode electrode is placed in soil surface。The present invention mainly produces and be discharged into the organic matter of root with photosynthesis of plant is fuel, it is to avoid electrogenesis microorganism in sewage organic for fuel time, the organic inhibitory action to electrogenesis microorganism, thus causing the problem that efficiency of fuel cell generation is low。Simultaneously the present invention is using plant as fuel supplier, it is achieved recycling of the energy of plant carbon sequestration-secretion organic matter-electrogenesis, it is achieved that the green of fuel supplies。
As mentioned above, although people have developed the method for multiple-microorganism battery repairing polluted soil, but all there are disadvantages that, such as: 1, in the cathode electrode of microbiological fuel cell, oxygen occurs the kinetic coefficient of reduction reaction relatively low in neutral conditions, thus limiting its use as the final electron acceptor of negative electrode, govern the response speed of whole reaction；2, microbiological fuel cell internal resistance is relatively big, reduces output, hinders the degradation efficiency of microbiological fuel cell；3, a corresponding negative electrode of anode, owing to anode surface area is limited, the microbial degradation of pollutant in soil is restricted；4, for repairing pollution in wide area soil, rehabilitation cost is higher。
All this kind, result in the range of application of said method and using value all receives certain restriction, it is impossible to promotes on a large scale。
For these reasons, administering field at contaminated soil at present, the contaminated soil remediation apparatus and method for removal effect novel, with low cost, respond well, high still have tight demand。Also precisely in order to solve this demand, the applicant in December in 2005 within 22nd, have submitted application number be 201510970668.3, denomination of invention be the application for a patent for invention of " a kind of electric power couples the method for repairing polluted soil with microbiological fuel cell ", this application is by specific electric power-microbiological fuel cell coupling device, Organic Pollution and/or heavy-metal contaminated soil can be repaired, it is possible to obtain good repairing effect。
But wherein for the reparation of heavy metal, remain a need for improving further the removal efficiency of heavy metal, inventor is carrying out correlational study always, tries hard to the novel restorative procedure developing combined contamination soil, farthest improves the removal efficiency of Organic substance and heavy metal especially heavy metal。Still at present the research emphasis in soil remediation field and focus, the power place that the present invention is accomplished especially and basis are not leaned on for these。
Summary of the invention
In order to farthest improve the polluted composite soil repairing method that Organic Pollution is removed and heavy metal pollution is removed, and the novel method of research and development reparation combined contamination soil, the present inventor is from practical application, the method that microbiological fuel cell is repaired combined contamination soil has carried out substantial amounts of further investigation, after having paid creative work, thus completing the present invention。
Specifically, first aspect, the invention mainly relates to the method that a kind of electric power-fuel cell coupling device repairs combined contamination soil, described method comprises the steps:
S1: make test soil sample
In soil sample groove, load contaminated soil, and insert two hollow electrode cylinders with holes, connect positive pole and the negative pole of DC source respectively, as electric power anode (hereinafter referred to as EK anode) and electric power negative electrode (hereinafter referred to as EK negative electrode)；
S2: electric power is initially repaired
In EK cathode tube, load solution electrode, in EK anode canister, load deionized water, open DC source and carry out energising reparation, and control the pH value of EK anodic dissolution and the pH value of EK cathode solution；
S3: make coupling device
After electric power has initially been repaired, pour out the solution electrode in EK negative electrode, disconnect the connection of EK anode and DC power anode, and the soil between EK anode and EK negative electrode uniformly inserts many anode of microbial fuel cell (hereinafter referred to as MFC anode), aperture on EK anode outer wall is sealed, thus original EK anode becomes microorganism fuel cell cathode (hereinafter referred to as MFC negative electrode), described many MFC anodes are sequentially connected with wire successively, and connect with described MFC negative electrode through external resistance；Being inserted into an electrode as new electric power anode (hereinafter referred to as new EK anode) at described MFC cathode tube, described new EK anode is connected with the positive pole of DC source, thus obtaining coupling device；
S4: coupling is repaired
In EK cathode tube, load solution electrode, open DC source and carry out electric power-microbiological fuel cell coupling reparation, and control the pH value of solution in described EK cathode tube, until completing to repair。
Repair in the method for combined contamination soil at the electric power-fuel cell coupling device of the present invention, in described step S1, the rounded cylindrical form that said two hollow electrode cylinder (i.e. described EK anode and EK negative electrode) with holes is hollow, its outer tube wall is evenly distributed with the aperture of aperture 1-3mm, the quantity of aperture does not have special considered critical, as long as it disclosure satisfy that soil treatment, those skilled in the art can carry out suitable selection and determine, this is its conventional capability that should have, and is no longer described in detail at this。The periphery of the barrel of EK anode and EK negative electrode is wound with filter cloth to prevent soil from entering cylinder interior, but and does not interfere with passing freely through of pollutant。
Repair in the method for combined contamination soil at the electric power-fuel cell coupling device of the present invention, in described step S2, described solution electrode (namely loads the solution electrode in EK cathode tube) for aqueous solutions such as EDTA (ethylenediaminetetraacetic acid) aqueous solution or NTA (aminotriacetic acid), the concentration of described solution electrode is 0.5-1.5mol/L, for instance can be 0.5mol/L, 1mol/L or 1.5mol/L。
Repairing in the method for combined contamination soil at the electric power-fuel cell coupling device of the present invention, in described step S2, the pH value controlling EK anodic dissolution is 6-7, for instance can be 6,6.5 or 7；And the pH value controlling EK cathode solution is 6-8, for instance can be 6,6.5,7,7.5 or 8；The pH value most preferably controlling EK anodic dissolution and EK cathode solution is 6.5。
Wherein, the means of described control ph and method can be neutralized by circulation or apply the modes such as ion exchange membrane and be controlled, and these are also all the routine techniques means in this area, are no longer described in detail at this。
Repair in the method for combined contamination soil at the electric power-fuel cell coupling device of the present invention, in described step S2, power-on voltage does not have specific considered critical, suitable determination (generally can select 5-200V as the case may be) can be carried out according to the volume size of soil sample, this is the routine techniques ability of those skilled in the art, is no longer described in detail at this。
Repair in the method for combined contamination soil at the electric power-fuel cell coupling device of the present invention, in described step S2, (the prolongation over time when the heavy metal in contaminated soil and organic contamination substrate concentration do not continue to reduce, reduce only small or stop reducing), just it is believed that electric power has initially been repaired, the operation of subsequent step S3 can now just be carried out。
Repair in the method for combined contamination soil at the electric power-fuel cell coupling device of the present invention, in described step S3, the electrode that described MFC anode is well known in, can be obtained by multiple commercial channel, no longer be described in detail at this。Its radical of described MFC anode can carry out suitable selection according to the distance between the volume of pending soil and/or described EK anode and described EK negative electrode and determine, it can be such as 5-20 root, such as 5,10,15 or 20, the selection of its quantity is the means that those skilled in the art can have, and is no longer described in detail at this。
Repair in the method for combined contamination soil at the electric power-fuel cell coupling device of the present invention, in described step S3, after the aperture on original EK anode outer wall is sealed, thus original EK anode becomes microorganism fuel cell cathode, the described means sealing aperture can be such as use the material not having any permeability and have excellent anticorrosive to block, or directly use exactly can by the effective pore-free electrode jacket casing of tight for EK anode cylinder fit outside EK anode, thus completing the closure of aperture, those skilled in the art can carry out suitable selection, no longer it is described in detail at this。
Repair in the method for combined contamination soil at the electric power-fuel cell coupling device of the present invention, in described step S3, the resistance sizes of described external resistance is generally 10-1000 Ω, can be such as 10 Ω, 50 Ω, 100 Ω, 200 Ω, 300 Ω, 400 Ω, 500 Ω, 600 Ω, 700 Ω, 800 Ω, 900 Ω or 1000 Ω, can according to the volume size of pending soil sample, many MFC anodes distance each other, distance etc. between MFC negative electrode and EK negative electrode carries out suitable selection, this is the routine techniques knowledge that those skilled in the art possess, no longer it is described in detail at this。
Repair in the method for combined contamination soil at the electric power-fuel cell coupling device of the present invention, in described step S3, described new EK anode can be the conventional anodes in this area, it can be such as graphite rod, those skilled in the art can carry out suitable selection and determine, are no longer described in detail at this。
Repair in the method for combined contamination soil at the electric power-fuel cell coupling device of the present invention, the acetic acid aqueous solution that solution electrode is molar concentration 0.8-1.2mmol/L in described step S4, in described EK cathode cylinder。
Repairing in the method for combined contamination soil at the electric power-fuel cell coupling device of the present invention, in described step S4, the pH value controlling described EK cathode solution is 6-8, for instance can be 6,6.5,7,7.5 or 8, it is most preferred that be 6.5。
Wherein, described control device and method, with the control in step S2, are no longer described in detail at this。
Repair in the method for combined contamination soil at the electric power-fuel cell coupling device of the present invention, in described step S4, (the prolongation over time when the heavy metal in contaminated soil and organic contamination substrate concentration do not continue to reduce, reduce only small or stop reducing), namely the prolongation that the removal efficiency of last heavy metal and organic pollution is over time no longer changes, but when tending towards stability, just it is believed that complete to repair, now can stop operation。
Second aspect, the invention still further relates to described electric power-fuel cell coupling device and repairs the method for combined contamination soil purposes in soil remediation。
Finding through research, the described electric power of the present invention-fuel cell coupling device is repaired the method for combined contamination soil and is had excellent heavy metal and Organic substance removal efficiency, thus may be used in soil remediation field。
As mentioned above, the invention provides the method that a kind of electric power-microbiological fuel cell coupling device repairs combined contamination soil, described method is by unique method step, the electrode structure of uniqueness and/or the composite portfolio of various technological parameter and works in coordination with, thus achieving the repairing effect of good combined contamination soil, heavy metal and Organic substance have good removal effect simultaneously, especially the removal efficiency of heavy metal is very high, there is very excellent heavy metals removal effect, have a good application prospect and industrial production potential in environmental improvement method。
Accompanying drawing explanation
In order to be illustrated more clearly that the described apparatus and method of the present invention, below the accompanying drawing used required during embodiment is described is described and introduces。
Fig. 1 is the structural representation of the initial prosthetic device of the electric power used in the method for the invention step S1-S2。
Fig. 2 is the structural representation of the coupling prosthetic device used in the method for the invention step S3-S4。
Fig. 3 is the structural representation of EK anode of the present invention (when aperture therein is blocked upper, just become the MFC negative electrode in the coupling device of step S3-S4) and EK negative electrode。
Wherein, the corresponding relation of the elements/components of each numeral numbering and/or code name and device of the present invention is as follows: 1, DC source；2, EK anode or MFC negative electrode (refer to the EK anode in the initial prosthetic device of electric power in Fig. 1, and refer to the MFC negative electrode in coupling device in Fig. 2)；3, EK negative electrode；4, soil；5, new EK anode；6, MFC anode；7, external resistance；8, wire。
Detailed description of the invention
Below by specific embodiment, the present invention is described in detail; but the purposes of these exemplary embodiments and purpose are only used for enumerating the present invention; not the real protection scope of the present invention is constituted any type of any restriction, more non-protection scope of the present invention is limited thereto。
Wherein, with reference to shown in Fig. 1, the initial prosthetic device of electric power in step S1-S2 of the present invention includes two the hollow electrode cylinders being connected respectively with DC source 1, namely loads soil 4 (contaminated soil namely to be repaired) between EK anode 2 and EK negative electrode 3, EK anode 2 and EK negative electrode 3。
Wherein, with reference to shown in Fig. 3, described EK anode 2 and EK negative electrode 3 are hollow cylindrical, and are evenly distributed with the aperture that aperture is 1-3mm on the outer wall。In actual soil remediation process, the periphery of the barrel of described KE anode 2 and EK negative electrode 3 is wound with filter cloth to prevent soil from entering cylinder interior, solution electrode can be loaded in cylinder, the thickness of filter cloth should moderate (such as solution electrode will not ooze out loss, but the pollutant in soil can enter in cylinder through filter cloth at all multiactions such as electric field forces)。
Wherein, with reference to shown in Fig. 2, coupling device in step S3-S4 of the present invention includes DC source 1, the EK negative electrode 3 being connected with DC source 1, the new EK anode 5 being connected with DC source 1, this new EK anode 5 is placed on the inside of MFC negative electrode 2 and (is sealed by the aperture on the outer wall of original EK anode 2, or directly use exactly can by the effective pore-free electrode jacket casing of tight for the cylinder of EK anode 2 fit in the outside of EK anode 2, thus obtaining this MFC negative electrode 2), in described soil 4, namely many MFC anodes 6 are inserted between described EK negative electrode and MFC negative electrode 2, described MFC anode 6 sequentially couples together with wire 8, and be connected with MFC negative electrode 2 through external resistance 7。
Embodiment 1: the reparation to Cu-benzopyrene combined contamination soil
S1: make test soil sample
Contaminated soil is loaded (wherein in soil sample groove (soil sample groove is of a size of 12cm (length) × 5cm (width) × 10cm (height)), Cu and benzopyrene content respectively 200mg/kg and 20mg/kg, the biodiversity degree of soil is 25%), soil height is that 9-10cm is high, then two uniform hollow electrode cylinders with holes are inserted at the two ends on long limit, the outer wall of said two hollow electrode cylinder is evenly distributed with the aperture that aperture is 2mm, and at the outermost winding filter cloth of outer wall, said two hollow electrode cylinder connects positive pole and the negative pole of DC source respectively, as EK anode and EK negative electrode, two short side edge of described EK anode and EK cathode distance soil sample groove are 1cm；
S2: electric power is initially repaired
Loading the EDTA aqueous solution that concentration is 1mol/L in EK cathode tube, load deionized water in EK anode canister, open DC source and carry out energising reparation, power-on voltage is 5V, and the pH value of the pH value and EK cathode solution controlling EK anodic dissolution is 6.5；When the heavy metal in contaminated soil and organic contamination substrate concentration do not continue to reduce (prolongation over time reduces only small or stops reducing), electric power has initially been repaired；
S3: make coupling device
After electric power has initially been repaired, pour out the solution electrode in EK negative electrode, disconnect the connection of EK anode and DC power anode, and the soil between EK anode and EK negative electrode uniformly inserts 10 MFC anodes, closely it is set with an effective pore-free electrode cylinder to be sealed by the aperture on barrel in the outside of EK anode, thus original EK anode becomes MFC negative electrode, described 10 MFC anodes are sequentially connected with wire successively, and connect with described MFC negative electrode through the external resistance that resistance value is 100 Ω；Being inserted into a graphite rod as new EK anode at described MFC cathode tube, described new EK anode is connected with the positive pole of DC source, thus obtaining coupling device；
S4: coupling is repaired
Loading concentration in EK cathode tube is the acetic acid aqueous solution of 1mol/L, open DC source and carry out electric power-microbiological fuel cell coupling reparation, power-on voltage is 5V, and to control the pH value of solution in described EK cathode tube be 6.5, when the removal efficiency prolongation over time of last heavy metal and organic pollution no longer changes, but when tending towards stability, complete to repair。
After reparation completes, the Cu in contaminated soil and benzopyrene content is measured at this, finding the removal efficiency of Cu and benzopyrene content respectively 97.2% and 96.5%, removal efficiency computing formula is: removal efficiency (%)=[after initial amount (%)-reparations content]/initial amount (%) × 100% (lower together)。
Embodiment 2-3: the reparation to Cu-benzopyrene combined contamination soil
Embodiment 2: except the NTA aqueous solution that the EDTA aqueous solution in the EK cathode tube of step S2 replaces with same concentrations, other operation is all constant, thus being operated with the same way with embodiment 1, obtains embodiment 2。
Embodiment 3: except the EDTA aqueous solution in the EK cathode tube of step S2 is replaced with deionized water, other operation is all constant, thus being operated with the same way with embodiment 1, obtains embodiment 3。
The investigation result of solution electrode in EK cathode tube in step S2 is listed in the table below in 1 by embodiment 1-3。
Table 1
As can be seen here, in the restorative procedure of the present invention, when being added without EDTA aqueous solution or NTA aqueous solution in the EK cathode tube of step S2, the removal efficiency making Cu is substantially reduced, the removal efficiency of benzopyrene is affected less。This proof only adds specific solution electrode, could obtain best heavy metal removing effect。
Embodiment 4-8: the reparation to Cu-benzopyrene combined contamination soil
Except the pH value of the EK anodic dissolution changed in step S2 and EK cathode solution, other operation is all constant, thus being operated with the same way with embodiment 1 respectively, obtains embodiment 4-8；Wherein the removal efficiency result of used pH value, final Cu and benzopyrene is shown in table 2 below。
Table 2
As can be seen here, step S2 control extremely important for the pH value of EK anode electrode solution and EK cathode electrode solution, when both are 6.5, best heavy metal and Organic substance removal efficiency can be obtained, and when change therein any one time (even if another is still 6.5), but still result in heavy metal and organic removal efficiency has significant reduction, this proves that the pH value of anode electrode solution and cathode electrode solution has mutual promotion and synergism, only could obtain best collaborative facilitation effect when being all 6.5。
Embodiment 9: the reparation to Cu-benzopyrene combined contamination soil
Except in step S3 not except the outside of EK anode is closely set with an effective pore-free electrode cylinder and is sealed by the aperture on barrel, other operation is all constant, thus being operated with the same way with embodiment 1, obtains embodiment 9。
After running, measure the Cu in soil sample and benzopyrene content, it has been found that the removal efficiency of Cu and benzopyrene content respectively 75.4% and 94.9%。
As can be seen here, when not sealed by the aperture on EK anode barrel, the removal efficiency making heavy metal having obvious reduction, the clearance of benzopyrene also has a degree of decline simultaneously。This proof can produce beyond thought technique effect when being sealed by aperture。
Embodiment 10-13: the reparation to Cu-benzopyrene combined contamination soil
Except the pH value of the EK cathode solution changed in step S4, other operation is all constant, thus being operated with the same way with embodiment 1 respectively, obtains embodiment 10-13；Wherein the removal efficiency result of used pH value, final Cu and benzopyrene is shown in table 3 below。
Table 3
As can be seen here, in the restorative procedure of the present invention, in step S4, the pH value of EK cathode electrode solution controls that final removal efficiency is had significant impact, the removal effect while of could obtaining best heavy metal when being only 6.5 and be organic, and when changing, all causing that removal efficiency has significant reduction, especially organic removal efficiency has and significantly substantially reduces。
Embodiment 14: the reparation to Cu-benzopyrene combined contamination soil
It is the acetic acid aqueous solution of 1mol/L except not loading concentration in step s 4 in EK cathode cylinder and is not turned on DC source and is energized, but it is modified as outside the aqueous solution of nitric acid adding 1mol/L in MFC cathode tube, other operation is all constant (does not namely carry out direct current energising process in step S4, and do not add solution electrode in EK cathode tube, but in MFC cathode tube, add solution electrode), thus being operated with the same way with embodiment 1, obtain embodiment 14。
After running, measure the Cu in soil sample and benzopyrene content, it has been found that the removal efficiency of Cu and benzopyrene content respectively 89.4% and 93.9%。
The data of 1 are visible in conjunction with the embodiments, and in the 3rd step electric power-microorganism battery Combined Treatment process, if not applying electric field but being directly added into acid in MFC cathode tube, then the clearance of Cu and benzopyrene all decreases。This illustrates that the effect of EK is except producing acid and thinking that MFC negative electrode provides sour environment, it is also possible to stimulate the electrogenesis microorganism in soil that Organic substance is decomposed by weak electric field。Visible, the electric power-necessity of microorganism battery Combined Treatment, importance and unobviousness。
Embodiment 15: the reparation to Cu-benzopyrene combined contamination soil
(namely not carrying out coupling to repair) except only carrying out step S1-S2, other operation is all constant, thus repeating to implement embodiment 1, obtains embodiment 15。
After operation, measure the content of the Cu in soil sample and benzopyrene, it has been found that Cu removal efficiency and benzopyrene removal efficiency respectively 91.7% and 52.5%。
As can be seen here, when using single electric power elimination, heavy metal and organic removal efficiency have the dramatic drop-off of highly significant, and especially organic removal effect is greatly lowered。Thus demonstrate the electric power-necessity of microbiological fuel cell coupling device coupling, importance and unobviousness。
Embodiment 16: the reparation to Cu-benzopyrene combined contamination soil
(namely not carrying out electric power initially to repair) except only carrying out step S3-S4, other operation is all constant, thus repeating to implement embodiment 1, obtains embodiment 16
After operation, measure the content of the average Cu in soil sample and benzopyrene, it has been found that Cu removal efficiency and benzopyrene removal efficiency respectively 71.2% and 67.4%。
As can be seen here, when not carrying out electric power and initially repairing, heavy metal and organic removal efficiency all have and are significantly greatly lowered, and this proves the electric power-necessity of microbiological fuel cell coupling device coupling, importance and unobviousness further。
Can being found out apparently by above-mentioned all embodiments, when the electric power-microbiological fuel cell coupling device adopting the present invention repairs the method for combined pollution, its heavy metal and organic pollution all have significant removal efficiency。It can also be seen that, the removal efficiency that the method for the present invention to be significantly better than under similarity condition when being used alone electric power or microbiological fuel cell and change some technology characteristics (such as the solution electrode pH value of different step, the EK anode canister outer wall non-closure of aperture etc.), this demonstrate that the method for the present invention has more excellent pollutant removing effect than art methods, thus having good prospect and industrial production potential in actual applications。
Although for the purpose illustrated and describe, and describe structure and processing procedure shown in the above-mentioned embodiment of the present invention and accompanying drawing。But these are not detailed descriptions, can not scope of the invention is limited to this。For a person skilled in the art, the above-mentioned embodiment of the present invention can be made numerous modifications and variations, and these all of amendments and/or change all include within the claim limited range of the such as present invention, without departing from the scope and spirit of such as described claim invention defined。
Claims (9)
1. the method that electric power-fuel cell coupling device repairs combined contamination soil, described method comprises the steps:
S1: make test soil sample
In soil sample groove, load contaminated soil, and insert two hollow electrode cylinders with holes, connect positive pole and the negative pole of DC source respectively, as electric power anode (hereinafter referred to as EK anode) and electric power negative electrode (hereinafter referred to as EK negative electrode)；
S2: electric power is initially repaired
In EK cathode tube, load solution electrode, in EK anode canister, load deionized water, open DC source and carry out energising reparation, and control the pH value of EK anodic dissolution and the pH value of EK cathode solution；
S3: make coupling device
After electric power has initially been repaired, pour out the solution electrode in EK negative electrode, disconnect the connection of EK anode and DC power anode, and the soil between EK anode and EK negative electrode uniformly inserts many anode of microbial fuel cell (hereinafter referred to as MFC anode), aperture on EK anode outer wall is sealed, thus original EK anode becomes microorganism fuel cell cathode (hereinafter referred to as MFC negative electrode), described many MFC anodes are sequentially connected with wire successively, and connect with described MFC negative electrode through external resistance；Being inserted into an electrode as new electric power anode (hereinafter referred to as new EK anode) at described MFC cathode tube, described new EK anode is connected with the positive pole of DC source, thus obtaining coupling device；
S4: coupling is repaired
In EK cathode tube, load solution electrode, open DC source and carry out electric power-microbiological fuel cell coupling reparation, and control the pH value of solution in described EK cathode tube, until completing to repair。
2. the method that electric power-fuel cell coupling device as claimed in claim 1 repairs combined contamination soil, it is characterized in that: in described step S2, described solution electrode is the aqueous solution such as EDTA (ethylenediaminetetraacetic acid) aqueous solution or NTA (aminotriacetic acid), and the concentration of described solution electrode is 0.5-1.5mol/L。
3. the method that electric power-fuel cell coupling device as claimed in claim 1 or 2 repairs combined contamination soil, it is characterised in that: in described step S2, the pH value controlling EK anodic dissolution is 6-7, for instance can be 6,6.5 or 7；And the pH value controlling EK cathode solution is 6-8, for instance can be 6,6.5,7,7.5 or 8；The pH value most preferably controlling EK anodic dissolution and EK cathode solution is 6.5。
4. the method that the electric power-fuel cell coupling device stated such as any one of claim 1-3 repairs combined contamination soil, it is characterised in that: in described step S2, power-on voltage is 5-200V。
5. the method that the electric power-fuel cell coupling device stated such as any one of claim 1-4 repairs combined contamination soil, it is characterised in that: in described step S3, the resistance sizes of described external resistance is generally 10-1000 Ω。
6. the method that the electric power as described in any one of claim 1-5-fuel cell coupling device repairs combined contamination soil, it is characterized in that: in described step S4, the acetic acid aqueous solution that solution electrode is molar concentration 0.8-1.2mmol/L in described EK cathode cylinder。
7. the method that the electric power as described in any one of claim 1-6-fuel cell coupling device repairs combined contamination soil, it is characterised in that: in described step S4, the pH value controlling described EK cathode solution is 6-8。
8. the method that the electric power as described in any one of claim 1-6-fuel cell coupling device repairs combined contamination soil, it is characterised in that: in described step S4, the pH value controlling described EK cathode solution is 6.5。
9. the electric power as described in any one of claim 1-8-fuel cell coupling device repairs the method for combined contamination soil purposes in soil remediation。
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