CN106885833A - A kind of microbiological fuel cell and its preparation and the application in water quality early-warning - Google Patents
A kind of microbiological fuel cell and its preparation and the application in water quality early-warning Download PDFInfo
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Abstract
The invention provides a kind of microbiological fuel cell, including：Anode chamber, is communicated with anode inlet channel and anode outlet conduit in the anode chamber；It is arranged at the biological anode in the anode inlet channel；Relative to the cathode chamber that the anode chamber is set, negative electrode inlet channel and negative electrode outlet conduit are communicated with the cathode chamber；It is arranged at the biological-cathode in the negative electrode inlet channel；And it is arranged at the amberplex between the anode chamber and the cathode chamber；And preparation method, the microbiological fuel cell there is provided microorganism fuel cell are for water quality early-warning device and water quality early-warning method., using biological-cathode or biological anode as sensing unit, different water quality early-warning needs are met by according to different water quality selections, greatly improve the scope of application of microbiological fuel cell.
Description
Technical field
The present invention relates to water quality early-warning field, and in particular to a kind of microbiological fuel cell and its preparation and in water quality early-warning
In application.
Background technology
Water quality monitoring is all particularly significant for guarantee environment safety and health.Water quality early-warning based on biology sensor
Device (or water monitoring device) is because comprehensive water-body toxicity can be monitored, and react the toxic substance of bioavailability in water body
Matter concentration and receive significant attention.The work of microbiological fuel cell (Microbial Fuel Cell, abbreviation MFC) is depended on
Anodic oxidation reactionses and cathodic reduction reaction, and microorganism can be used as catalysis by anodic oxidation reactionses and cathodic reduction reaction
Agent.Water quality early-warning device based on principle of microbial fuel cells is using bioelectrode as sensing unit, and the electric current to export
Signal intensity is conducive to continuous on-line early warning as the index of the water body Poisoning material concentration that has that it's too late.
It is single as sensitivity using biological anode in the existing water quality early-warning device based on principle of microbial fuel cells
Unit.But the microbiological fuel cell water quality early-warning device that biological anode is sensing unit is solely based on, its water body requirement to be measured
Anaerobic condition, needs the background organic matter of higher concentration in water body, to maintain biological anode activity and export the electric current base of stabilization
Line.If oxygen concentration is higher in water body, its sensitivity can step-down；If lacking background organic matter in water body, outside is needed to add
Plus, so as to increased operating cost, especially when organic matter is added in the form of mixing with liquid, its diluting effect can also influence
The sensitivity of device.
The content of the invention
In view of the shortcomings of the prior art, the present invention is intended to provide a kind of microbiological fuel cell and its preparation and pre- in water quality
Application in police, using biological-cathode or biological anode as sensing unit, disclosure satisfy that not by according to different water quality selections
Same water quality early-warning needs, and greatly improves the scope of application of microbiological fuel cell.
One aspect of the present invention provides a kind of microbiological fuel cell, including：
Anode chamber, is communicated with anode inlet channel and anode outlet conduit in the anode chamber；
It is arranged at the biological anode in the anode inlet channel；
Relative to the cathode chamber that the anode chamber is set, negative electrode inlet channel is communicated with the cathode chamber and negative electrode goes out
Waterpipe；
It is arranged at the biological-cathode in the negative electrode inlet channel；And
It is arranged at the amberplex between the anode chamber and the cathode chamber.
Present inventor has found under study for action, by constructing the Microbial fuel with biological anode and biological-cathode
Battery, can be entered using biological-cathode or biological anode according to the oxygen content of water quality and content of organics selection as sensing unit
Row water quality early-warning, thus overcomes the microbiological fuel cell in the prior art with biological anode as sensing unit and is only capable of being applicable
The defect of hypoxemia and content of organics water body high.Further, it is respectively provided with by by the biological anode and biological-cathode
In in negative electrode inlet channel and anode inlet channel, anode chamber and cathode chamber are arranged at compared to by biological anode and biological-cathode
Interior, the liquid of inflow can more fully be penetrated and flow through biological-cathode and biological anode.
According to the present invention, the amberplex can be cation-exchange membrane or anion-exchange membrane, for separating
Anode chamber is stated with the cathode chamber.In the present invention, using cation-exchange membrane.
According to the present invention, biological anode is used to provide electronics primary source for biological-cathode, and biological-cathode is used to receive electricity
Son, so that circuit communication is completed, without additional power source.
According to the present invention, draw electric material can by the method including bundling or compressing and biological anode, biological-cathode or
Miscellaneous part in circuit is connected, described to draw the metal that electric material be relatively inert, preferably thread, ring plate shape or screw
The Titanium or gold of shape.The electric material that draws used in the present invention is ring-type titanium sheet.
One of the invention preferred embodiment in, the anode inlet channel and the side wall of the anode chamber or bottom
Portion is connected, and anode outlet conduit is connected with the top of the anode chamber；The side wall of the negative electrode inlet channel and the cathode chamber
Or bottom connects, the negative electrode outlet conduit is connected with the top of the cathode chamber.
It is of the invention another preferred embodiment in, the biological-cathode is with oxygen, proton, nitrate or dioxy
Change carbon is electron acceptor.
According to the present invention, when biological-cathode is with oxygen as electron acceptor, it is adaptable to which early warning oxygen content is high and content of organics
Low water body；During with proton as electron acceptor, it is adaptable to early warning low oxygen content and the low water body of content of organics；It is with nitrate
During electron acceptor, it is adaptable to early warning underground water or denitrification sewage；During with carbon dioxide as electron acceptor, it is adaptable to early warning hypoxemia
Content and the water body that content of organics is low but inorganic carbon source is abundant, such as water body of the anaerobic digestion process in sewage treatment process.
Another aspect of the present invention provides a kind of preparation method of microbiological fuel cell, including：
Microbiological fuel cell precast body is provided, the microbiological fuel cell precast body includes anode chamber, is arranged at institute
State the anode material in anode inlet channel, cathode chamber, the cathode material being arranged in the negative electrode inlet channel and setting
Amberplex between the anode chamber and the cathode chamber；
Anode mixture liquid and negative electrode mixed liquor are provided, the anode mixture liquid includes anolyte and inoculation liquid, the negative electrode
Mixed liquor includes catholyte and inoculation liquid；
The anode material of the microbiological fuel cell precast body and cathode material are electrically connected with, and the anode is mixed
Close liquid and be passed through anode inlet channel, flow through the anode material to penetrate, and the negative electrode mixed liquor is passed through negative electrode water inlet pipe
Road, the cathode material is flowed through to penetrate, by microbial acclimation make on the anode material grow anaerobic type microbial film with
And make to grow aerobic microbial film on the cathode material, until outputting current steadily；
Wherein, the anolyte has low oxygen content and a content of organics high, and the catholyte has elevated oxygen level and low
Content of organics.
Present inventor has found under study for action, makes the anode material and negative electrode of the microbiological fuel cell precast body
After material is electrically connected with, the anolyte of the low oxygen content and content of organics high is passed through anode inlet channel, to penetrate stream
The anode material is crossed, by microbial acclimation process, aerobic microorganism is dead, and anaerobic type microorganism is then on anode material
Homoepitaxial, forms anaerobic type microbial thin film, so as to constitute biological anode；At the same time, described will have elevated oxygen level and
The catholyte of low content of organics is passed through negative electrode inlet channel, and the cathode material is flowed through to penetrate, by microbial acclimation mistake
Journey, anaerobic type microorganism is dead, the aerobic microorganism then homoepitaxial on cathode material, forms aerobic microbial thin film,
So as to constitute biological-cathode；When microbial acclimation process is completed, the current signal of output tends towards stability.
By the above method, microbiological fuel cell can be simply and efficiently prepared, because negative electrode mixed liquor and anode are mixed
Close liquid and can continuously penetrate and flow through the cathode material and anode material, be conducive to the shape in whole anode material and cathode material
Into uniform and thin microbial film, the structure of microbial film is optimized.As long as and by the anode of anode inlet channel porch
Liquid switches to water sample to be measured, it is possible to which it is the microbiological fuel cell of sensing unit to be formed based on biological anode；On the other hand, only
The catholyte of negative electrode inlet channel porch is switched into water sample to be measured, it is possible to which it is sensing unit to be formed based on biological-cathode
Microbiological fuel cell.
According to the present invention, the anode material and cathode material can be plane or three-dimensional carbon material, including deposit, apply
Smear, the mode such as redox be modified after carbon material, can also be electric conductivity non-carbon material high and good biocompatibility,
Preferably carbon cloth or carbon felt, more preferably thickness are the carbon felt of 3mm.
According to the present invention, anolyte can be the artificial sewage prepared, such as by organic matter, trace element, vitamin etc.
The organic liquid mixture for being available for microbe survival of configuration；Can also be given up using low oxygen content and the reality that there are high-enriched organics
Water.
According to the present invention, catholyte can be the artificial sewage prepared, such as by inorganic salts, trace element, vitamin etc.
Configuration the inorganic mixed liquor for being available for microbe survival, it would however also be possible to employ elevated oxygen level and exist low concentration organic matter reality
Waste water.
It is of the invention another preferred embodiment in, the low oxygen content is less than 2mg/L, preferably 0mg/L-
1mg/L, the elevated oxygen level is more than 2mg/L, preferably 6mg/L-8mg/L；The low content of organics is less than 200mg/
L, preferably 0mg/L-50mg/L, the content of organics high are more than 200mg/L, preferably 500mg/L-1500mg/L.
It is of the invention another preferred embodiment in, the inoculation liquid is that can continue the microorganism of normal electricity production
The anode mixture liquid of fuel cell and the mixed solution of negative electrode mixed liquor, for example, run half a year and the Microbial fuel for normally producing electricity
The anode mixture liquid of battery and the mixed solution of negative electrode mixed liquor.In addition it is also possible to directly use the micro- life of aerobic screened
Thing and anaerobic type microorganism shorten the time of microbial acclimation, and then shorten respectively as negative electrode inoculation liquid and anode inoculation liquid
The preparation time of battery.
It is of the invention another preferred embodiment in, the inoculum concentration of the inoculation liquid is preferably based on the anode
The 5-15% of the cumulative volume of negative electrode mixed liquor in the cumulative volume or the cathode chamber of room Anodic mixed liquor.
It is of the invention another preferred embodiment in, the anode mixture liquid flows through the flow velocity of the anode material
It is 0.1mL/min-10mL/min；The flow velocity that the negative electrode mixed liquor flows through the cathode material is 0.1mL/min-10mL/
min。
According to the present invention, above-mentioned flow rates are conducive to avoiding that waterpower turbulence is smaller caused by flow velocity is too low, receive mass transfer
Limit causes the problem that the response time of device is more long and sensitivity is not high；And can avoid because flow velocity is too high, flow shear mistake
It is big to be unfavorable for that microorganism adheres on anode material and cathode material respectively, so that the problem that the startup time of device is more long.
Further aspect of the present invention provides a kind of water quality early-warning device, including：According to above-mentioned microbiological fuel cell and
Electric signal tape deck.
According to the present invention, the operation principle of the water quality early-warning device is as follows：Organic matter is made in the microorganism of biological anode
Electronics is produced with lower generation oxidation reaction, and is transferred to biological anode, biological-cathode, the electricity of biological-cathode are reached by external circuit
Sub- acceptor obtains the electronics, so as to form electric current while realizing the reduction process of electron acceptor.When water sample to be measured is passed through into anode
When inlet channel or negative electrode inlet channel carry out early warning, the unexpected appearance of water sample Poisoning material or the change of content of organics are equal
The activity of biological anode or biological-cathode can be respectively influenceed, causes the enhancing of current signal or decrease such that it is able to realize water quality
The purpose of early warning.
Present inventor has found under study for action, can be as sensitivity as a result of biological anode and biological-cathode
The microbiological fuel cell of unit, as the prewarning unit of water quality early-warning device, can widen the scope of application of water body to be measured, gram
Having taken traditional water quality early-warning device only can be with biological anode as sensing unit early warning oxygen content is low and content of organics water high
The defect of body.
On the other hand, the influence due to toxicant to biological anode and biological-cathode is to weaken current signal, is had
Influence of the machine thing to biological anode is to strengthen current signal, and the influence to biological-cathode is to weaken current signal.Work as water body
In containing active toxicant (such as agricultural chemicals, heavy metal, formaldehyde etc.) for suppressing anode microorganism catalysis anodic oxidation reactionses when,
The current signal of output reduces, and when the organic matter in water body increases simultaneously, can cause the current signal of output strengthens, both
Positive and negative counteracting, causes electric signal unchanged or even increases, it is impossible to effectively realize early warning.And organic matter and toxicant are to biological cloudy
Pole is inhibitory action, in these cases, remains to maintain accurate early warning.
According to the present invention, the electric signal tape deck is used for record current signal magnitude, specifically, can be by determining electricity
The voltage or direct measure electric current at two ends is hindered to realize.The electric signal tape deck can specifically be enumerated as electrochemical operation
Stand, the electric signal data sampling system such as electrical appliance, the universal meter such as bulb etc..Preferably, using electrochemical workstation as described
Electric signal tape deck, in addition to being able to record that the current signal size that battery is produced, additionally it is possible to apply electricity as additional power source
Pressure, with strengthening electric current signal, so as to the susceptibility of prior-warning device of increasing water quality.
According to the present invention, the water quality early-warning device also includes aerator and water pump.The aerator is used for the moon
Pole room provides oxygen as electron acceptor；The water pump is used to pump into electrode with constant flow velocity to anode chamber and cathode chamber respectively
Liquid or water sample to be measured.
Further aspect of the present invention provides a kind of method that above-mentioned water quality early-warning device carries out water quality early-warning, including：Make described
The biological anode and biological-cathode of microbiological fuel cell are electrically connected with by the electric signal tape deck, are remembered by electric signal
The change in electric of recording device carries out early warning,
When water sample to be measured has low oxygen content and content of organics high, the biological anode with the microbiological fuel cell is
Sensing unit carries out water quality early-warning；
When water sample to be measured has elevated oxygen level and low content of organics, the biological-cathode with the microbiological fuel cell is
Sensing unit carries out water quality early-warning.
One of the invention preferred embodiment in, be sensitive with the biological anode of the microbiological fuel cell
When unit carries out water quality early-warning, water sample to be measured is passed through the anode inlet channel, the biological anode is flowed through to penetrate；With
The biological-cathode of the microbiological fuel cell for sensing unit carry out water quality early-warning when, water sample to be measured is passed through the negative electrode and is entered
Waterpipe, the biological-cathode is flowed through to penetrate.
When water quality early-warning is carried out as sensing unit with the biological anode of the microbiological fuel cell, by anode mixture liquid
Water sample to be measured is replaced with, and is introduced into anode inlet channel, after forming stabling current, if the content of organics in water sample to be measured becomes
Height, the electronics of organic matter release becomes many, and current signal enhancing is capable of achieving the purpose of water quality early-warning.With the Microbial fuel
The biological-cathode of battery for sensing unit carry out water quality early-warning when, negative electrode mixed liquor is replaced with into water sample to be measured, and introduce negative electrode
In inlet channel, after forming stabling current, if the content of organics in cathode chamber is uprised, the electron acceptor as biological-cathode
Another electronics is originated, and makes electron acceptor that the ability reduction of electronics is obtained from biological-cathode, and current signal weakens, and can also realize water
The purpose of matter early warning.
Brief description of the drawings
Fig. 1 is the structural representation of microbiological fuel cell in the specific embodiment of the present invention.
Fig. 2 illustrates for the principle for carrying out water quality early-warning using water quality early-warning device in the specific embodiment of the present invention
Figure.
Fig. 3 be the specific embodiment of the present invention in use water quality early-warning device, with biological-cathode as sensing unit
Carry out the situation of change schematic diagram of the output current of water quality early-warning.
Fig. 4 be the specific embodiment of the present invention in use water quality early-warning device, with biological anode as sensing unit
Carry out the situation of change schematic diagram of the output current of water quality early-warning.
Fig. 5 be the specific embodiment of the present invention in use water quality early-warning device, with biological-cathode as sensing unit
Early warning contains the situation of change schematic diagram of the output current of the water sample to be measured of toxicant.
Fig. 6 be the specific embodiment of the present invention in use water quality early-warning device, with biological anode as sensing unit
Early warning contains the situation of change schematic diagram of the output current of the water sample to be measured of toxicant.
Description of reference numerals：1- microbiological fuel cells；2- biology anodes；3- biological-cathodes；4- amberplexes；5- sun
Pole inlet channel；6- negative electrode inlet channels；7- anode outlet conduits；8- negative electrode outlet conduits；9- electrochemical workstations；10- sun
Pole room；11- cathode chambers；12- aerators.
Specific embodiment
The present invention is conducted further description with embodiment below, it is noted that these embodiments are exemplary only,
Spirit and scope of the invention are not limited in any way.
Embodiment 1
In the present embodiment, with reference to Fig. 1, to the microbiological fuel cell 1 in the specific embodiment of the present invention
Structure is illustrated.A kind of microbiological fuel cell 1 as shown in Figure 1, it includes：
Anode chamber 10, is communicated with anode inlet channel 5 and anode outlet conduit 7 in the anode chamber 10；
It is arranged at the biological anode 2 in the anode inlet channel 5；
Cathode chamber 11, is communicated with negative electrode inlet channel 6 and negative electrode outlet conduit 8 on the cathode chamber 11；
It is arranged at the biological-cathode 3 in the negative electrode inlet channel 6；
And it is arranged at the cation-exchange membrane 4 between the anode chamber 10 and the cathode chamber 11.
Embodiment 2
In the present embodiment, with reference to Fig. 2, to the microbiological fuel cell 1 in the specific embodiment of the present invention
Preparation method is illustrated.
Microbiological fuel cell precast body is provided：Including anode chamber 10, the anode being arranged in the anode inlet channel 5
Material, cathode chamber 11, the cathode material being arranged in the negative electrode inlet channel 6 and it is arranged at the anode chamber 10 and described
Amberplex 4 between cathode chamber 11.The anode material and cathode material for using using the carbon felt that 3mm is thick, hand over by cation
Film is changed for amberplex 4.
Anolyte is provided (to addition 0.82g NaAc, 0.125g NH in the deionized water of 1000mL4Cl, 0.13g KCl,
0.332g NaH2PO4·2H2O, 1.032g Na2HPO4·12H2O, 12.5ml minor metallic element solution (composition is shown in Table 1) with
And the mixed liquor of 5ml vitamin solutions (composition is shown in Table 2)), catholyte (1.0g NaHCO are added in the deionized water of 1000mL3,
0.125g NH4Cl, 0.332g NaH2PO4·2H2O, 0.13g KCl, 1.032g Na2HPO4·12H2The micro gold of O, 12.5ml
The mixed liquor of category Element Solution and 5ml vitamin solutions) and an inoculation liquid (operation half a year and the MFC anodes for normally producing electricity
The mixed solution of mixed liquor and negative electrode mixed liquor).Wherein, the content of organics COD in anolyte is 700mg/L, and oxygen content is
0.5mg/L；Content of organics COD in catholyte is 20mg/L, and oxygen content is 8mg/L.The inoculation liquid is added separately to sun
In pole liquid and catholyte, negative electrode mixed liquor and anode mixture liquid are obtained, inoculum concentration is anode mixture liquid or negative electrode mixed liquor
10% (V/V).
By bundling the method for drawing electric material of ring-type titanium sheet, make the anode material of the microbiological fuel cell precast body
It is electrically connected with cathode material.The anode mixture liquid is passed through anode inlet channel 5, negative electrode mixed liquor is worn with 6mL/min
The cathode material is flowed through thoroughly, and anode mixture liquid is penetrated with 6mL/min and flow through the anode material, by microbial acclimation
Make to grow anaerobic type microbial film on the anode material and make to grow aerobic microbial film on the cathode material, treat defeated
The domestication of explanation microbial film is completed when going out current signal stable, that is, obtain the microbiological fuel cell 1 in the present embodiment.
The minor metallic element solution of table 1 is prepared
The micro-element solution of table 2 is prepared
Embodiment 3
In the present embodiment, with reference to Fig. 2, to the microbiological fuel cell 1 in the specific embodiment of the present invention
Preparation method is illustrated.The present embodiment provides a water quality early-warning device, and it is fired by the microorganism including being provided in embodiment 1
Material battery 1, an electrochemical workstation 9 and an aerator 12 are constituted.As shown in Figure 2, the biological anode of microbiological fuel cell 1
2 and biological-cathode 3 be electrically connected with by electrochemical workstation 9, organic matter is aoxidized under the microbial action of biological anode 2
Reaction produces electronics, and is transferred to biological anode 2, and biological-cathode 3 is reached by external circuit, and biological-cathode 3 sets equipped with aeration
Standby 12, oxygen is provided as electron acceptor to biological-cathode 3 for providing, the electronics is obtained, so as to form electric current realize simultaneously
The reduction process of electron acceptor.Additionally, water quality early-warning device also includes water pump；Water pump is used for respectively to anode chamber 10 and cathode chamber
11 pump into water sample to be measured with constant flow velocity.When by water sample to be measured be passed through anode inlet channel 5 or negative electrode inlet channel 6 carry out it is pre-
When alert, the change of content of organics can cause enhancing or the decrease of current signal in water sample such that it is able to realize water quality early-warning
Purpose.
Embodiment 4
Fig. 3 for the present embodiment provide one with biological-cathode as sensing unit carries out water quality early-warning when output current change
Situation schematic diagram.Specifically, the moment of battery current stabilization is designated as initial time, successively 0.2h, 1h after initial time,
To artificial addition 0.0005% in negative electrode mixed liquor, (V/V%, the cumulative volume with negative electrode mixed liquor in cathode chamber is during 1.8h
100% meter) formaldehyde (toxicant can be abbreviated as poisonous substance), the formaldehyde of 0.001% volume ratio and 0.0025% volume ratio first
Aldehyde, and record the situation of change of output current.From figure 3, it can be seen that when formaldehyde is not added, output current is more stable.When
After adding the formaldehyde of 0.0005-0.0025% volume ratios, electric current declines very soon, and with the increase of concentration of formaldehyde, the lower range of decrease
Degree increases.The water quality early-warning device PARA FORMALDEHYDE PRILLS(91,95) of the present embodiment has response higher, and after toxicant is removed, device performance can be
Recover in short time, when with biological-cathode as sensing unit, can and water body of without organic matter high as oxygen content company
Continuous on-line early warning, and sensitivity is higher than water quality early-warning device of the tradition based on biological anode.
Embodiment 5
Fig. 4 for the present embodiment provide one with biological anode as sensing unit carries out water quality early-warning when output current change
Situation schematic diagram.Specifically, the moment of battery current stabilization is designated as initial time, successively 0.5h, 1.2h after initial time,
To artificial addition 0.005% in anode mixed liquor, (V/V%, the cumulative volume with anode chamber's Anodic mixed liquor is 100% during 2.8h
Meter) formaldehyde, the formaldehyde of 0.01% volume ratio and 0.02% volume ratio formaldehyde, and record the situation of change of output current.From
Fig. 4 can be seen that when formaldehyde is not added, and output current is more stable.After adding the formaldehyde of 0.005-0.02% volume ratios, electricity
Flow down drop very fast, and with the increase of concentration of formaldehyde, fall increases.Illustrate the water quality early-warning device of the present embodiment to first
Aldehyde has response higher, and after toxicant is removed, device performance can recover in a short time, when with biological anode as sensitivity
During unit, it is possible to achieve continuous on-line early warning of the Anaerobic Rich containing organic matter water body.When pre- as sensing unit water quality with biological anode
Alarm device water body requirement anaerobism to be measured and organic matter abundance, and device sensitivity is less than based on the water that biological-cathode is sensing unit
Matter prior-warning device.
Embodiment 6
Fig. 5 for the present embodiment provide one with biological-cathode as sensing unit carries out water quality early-warning when output current change
Situation schematic diagram.Specifically, the moment of battery current stabilization is designated as initial time, it is mixed to negative electrode in 0.2h after initial time
The formaldehyde of 0.0005% (V/V%, the cumulative volume of negative electrode mixed liquor is counted as 100% with cathode chamber) of artificial addition in liquid is closed,
To the acetic acid of the formaldehyde of artificial addition 0.0005% and 0.2mM (0.0164g/L) in negative electrode mixed liquor during 0.9h after initial time
(organic matter), and record the situation of change of output current.It can be found that making because formaldehyde and acetic acid are suppression to biological-cathode
With the signal output of device can decline when organic matter and toxicant increase simultaneously, and this kind of situation is due to organic matter and toxicity
Material has inhibitory action to biological-cathode, it is ensured that device normal work.
Embodiment 7
Fig. 6 for the present embodiment provide one with biological anode as sensing unit carries out water quality early-warning when output current change
Situation schematic diagram.Specifically, the moment of battery current stabilization is designated as initial time, it is mixed to negative electrode in 0.2h after initial time
Close the formaldehyde of 0.0005% (V/V%, the cumulative volume of negative electrode mixed liquor is counted as 100% with cathode chamber) of artificial addition in liquid with
The acetic acid of 5mM, in 1h after initial time to the acetic acid of the formaldehyde of artificial addition 0.0005% and 0.3mM in negative electrode mixed liquor,
In 1.6h after initial time to the acetic acid of the formaldehyde of artificial addition 0.0005% and 10mM in negative electrode mixed liquor, and record output
The situation of change of electric current.It can be found that because formaldehyde and acetic acid are positive and negative negative function to biological-cathode, to same in water body to be measured
Change in electric when Shi Zengjia organic matters and toxicant, due to organic matter and toxicant biological anode can be produced it is positive and negative
Negative function, electric signal is reactionless, or even increases, early warning failure.
Although the present invention has been described in detail, it will be understood by those skilled in the art that in spirit and scope of the invention
Modification will be apparent.However, it should be understood that each side of present invention record, different specific embodiments
Each several part and the various features enumerated can be combined or all or part of exchange.In each above-mentioned specific embodiment, that
A little implementation methods with reference to another embodiment can be combined suitably with other embodiment, and this is by by this area skill
Art personnel are to understand.Additionally, it will be understood to those of skill in the art that description above is only the mode of example, not purport
In the limitation present invention.
Claims (10)
1. a kind of microbiological fuel cell, including：
Anode chamber, is communicated with anode inlet channel and anode outlet conduit in the anode chamber；
It is arranged at the biological anode in the anode inlet channel；
Relative to the cathode chamber that the anode chamber is set, negative electrode inlet channel and negative electrode outlet pipe are communicated with the cathode chamber
Road；
It is arranged at the biological-cathode in the negative electrode inlet channel；And
It is arranged at the amberplex between the anode chamber and the cathode chamber.
2. microbiological fuel cell according to claim 1, it is characterised in that the biological-cathode is with oxygen, proton, nitre
Hydrochlorate or carbon dioxide are electron acceptor.
3. a kind of preparation method of microbiological fuel cell according to claim 1 and 2, including：
Microbiological fuel cell precast body is provided, the microbiological fuel cell precast body includes anode chamber, is arranged at anode and enters
Anode material, cathode chamber in waterpipe, the cathode material being arranged in negative electrode inlet channel and it is arranged at the anode chamber
And the amberplex between the cathode chamber；
Anode mixture liquid and negative electrode mixed liquor are provided, the anode mixture liquid includes anolyte and inoculation liquid, the negative electrode mixing
Liquid includes catholyte and inoculation liquid；
The anode material of the microbiological fuel cell precast body and cathode material are electrically connected with, and by the anode mixture liquid
It is passed through the anode inlet channel, the anode material is flowed through to penetrate, and the negative electrode mixed liquor is passed through into the negative electrode
Waterpipe, the cathode material is flowed through to penetrate, and makes to grow anaerobic type microorganism on the anode material by microbial acclimation
Film and make on the cathode material grow aerobic microbial film, until outputting current steadily；
Wherein, the anolyte has low oxygen content and a content of organics high, and the catholyte has elevated oxygen level and low organic
Thing content.
4. preparation method according to claim 3, it is characterised in that the low oxygen content is less than 2mg/L, preferably
0mg/L-1mg/L；The elevated oxygen level is more than 2mg/L, preferably 6mg/L-8mg/L；The low content of organics be less than
200mg/L, preferably 0mg/L-50mg/L；The content of organics high is more than 200mg/L, preferably 500mg/L-
1500mg/L。
5. the preparation method according to claim 3 or 4, it is characterised in that the inoculation liquid is can to continue normal electricity production
Microbiological fuel cell the anode mixture liquid and the mixed solution of the negative electrode mixed liquor；The inoculum concentration of the inoculation liquid
It is preferably based on the total of negative electrode mixed liquor described in the cumulative volume of anode mixture liquid described in the anode chamber or the cathode chamber
The 5-15% of volume.
6. the preparation method according to any one in claim 3-5, it is characterised in that the anode mixture liquid flows through institute
The flow velocity for stating anode material is 0.1mL/min-10mL/min；The flow velocity that the negative electrode mixed liquor flows through the cathode material is
0.1mL/min-10mL/min。
7. a kind of water quality early-warning device, including：
Microbiological fuel cell according to claim 1 and 2 or the preparation according to any one in claim 3-6
Microbiological fuel cell prepared by method；And
Electric signal tape deck.
8. water quality early-warning device according to claim 7, it is characterised in that the electric signal tape deck is electrochemistry work
Stand.
9. a kind of method that water quality early-warning device using according to claim 7 or 8 carries out water quality early-warning, including：Make institute
The biological anode and biological-cathode for stating microbiological fuel cell are electrically connected with by the electric signal tape deck, by the electricity
The change in electric of signal recording apparatus carries out early warning,
When water sample to be measured has low oxygen content and content of organics high, the described biological anode with the microbiological fuel cell is
Sensing unit carries out water quality early-warning；
When water sample to be measured has elevated oxygen level and low content of organics, the biological-cathode with the microbiological fuel cell is
Sensing unit carries out water quality early-warning.
10. the method for water quality early-warning according to claim 9, it is characterised in that
When water quality early-warning is carried out as sensing unit with the described biological anode of the microbiological fuel cell, water sample to be measured is led to
Enter the anode inlet channel, the biological anode is flowed through to penetrate；
When water quality early-warning is carried out as sensing unit with the biological-cathode of the microbiological fuel cell, water sample to be measured is led to
Enter the negative electrode inlet channel, the biological-cathode is flowed through to penetrate.
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