CN107045012B - A kind of microbiological fuel cell toxic sensors and operation method - Google Patents
A kind of microbiological fuel cell toxic sensors and operation method Download PDFInfo
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/18—Water
- G01N33/1813—Water specific cations in water, e.g. heavy metals
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/18—Water
- G01N33/186—Water using one or more living organisms, e.g. a fish
- G01N33/1866—Water using one or more living organisms, e.g. a fish using microorganisms
Abstract
A kind of microbiological fuel cell toxic sensors and operation method, belong to new energy and field of environment engineering technology.Reaction unit is dual chamber MFC, and centre is separated by cation-exchange membrane；Cathode chamber is nutrient solution and is aerated, while cathode chamber is connected to nutrition liquid bath via peristaltic pump and constitutes circulation line；Anode chamber is heavy metal wastewater thereby, and anode chamber is connected to heavy metal wastewater thereby slot via peristaltic pump and constitutes circulation line；The anode material of anode chamber uses carbon brush, and the cathode material of cathode chamber uses carbon felt；Cathode and anode are linked together by external resistor, and the both ends of external resistor connect voltage data acquisition system；Voltage can carry out toxicity detection after reaching stable in optimal conditions.Cathode chamber circulation autogamy nutrient solution is simultaneously aerated, and anode chamber recycles the waste water containing heavy metal.The system is detected from toxicant minimum concentration, and the removal rate after 12h is run in voltage stabilization can reach 90% or more.
Description
Technical field
The invention belongs to new energy and field of environment engineering technology, and in particular to a kind of new type of microbial fuel cell toxicity
Sensor, by this method can direct-on-line monitor the toxicant in water and design according to the percentage of inhibiting rate early warning dress
It sets.
Background technique
Heavy metal in water body is mainly derived from natural environment and human activity, and heavy metal is entered in environment and constantly carried out
Migration conversion, cause serious secondary pollution.Antibiotic (antibiotics) refers to antipathogen or other are active
A kind of secondary metabolite, can intervene a kind of chemical substance of other living cells development functions, it can be by microbial culture medium
With extraction or chemical synthesis and semi-synthetic compound in the metabolin of high animals and plants.The abuse of antibiotic makes to live extensively
Antibiotic in waste water and medical treatment, animal husbandry waste water severely exceeds, and sewage treatment plant is also below standard to the processing of antibiotic,
To the control that antibiotic is not stringent in effluent quality.
The general colorless and odorless of a small amount of heavy metal in water environment, is difficult to be noticeable, and heavy metal passes through long-term accumulation in life
It in object, is not easy to be degraded, threatens the life and health of the mankind.China belongs to the very serious country of heavy metal pollution, exceeded weight
Metal mainly has Cu, Zn, Cr, Cd, Pb, Hg, As etc., such as mainly from industrial pollution: plating, battery manufacture, process hides, chemical fertilizer work
Industry.The harm of human body is mainly swallowed by respiratory tract sucking, oral area intake and skin to be absorbed into human body, Cr, Cd etc. non-
Binding site on the necessary indispensable elements competitive substitution microorganism wall such as element and Cu, Zn, reacts with aglucon, generates murder by poisoning
Effect.Although the toxicity of heavy metal is early known, heavy metal pollution of water body is still under the main trend of global industry
Show increasingly severe trend.
The method for being currently used in detection Heavy Metals in Waters is more, mainly there is atomic absorption spectrography (AAS), atomic fluorescence spectrophotometry
Method, stripping voltammetry, inductively coupled plasma body method, biological enzyme inhibition, aptamer method, immunoassay etc..Mostly
Counting method due to its is costly, detection is time-consuming, sample need interference for being pre-treated to reduce signal etc. limitation and cannot
Carry out the application of large-scale experiment equipment.And the improvement of detection method in recent years also improves its testing conditions, time-consuming short, processing
Sample is simple, but there is still a need for further increase for the repeatability detected.Microbiological fuel cell is one has development prospect very much
Technology, it provides a kind of electricity production and the efficient combination method that carries out simultaneously of detection, and cardinal principle method is will to contain weight
The waste water of metal is placed in anode of microbial fuel cell room, under certain condition, what MFC electricity production or electric current and anode chamber were added
The concentration or micro organism quantity of metabolizable substrate are directly proportional, meanwhile, when heavy metal enters anode chamber, will lead under MFC electricity production
Drop, and the decline of electric current is with noxious material that there are certain correlations, and the concentration of heavy metal can be estimated according to this correlation.It is real
Test reactor anode and use opposite anaerobic environment, cathode uses Air Exposure, be used as electron acceptor using oxygen, oxygen inexpensively and
It is resourceful, it is extremely limited as the MFC of the electron acceptor current density generated and output power using it.This is because oxygen
Solubility is limited in water, and redox rate on the electrode is more equal to play the role of certain restrictions to MFC performance.
Studies have shown that heavy metal such as Cu, Zn in recent years etc. can be used for quickly detecting with single chamber MFC, Wu Feng (2009)
Research with Liu (2014) etc. fully confirms the feasibility that MFC is detected as heavy metal sensor.Due to MFC voltage and defeated
Power limited out needs to reconfigure waste water after having detected every time, increases voltage, insufficient for cleaning, and voltage restores effect
The bad reactor of fruit gives cleaning again or the method for repeatedly changing water.It is external to follow with the detection of high-concentration heavy metal waste water
Endless tube road, which is easy to be corroded, to be even easier to block, and should be replaced pipeline in time, be checked circuit.Therefore, which reads operation ring
Border is more demanding, while the extension for also limiting sensor is implemented and used, and dry sensor further need to be sought and be ground
Study carefully.
Summary of the invention
The present invention is provided under a kind of Optimal Parameters, voltage reaches stablize after, heavy metal concentration and reactor electricity production are presented
Good linear relationship.The MFC basic unit that this system uses is typical dual chamber MFC, and centre is separated by cation-exchange membrane.
Cathode chamber circulation autogamy nutrient solution is simultaneously aerated, and circulation various concentration heavy metal wastewater thereby to be measured in anode chamber's is simultaneously closed.The system passes through
The feasibility and accuracy of the situation of change design MFC sensor of external circuit electricity.
Microbiological fuel cell toxic sensors: reaction unit is dual chamber MFC, and centre is separated by cation-exchange membrane；Yin
Pole room is nutrient solution and is aerated, while cathode chamber is connected to nutrition liquid bath via peristaltic pump and constitutes circulation line；Anode chamber is
Heavy metal wastewater thereby, anode chamber are connected to heavy metal wastewater thereby slot via peristaltic pump and constitute circulation line；The anode material of anode chamber
Using carbon brush, carbon brush is crafted using carbon fiber and titanium silk as raw material, and the cathode material of cathode chamber uses carbon felt；Cathode and anode
It is linked together by external resistor, the both ends of external resistor connect voltage data acquisition system；
The main body of reaction unit of the present invention is made of organic glass；Battalion is provided using from water distribution for electricity production bacterium
Matrix is supported, anode electrode material uses carbon brush, and carbon brush is crafted using carbon fiber and titanium silk as raw material, and carbon brush is through acetone soak mistake
Night is placed in Muffle furnace 450 and heats 30min after taking-up；Cathode material uses carbon felt, and carbon felt material processing method is as follows: 1) will buy
To carbon felt be cut into after cube and be put into deionized water, then carbon felt submergence is impregnated 24 hours in deionized water；It will leaching
The material soaked is washed with deionized water 3-5 and hydrochloric acid is added thereto after, so that liquid level was not had material, after being sealed with preservative film
Conical flask is put into closet, material is allowed to impregnate 24 hours；4) it by hydrochloric acid soaked material deionized water rinse multipass, washes
The hydrochloric acid of its surface residual is removed, finally impregnates in deionized water again 24 hours, then uses deionized water cleaning material；
After assembling reactor, experimental data is acquired using capture card connection computer, primary every 1min acquisition
Voltage.Reactor is run at room temperature, adjusts temperature using water-bath.
Operation method, comprising the following steps:
Multiple groups dual chamber MFC reactor is established, to prevent certain reactors from running improper, every group of structure of reactor and material phase
Together.
1) autogamy culture solution: anode is used as substrate using glucose (1.0g/L), other compositions are as follows: NaAc (1.64g/
L)、NH4Cl(1.5g/L)、KCL(0.001g/L)、CaCl2(0.001g/L)、MgCl2(0.001g/L), phosphate buffer solution
(Na2HPO4 2.75g/L、KH2PO43.0g/L)；Cathode uses sodium bicarbonate (1.0g/L) for electron acceptor, other compositions
It is as follows: NaAc (1.64g/L), NH4Cl(1.5g/L)、KCL(0.001g/L)、CaCl2(0.001g/L)、MgCl2(0.001g/
L), phosphate buffer solution (Na2HPO4 2.75g/L、KH2PO43.0g/L)；Cathode and anode autogamy culture solution are ready-to-use,
Adjusting pH is 7.0 or so, and dark place can be reserved for 12h；
2) seed sludge and cultivate: startup stage cathode, which is all made of, is derived from the inoculation of water factory's aerobic activated sludge, and anode uses
Anaerobic activated sludge inoculation, takes supernatant after free settling, inoculation liquid using corresponding male/female pole autogamy culture solution with it is corresponding
Good/anaerobic sludge supernatant is the culture of 6:4 scale batch by the ratio between volume, and the period is 2~3 days, and battery can produce electricity after a week,
Then it is changed to continuous culture (intaking using peristaltic pump outer circulation), continuously culture solution uses pair in step (1) completely when culture
The autogamy culture solution answered is cultivated；The corresponding voltage of detection external resistance during the cultivation process；
External resistance is between 500~1500 Ω during above-mentioned culture, preferably 1000 Ω；Outer circulation rate 0.2~
Between 1.5mL/min, preferably
1.0mL/min。
It is preferred that: used microbiological fuel cell cycle period was at 3~5 days, and single MFC steady voltage is (generally in 200mv
It can be detected up and down).
3) relation curve of heavy metal various criterion concentration and inhibiting rate to be measured is established, cathode circulation is dirty during detecting herein
Water is constant, and anode circulation liquid is heavy metal (standard heavy metal concentration) and glucose solution (1.0g/ containing various criterion concentration
L), cycle detection is carried out, and calculates electricity (formula 1-2) and inhibiting rate (formula 1-3), circulation and external voltage are identical as step (2)；
Electricity calculates:
Q- electricity in formula, C；Average current, mA；t1,t2The start node and terminal of detection time)
Inhibiting rate calculates:
R- inhibiting rate in formula, %；QsStablize electricity, the electricity before heavy metal to be measured in detection time is not added for step (2)
Amount, C；QdElectricity after inhibition, for the electricity in detection time after addition detection heavy metal to be measured, C；When stablizing the detection of electricity
Between it is identical as the detection time of electricity after inhibition, wherein calculate inhibiting rate when, about in the calculating of electricityAverage current is adopted
It is calculated with the calculation of A=U/R.
4) then heavy metal containing sewage to be measured is added in glucose solution (1.0g/L) and carries out anode circulation, other with
Step (3) condition is identical, carries out detection inhibiting rate, so that the concentration of heavy metal containing sewage to be measured be calculated.
Experimental method:
1) determine external resistance using maximum power density: polarization curve (Polarization Curve) is analysis microorganism
The basic tool of fuel cell, for indicating the relationship of cell voltage and electric current, the general polarization curve by measuring total battery
To analyze the polarization phenomena of battery.Experiment is measured by galvanostatic method, and outer circulation rate chooses 1mL/min, by disconnecting dispatch from foreign news agency
Resistance makes open-circuit voltage reach maximum to reconnect variable rheostat, change dispatch from foreign news agency resistance value (10000 Ω, 5000 Ω, 3000 Ω, 2000 Ω,
1000 Ω, 800 Ω, 500 Ω, 300 Ω, 200 Ω, 100 Ω, 80 Ω, 50 Ω, 30 Ω, 10 Ω) it is recorded every 10min and stablizes electricity
It presses and calculates maximum power density.It calculates power density (Power Density) and uses area power density (formula 1-1), pass through
Polarization curve Slope Method obtains the internal resistance of battery, and the stability of battery is determined with this, and the ratio of battery similar in internal resistance is thought in experiment
It is more stable.
Calculation formula: area power density: PA=U2/ RA (formula 1-1)
P in formulaAArea power density (W/m2)；U- external resistance voltage, R- external resistance, Ω；A- single chamber effective area cm2；
Outer connecting resistance and the domestication of outer circulation rate: external resistance is chosen 500~1500 Ω and is tested, and calculates reactor
Maximum power density (Fig. 2), the power density when external resistance is 1000 Ω is maximum as the result is shown, determines that external resistance is 1000
Ω；
2) outer circulation rate choose different hydraulic detention times (HRT) 20,30,40,60,120min tested (table 1),
The result shows that power density when HRT is 60min is maximum, but the internal resistance in 20,30,40min is similar, it is believed that sensor
More stable, final to determine that HRT is 30min, being scaled outer circulation rate is 0.933mL/min.It is in later experiments that external resistance is true
It is set to 1000 Ω, outer circulation rate is determined as 0.933mL/min.
The domestication of the expression outer circulation rate of table 1
3) determination of detection time and scavenging period is the main indicator of MFC sensor, and detection time is too long, is not achieved fast
The purpose of speed detection, detection time is too short, and not exclusively, signal is unobvious, does not react the effect of sensor for reaction.Experiment passes through
Sensor detection time can be determined (Fig. 3) within the scope of certain chromium concn, such as choose 0.3~0.8mg/ of chromium ion concentration
L, Preliminary detection time are 40,60,80,100min.The result shows that (R when detection time is 60min2=0.9580) electricity and chromium
Concentration is in preferable linear relationship, determines that detection time is 60min.After detection is completed every time, sensor need to be cleaned, clearly
Washing lotion is cleaned using pure glucose solution (1.0g/L) (ready-to-use), when guaranteeing to detect next time residual heavy metal from
The influence of son.Every time clean to voltage be down to 60mV or so think cleaning complete, the time around here is determined as scavenging period, by scheming
3 know that scavenging period is about 10min.
5) determination of detection range: the relationship of observation inhibiting rate and heavy metal concentration is it is found that true when inhibiting rate is positive
It is set to the detection limit of chromium ion, thinks that anode chamber microbiological is almost inhibited when inhibiting rate tends to be constant, a huge sum of money at this time
Belong to concentration and be determined as maximum detectable concentration, thus can determine the detection range of every heavy metal species.
6) determination of linear equation: so that the inhibiting rate and heavy metal concentration in detection range are in fine routing sexual intercourse,
Thus linear equation is obtained.It can be applied to well in actual sewage according to this linear equation and heavy metal ion is carried out online
Detection, it will be appreciated, however, that actual sewage is different and experimental implementation, practical inhibiting rate can greatly increase, so should be appropriate
Reduce its detection range.On-line checking can be carried out to heavy metal by sensor according to the present invention, and it is dense to obtain heavy metal in real time
Degree can carry out appropriate adjusting to processing equipment according to heavy metal.Double-chamber microbiological fuel cell heavy metal sensor and previous
Research compares, and detection time is shorter, and detection range is bigger, and sensitivity is higher.
MFC on-line quick detection heavy metal method provided by the invention, is shown experimentally that, reactor, which is compared, relatively to be had down
Following advantage: 1) sensor can quickly detect the heavy metal concentration in water；2) the quick early warning water quality toxicity effect of sensor energy,
And effectively sewage disposal device is improved by the variation of electricity；3) reactor can not only achieve the purpose that early warning, to low
The heavy metal pollution of concentration, can be removed and fast quick-recovery within a certain period of time.
Detailed description of the invention
Fig. 1 shows the structures of sensor.
The domestication of Fig. 2 expression external resistance.
Fig. 3 indicates detection time optimization.
Fig. 4 indicates chromium ion detection and fitting.
Fig. 5 indicates cadmium ion detection and fitting.
Fig. 6 indicates copper ion detection and fitting.
Specific embodiment
Three example specific explanations inventions can hereinafter be passed through.Cr is hereinafter detected by application method of the invention6+、
Cd2+、Cu2+Two heavy metal species, and be compared with correlative study before.
Reactor configuration: reactor body used by this experiment is made of organic glass, and anode chamber is cylindric (straight
Diameter 3cm, long 3cm), effective volume (V) is 28cm3, ceiling there are two diameter 1cm aperture, usually blocked with rubber plug.Cathode chamber
Construct it is identical, single chamber effective area (A) be 7.065cm2.Proton exchange membrane (CMI-7000, Membranes are used among two Room
International Inc., USA) it separates.Nutrient matrix anode electrode material is provided using carbon using from water distribution for electricity production bacterium
Brush, carbon brush are crafted using carbon fiber and titanium silk as raw material, brush head long 3cm, diameter 3cm, the long 3cm of titanium silk handle, through acetone soak
Overnight, it is placed in Muffle furnace 450 after taking-up and heats 30min；Cathode material uses carbon felt, and carbon felt material processing method is as follows: 1) will
The carbon felt bought be cut into after the cube that side length is 0.5cm or so be put into it is to be processed in 250ml conical flask；2) to equipped with carbon felt
Deionized water is filled it up in conical flask, washes away the fine particle on its surface, repetitive operation, again to cone after deionized water becomes limpid
A certain amount of deionized water is added in shape bottle, guarantees that deionized water can submerge material, finally conical flask is put into closet and is allowed
Material is done after impregnating 24 hours to be handled in next step；3) soaked material is washed with deionized water to be added thereto after 3-5 times and is fitted
The dilute hydrochloric acid of amount, enables liquid level not have material, and conical flask is put into closet after being sealed with preservative film and makes material immersion 24 small
When after do in next step processing 4) by soaked material deionized water rinse multipass, wash away the hydrochloric acid of its surface residual, finally
Filled it up with again into conical flask conical flask is put into closet after deionized water allow material to impregnate 24 hours after it is clear with deionized water again
Wash after material add a small amount of deionized water submergence material put well it is spare.
After assembling reactor, experimental data is carried out using capture card (wound, Beijing are ground by 766 0B, middle Thailand) connection computer
Acquisition acquires primary voltage every 1min.Reactor is run at room temperature, using water-bath (DK-98-IIA, Stettlen, day
Saliva) adjust temperature.
Cultural method: establishing multiple groups dual chamber MFC reactor, to prevent certain reactors from running improper, every group of reactor knot
Structure is identical as material.
5) autogamy culture solution: anode is used as substrate using glucose (1.0g/L), and cathode uses sodium bicarbonate (1.0g/L)
For electron acceptor.Other constituents are identical: NaAc (1.64g/L), NH4Cl(1.5g/L)、KCL(0.001g/L)、CaCl2
(0.001g/L)、MgCl2(0.001g/L), phosphate buffer solution (Na2HPO4 2.75g/L、KH2PO43.0g/L) (autogamy is dirty
Water is ready-to-use, and adjusting pH is 7.0 or so, and dark place can be reserved for 12h).
2) seed sludge: startup stage cathode, which is all made of, is derived from the inoculation of water factory's aerobic activated sludge, and anode is living using anaerobism
Property sludge seeding (supernatant is taken after free settling).Inoculation liquid uses Yin/Yang pole from water distribution and good/anaerobic sludge supernatant volume
The ratio between be the culture of 6:4 scale batch (filling pole room with syringe every 2~3 days), battery can produce electricity after a week, be changed to continuous
It cultivates (being intake using peristaltic pump outer circulation), culture solution at this time uses the autogamy sewage in (1) to be cultivated completely.
3) external resistance preferably 1000 Ω between 500~1500 Ω during cultivating；Outer circulation rate is in 0.2~1.5mL/
Preferred 1.0mL/min between min.
Experimental method: 1) maximum power density: polarization curve (Polarization Curve) is analysis Microbial fuel
The basic tool of battery is generally divided by measuring the polarization curve of total battery for indicating the relationship of cell voltage and electric current
Analyse the polarization phenomena of battery.Experiment is measured by galvanostatic method, so that open-circuit voltage is reached maximum reconnection by disconnecting external resistance
Variable rheostat changes dispatch from foreign news agency resistance value (10000 Ω, 5000 Ω, 3000 Ω, 2000 Ω, 1000 Ω, 800 Ω, 500 Ω, 300 Ω, 200
Ω, 100 Ω, 80 Ω, 50 Ω, 30 Ω, 10 Ω) burning voltage is recorded every 10min and calculates maximum power density.Calculate power
Density (Power Density) uses area power density (formula 1-1), obtains the internal resistance of battery by polarization curve Slope Method,
The stability of battery is determined with this, experiment thinks that battery similar in internal resistance is more stable.
6) outer connecting resistance and the domestication of outer circulation rate: external resistance is chosen 500~1500 Ω and is tested, and calculates reactor
Maximum power density (Fig. 2), the power density when external resistance is 1000 Ω is maximum as the result is shown, determines that external resistance is 1000
Ω；Outer circulation rate choose different hydraulic detention times (HRT) 20,30,40,60,120min tested (table 1), as a result table
Bright, power density when HRT is 60min is maximum, but the internal resistance in 20,30,40min is similar, it is believed that and sensor is more stable,
Final to determine that HRT is 30min, being scaled outer circulation rate is 0.933mL/min.External resistance is determined as 1000 in later experiments
Ω, outer circulation rate are determined as 0.933mL/min.
The domestication of the expression outer circulation rate of table 1
3) determination of detection time and scavenging period is the main indicator of MFC sensor, and detection time is too long, is not achieved fast
The purpose of speed detection, detection time is too short, and not exclusively, signal is unobvious, does not react the effect of sensor for reaction.Experiment passes through
Sensor detection time can be determined (Fig. 3) within the scope of certain chromium concn, such as choose 0.3~0.8mg/ of chromium ion concentration
L, Preliminary detection time are 40,60,80,100min.The result shows that (R when detection time is 60min2=0.9580) electricity and chromium
Concentration is in preferable linear relationship, determines that detection time is 60min.After detection is completed every time, sensor need to be cleaned, clearly
Washing lotion is cleaned using pure glucose solution (1.0g/L) (ready-to-use), when guaranteeing to detect next time residual heavy metal from
The influence of son.Every time clean to voltage be down to 60mV or so think cleaning complete, the time around here is determined as scavenging period, by scheming
3 know that scavenging period is about 10min.
4) cathode circulation sewage is constant during heavy metal analysis, and anode circulation contains a different heavy metal concentration (standard huge sum of moneys
Belong to concentration) and glucose solution (1.0g/L) progress cycle detection, and calculate electricity (formula 1-2) and inhibiting rate (formula 1-3).
5) determination of detection range: the relationship of observation inhibiting rate and heavy metal concentration is it is found that true when inhibiting rate is positive
It is set to the detection limit of chromium ion, thinks that anode chamber microbiological is almost inhibited when inhibiting rate tends to be constant, chromium at this time is dense
Degree is determined as maximum detectable concentration, thus can determine the detection range of every heavy metal species.
6) determination of linear equation: inhibiting rate and heavy metal concentration in detection range are in fine routing sexual intercourse, thus
Obtain linear equation.It can be applied to well in actual sewage according to this linear equation and on-line checking is carried out to chromium ion, but
It is worth noting that, actual sewage is different and experimental implementation, practical inhibiting rate can greatly increase, so its inspection should be reduced suitably
Survey range.On-line checking can be carried out to heavy metal by sensor according to the present invention, and obtain heavy metal concentration in real time, according to weight
Metal can carry out appropriate adjusting to processing equipment.Double-chamber microbiological fuel cell heavy metal sensor is compared with previous research
Compared with detection time is shorter, and detection range is bigger, and sensitivity is higher.
Calculation formula: area power density: PA=U2/ RA (formula 1-1)
P in formulaAArea power density (W/m2)；R- external resistance, Ω；A- single chamber effective area cm2；
Electricity calculates:
Q- electricity in formula, C；Average current, mA；t1,t2Time interval)
Inhibiting rate calculates:
R- inhibiting rate in formula, %；QsStablize electricity, C；QdElectricity when detection, C；)
Cr in 1 water of example6+Detection
Sensor is impacted since chromium (VI) ion low concentration, records the situation of change of its voltage, and calculate suppression
Rate score (Fig. 4) processed.Wherein in detection range (0.3~10mg/L), heavy metal concentration presents linear well with inhibiting rate
Relationship, and obtain linear equation: RCr=5.879CCr+1.259(R2=0.9597).
Cd in 2 water of example2+Detection
Multiple groups dual chamber MFC reactor is established, test experience and fitting (Fig. 5) are similarly carried out.Wherein in detection range (0.4
~10mg/L) in, good linear relationship is presented in heavy metal concentration and inhibiting rate, and obtains linear equation: RCd=8.529CCd-
2.869(R2=0.9795).
Cu in 3 water of example2+Detection
Multiple groups dual chamber MFC reactor is established, test experience and fitting (Fig. 6) are similarly carried out.Inhibiting rate and copper ion concentration
Good linear relationship is presented always, but the blue precipitate of copper occurs in solution when copper ion concentration is 160mg/L, by
This can reduce the copper ion concentration in solution, so being more than that the copper concentration of 160mg/L cannot reuse the sensor and be examined
It surveys.The detection range of copper is 40~160mg/L, linear equation can be obtained in detection range: RCu=0.368CCu-10.197(R2=
0.9441)。
Sensor repeated experiment: in order to enable sensor longtime running, heavy metal sensor will aspire for stability accurately.Reaction
Device it is stable more than three months after, choose 8 groups of detection ranges in concentration detected (table 2).According to the line of each heavy metal
Property equation calculation detected value, each Concentration Testing is averaged three times, and calculates relative error.It can be seen from the table, four kinds of huge sum of moneys
The relative error of category is respectively less than 11%, illustrates DMFC sensor stabilization and energy longtime running.
The relative error of each heavy metal of table 2
。
Claims (5)
1. a kind of operation method of microbiological fuel cell toxic sensors, it is characterised in that the microbiological fuel cell poison
Property sensor response device be dual chamber MFC, centre separated by cation-exchange membrane；Cathode chamber is nutrient solution and is aerated, while yin
Pole room is connected to nutrition liquid bath via peristaltic pump and constitutes circulation line；Simultaneously for heavy metal wastewater thereby, anode chamber is via compacted for anode chamber
Dynamic pump is connected to heavy metal wastewater thereby slot and constitutes circulation line；The anode material of anode chamber uses carbon brush, carbon brush with carbon fiber and
Titanium silk is crafted for raw material, and the cathode material of cathode chamber uses carbon felt；Cathode and anode are linked together by external resistor,
The both ends of external resistor connect voltage data acquisition system；
The following steps are included:
(1) autogamy culture solution: anode is using 1.0g/L glucose as substrate, other compositions are as follows: NaAc 1.64g/L, NH4Cl
1.5g/L、KCl 0.001g/L、CaCl2 0.001g/L、MgCl2 0.001g/L、Na2HPO4 2.75g/L、KH2PO4 3.0g/
L；Cathode uses 1.0g/L sodium bicarbonate for electron acceptor, other compositions are as follows: NaAc 1.64g/L, NH4Cl 1.5g/L、
KCl 0.001g/L、CaCl2 0.001g/L、MgCl2 0.001g/L、Na2HPO4 2.75g/L、KH2PO43.0g/L；Cathode and
Anode autogamy culture solution is ready-to-use, and adjusting pH is 7.0 or so, and dark place can be reserved for 12h；
(2) seed sludge and cultivate: startup stage cathode, which is all made of, is derived from the inoculation of water factory's aerobic activated sludge, and anode uses anaerobism
Activated sludge inoculation, takes supernatant after free settling, inoculation liquid using corresponding male/female pole autogamy culture solution with it is corresponding it is good/
Anaerobic sludge supernatant is the culture of 6:4 scale batch by the ratio between volume, and the period is 2~3 days, and battery can produce electricity after a week, so
After be changed to continuous culture, culture solution uses the corresponding autogamy culture solution in step (1) to be cultivated completely when continuous culture；?
The corresponding voltage of external resistance is detected in incubation；
External resistance is between 500~1500 Ω during above-mentioned culture, and outer circulation rate is between 0.2~1.5mL/min；
(3) relation curve of heavy metal various criterion concentration and inhibiting rate to be measured is established, cathode circulation sewage during detecting herein
Constant, anode circulation liquid is the heavy metal containing various criterion concentration and 1.0g/L glucose solution, carries out cycle detection, and count
It calculates electricity (formula 1-2) and inhibiting rate (formula 1-3), circulation and external voltage are identical as step (2)；
Electricity calculates:
Q- electricity in formula, C；Average current, mA；t1,t2The start node and terminal of detection time)
Inhibiting rate calculates:
R- inhibiting rate in formula, %；QsStablize electricity, the electricity before heavy metal to be measured in detection time, C are not added for step (2)；
QdElectricity after inhibition, for the electricity in detection time after addition detection heavy metal to be measured, C；Stablize the detection time and suppression of electricity
The detection time of electricity is identical after system, in the calculating of electricityAverage current is calculated using the calculation of A=U/R；
(4) it then heavy metal containing sewage to be measured is added in 1.0g/L glucose solution carries out anode circulation, other and step
(3) condition is identical, carries out detection inhibiting rate, so that the concentration of heavy metal containing sewage to be measured be calculated.
2. according to method of claim 1, which is characterized in that outer 1000 Ω of connecting resistance；Outer circulation rate 1.0mL/min.
3. according to method of claim 1, which is characterized in that the determination of detection range: observation inhibiting rate and heavy metal concentration
Relationship, is determined as the detection limit of chromium ion when inhibiting rate is positive, think that anode chamber microbiological is several when inhibiting rate tends to be constant
It is inhibited, heavy metal concentration at this time is determined as maximum detectable concentration, thereby determines that the detection range of every heavy metal species.
4. according to method of claim 1, which is characterized in that the relation curve of heavy metal various criterion concentration and inhibiting rate to be measured
It is determined as linear equation: so that thus the inhibiting rate and heavy metal concentration in detection range obtain line in fine routing sexual intercourse
Property equation.
5. according to method of claim 1, which is characterized in that anode electrode material uses carbon brush, and carbon brush is with carbon fiber and titanium silk
It is crafted for raw material, carbon brush is stayed overnight through acetone soak, and Muffle furnace 450 is placed in after taking-up and heats 30min；Cathode material uses carbon
Felt, carbon felt material processing method are as follows: 1) carbon felt that will be bought, which is cut into after cube, is put into deionized water, then soaks carbon felt
Do not impregnate 24 hours in deionized water；Hydrochloric acid is added thereto after soaked material is washed with deionized water 3-5 times, makes liquid
Face can not there be material, conical flask is put into closet after being sealed with preservative film, material is allowed to impregnate 24 hours；4) by salt acid soak
Good material deionized water rinse multipass, washes away the hydrochloric acid of its surface residual, finally impregnates 24 hours in deionized water again,
Then deionized water cleaning material is used.
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| CN114594152A (en) * | 2022-03-25 | 2022-06-07 | 中国科学院重庆绿色智能技术研究院 | Method for real-time in-situ early warning of heavy metal pollution of water body |
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