CN113484397B - Bioelectrochemical method for detecting BOD in organic wastewater in real time in situ - Google Patents
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Abstract
The invention discloses a bioelectrochemical method for detecting BOD in organic wastewater in situ in real time, which comprises the following steps of 1): operating the bioelectrochemical reactor in a closed circuit in an MFC mode, and adding a seed solution to the anode chamber; 2): culturing the bioelectrode in a matrix solution until an electrode biological membrane is mature; 3): connecting a bioelectrochemical reactor with a potentiostat to construct a bioelectrochemical sensor and carrying out linear voltammetry scanning, wherein a bioelectrode is placed in a single organic matter solution containing different BOD concentrations, currents at different potentials are selected for fitting, an optimal signal output potential is determined, and a linear equation between an output current signal and the single organic matter concentration is obtained; 4): obtaining a linear equation of the output current signal and the concentration of each organic matter, and calculating the relative power generation rate of each organic matter relative to a single organic matter; 5): and calculating the relative power generation rate of the organic wastewater, and outputting an electric signal in the organic wastewater by the sensor to obtain the BOD concentration of the organic wastewater.
Description
Technical Field
The invention belongs to the field of biological sensors and water body pollutant detection, and relates to a pollutant detection technology based on bioelectrochemical reaction.
Background
BOD is the amount of dissolved oxygen required by aerobic microorganisms in wastewater to respire and consume organic pollutants, and is a key indicator for assessing the level of organic pollution and biodegradability in wastewater. Organic pollutants are one of the common pollutants in organic wastewater, cause water body hypoxia to destroy the ecology of the water body, and can be spread along with food chains to threaten human health. Existing organic pollution treatment technologies, such as electrochemical oxidation and biological processes, have different energy efficiencies for wastewater having different organic concentrations. Thus, real-time online BOD monitoring can avoid potential water quality hazards and improve the energy efficiency of the water treatment process.
The most common method for measuring BOD is the standard dilution method, which measures the difference of dissolved oxygen in the wastewater to be measured before and after 5 days of constant temperature culture to obtain the BOD content of the wastewater to be measured. Although the standard dilution method is widely used, its long measurement time (more than 5 days), complex measurement preparation process and offline test mode make it impossible to respond to contamination events in a timely manner. Furthermore, when the sample needs to be diluted, trace amounts of dissolved oxygen in the dilution water interfere with the measurement process, resulting in higher measurement errors (about)
). Therefore, the standard dilution method cannot meet the requirement of rapid and accurate BOD detection in actual wastewater monitoring and treatment.
The bioelectrochemical BOD sensor is a new BOD monitoring technology based on a bioelectrochemical reactor, and can detect the BOD of the wastewater through an electric signal generated by the bioelectrochemical reactor. Compared with the standard dilution method, the bioelectrochemical sensor usually utilizes the instant bioelectrochemical reaction and the BOD concentration of the organic wastewater to realize the BOD measurement of the organic wastewater, and does not need the whole BOD consumption process, thereby shortening the BOD detection time. The electrochemical biosensor does not need oxygen aeration and repeated microorganism inoculation, has wider detection range, and reduces the consumption of sample diluent, thereby simplifying the measurement process of BOD and reducing the test error.
At present, bioelectrochemical BOD sensors have different test methods using cell voltage, current density and coulomb quantity as electrical signals. The electrical signal of the bioelectrochemical BOD sensor is significantly affected by the organic matter content (including the type and composition ratio of the organic matter) in the wastewater, due to the different degrees to which different types of organic matter can be utilized by the electroactive microorganisms. At present, no bioelectrochemical BOD sensor can carry out BOD detection on actual organic wastewater with fluctuation of organic matter types and organic matter composition ratios. Furthermore, the developed bioelectrochemical BOD sensors have several drawbacks, respectively, which limit their use. Among them, the bioelectrochemical BOD sensor using the battery voltage and the current density as the electrical signals is also affected by other factors determining the BES performance, such as the structure of the reaction (including the electrode spacing, etc.), the cathode performance, and the measurement standards of different bioelectrochemical BOD sensors cannot be unified. Furthermore, the acquisition of electrical signals of cell voltage and current density requires the BES to run to a plateau in order to establish a linear relationship with the BOD concentration of the solution, which limits the detection range and measurement time of the sensor. Bioelectrochemical BOD sensors using coulomb quantities as electrical signals require long measurement times to completely consume the BOD to obtain the total charge flowing through the BES circuit. Although some researchers have attempted to reduce the reactor volume to reduce the time it takes for BOD to be completely consumed, the proportion of BOD consumed by planktonic microorganisms in the process increases, resulting in a decrease in accuracy and stability of the biosensor.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects of the prior art and provides a bioelectrochemical method for detecting BOD in organic wastewater in situ in real time. The method can carry out real-time online monitoring on the BOD concentration of the organic wastewater with complex components.
A bioelectrochemical method for detecting BOD in organic wastewater in situ in real time comprises the following steps:
step 1): operating a bioelectrochemical reactor in a closed circuit by taking a biological electrode as an anode and taking a non-biological electrode as a cathode through an MFC (micro-fuel cell) mode, adding an inoculation solution into an anode chamber of the bioelectrochemical reactor for inoculation, wherein the inoculation solution is a mixture of 50% of inoculum and 50% of matrix solution, the inoculation process lasts for five days, and the inoculation solution is replaced every day; the matrix solution was 50mM phosphate buffer containing 12.5mL L-1Trace minerals, 5mL L-1Vitamins and 1.50gBODL-1A bioavailable organic material; the inoculum is sewage containing microorganisms with electricity generation function;
step 2): after inoculation, culturing the bioelectrode in the matrix solution, and replacing the matrix solution every day until the electrode biofilm grows mature;
step 3): connecting a bioelectrochemical reactor with a potentiostat by a three-electrode system to construct a bioelectrochemical sensor and carrying out linear voltammetry scanning analysis, wherein a bioelectrode is placed in a single organic matter solution containing different BOD concentrations, scanning currents at different potentials are selected for linear fitting, the optimal signal output potential is determined, and a linear equation between the output current signal and the single organic matter concentration is obtained;
step 4): obtaining a linear equation of an output current signal and the concentration of each organic matter according to the optimal signal output potential, and calculating the relative power generation rate of each organic matter relative to the single organic matter;
step 5): and calculating the relative power generation rate of the organic wastewater according to the organic components of the organic wastewater and the output electric signals of the bioelectrochemical sensor in the organic wastewater so as to obtain the BOD concentration of the organic wastewater.
Preferably, the sewage containing the microorganisms with the electricity generating function in the step 1) is sewage containing the microorganisms with the electricity generating function in a natural environment or after artificial domestication, and comprises sewage of an anoxic section of an urban sewage treatment plant, slaughterhouse wastewater and effluent of a laboratory stable bioelectrochemical system.
Preferably, the microorganism with electricity generating function in step 1) refers to an electroactive microorganism with the ability of oxidizing organic matters to generate electricity, including microorganisms of genus Geobacter.
Preferably, the bioelectrochemical reactor in the step 1) is a reactor with a cubic two-chamber structure, wherein the anode chamber has an inner diameter of 35mm, a length of 40mm and a volume of 40mL, and the cathode chamber has an inner diameter of 35mm, a length of 20mm and a volume of 20 mL; the two chambers are separated by a cation exchange membrane.
Preferably, the step 1) is operated in a MFC closed circuit mode, which means that the bioelectrode and the non-bioelectrode are connected through a copper wire and an external resistor, in which electrochemical half-reactions can spontaneously occur on the bioelectrode and the non-bioelectrode, and electrons in the circuit are transferred from the bioelectrode to the non-bioelectrode.
Preferably, the step 2) of culturing the bioelectrode includes: after the inoculation process is finished, the bioelectrode is orderly batched in the matrix solutionPerforming mode culture, and replacing the matrix solution every day; wherein the cathode chamber solution was 50mM PBS solution containing 12.5mL L during the inoculation and culture-1Trace minerals, 5mL L-1Vitamins, which are replaced every 7 days; the mature growth of the electrode biological membrane means that the maximum voltage of the MFC constructed by the biological electrode can be repeatedly cycled for more than three periods, the cultured biological membrane can be considered to be mature, and the bioelectrochemical performance is relatively stable.
Preferably, the three-electrode system in step 3) is that a carbon-based material is used as a biological electrode, a foamed nickel air electrode is used as a non-biological electrode, and silver/silver chloride is used as a reference electrode, wherein the carbon-based material comprises a carbon brush, carbon cloth and a graphite sheet;
the linear voltammetric scanning analysis comprises the following steps: the potential of the bioelectrode is controlled by applying voltage between the bioelectrode and the reference electrode through a constant potential rectifier, linear volt-ampere scanning test is carried out, the scanning range is from-0.6V to-0.1V, and the scanning speed is 4mV s-1；
The linear fitting of the scanning currents at different potentials means that: and selecting the scanning current values of the bioelectrode in the single organic matter solution with gradient BOD concentration at different potentials for fitting, observing the fitting linearity of the current values at each potential, and selecting the potential value corresponding to the result with the highest linearity as the optimal electric signal output potential of the bioelectrochemical sensor.
Preferably, the calculating of the relative power generation rate of each organic matter relative to the single organic matter in the step 4) includes: and taking the ratio of the slope of the linear equation of the output current signal of the bioelectrochemical sensor and the concentration of each organic matter to the slope of the linear equation of the output signal of the bioelectrochemical sensor and the concentration of the single organic matter as the relative power generation rate of each organic matter relative to the single organic matter.
Preferably, in the step 5): calculating the relative power generation rate of the organic wastewater according to the components of the organic wastewater refers to that: the product of the relative power generation rate of different organic matters and the quantity of the matters is added to be used as the relative power generation rate of the organic wastewater.
Preferably, the single organic substance in step 3) and step 4) is sodium acetate, each organic substance in step 4) comprises sodium acetate, lactic acid and glucose, and the different organic substances in step 5) comprises sodium acetate, lactic acid and glucose.
The present application is further described below:
aiming at the problems in the prior art, a double-chamber bioelectrochemical reactor is constructed to be used as a bioelectrochemical biosensor, a bioelectrode is placed in a solution to be detected to carry out linear voltammetry scanning, and the BOD content of the organic wastewater is represented by selecting the current value of a diffusion section in the scanning process. The test method can quickly establish the relation between the BOD concentration of the organic wastewater and the electric signal of the bioelectrochemical reactor, shorten the test time and have less interference in the test process. In addition, the bioelectrochemical BOD sensor output signal correction method according to the relative power generation rate (eta) of the organic pollutants is firstly provided, so that the BOD concentration of the organic wastewater with different components can be accurately measured.
In order to solve the technical problem, the solution of the invention is as follows:
provides a bioelectrochemical method for detecting BOD in organic wastewater in situ in real time. The method can quickly obtain the electrical response of the BOD concentration of the organic wastewater, and can correct the electrical response according to the relative power generation rate of the organic wastewater, thereby realizing the real-time online monitoring of the BOD concentration of the organic wastewater with complex components.
(1) Linear voltammetric sweep detection method and potential selection of output electrical response
(2) Relative power production determination of single organic pollutants
(3) Bioelectrochemical sensor output signal correction method based on relative power generation rate
A bioelectrochemical method for real-time in-situ detection of BOD in organic wastewater can perform real-time on-line monitoring on BOD concentration of organic wastewater with complex components. Inoculating sewage containing electrogenesis functional microorganisms, and culturing a bioelectrode by using a bioavailable organic substance as a matrix. Linear voltammetric scanning is used to obtain the electrical response of the bioelectrode in organic wastewater. And selecting a proper electric response output potential to obtain a linear equation of the electric response signal of the bioelectrochemical sensor and the BOD concentration of the organic matters. And calculating the relative power generation rate of a certain organic matter according to a linear equation of the output current signal of the bioelectrochemical sensor and the concentration of other organic matters (BOD). And calculating the relative power generation rate of the organic wastewater according to the organic components (including the type of the organic matters and the amount ratio of different organic matters) of the organic wastewater, and correcting the output electric response of the bioelectrochemical sensor to obtain the BOD concentration of the organic wastewater.
Wherein the wastewater contains functional microorganisms required by a sensor system, such as microorganisms belonging to the genus Geobacter.
Wherein the bioelectrode is cultured in a solution containing bioavailable organic substances (including sodium acetate, lactic acid, glucose, etc.), the specific solution component is 50mM PBS, and 1.5g BOD L is added-1Bioavailable organic, 12.5mL L-1Mineral, 5mL L-1And (3) vitamins.
Wherein the sweep rate is 4mV s-1And scanning linear voltammetry scan in a range of-0.6V to-0.1V (vs. Ag/AgCl) to obtain the electric response of the bioelectrode in the organic wastewater.
Wherein, the potential selection needs to ensure the linearity R of the relation between the scanning current and the BOD concentration under the potential2Over 0.99.
The bioelectrode is used for testing the linear relation between the bioelectrochemical response and the BOD concentration in a solution of a certain organic matter with different BOD concentrations, and the ratio of the slope of a linear equation of the bioelectrochemical sensor output current signal and the concentration of the certain organic matter (BOD meter) and the slope of a linear equation of the bioelectrochemical sensor output signal and the concentration of sodium acetate (BOD meter) is used as the relative electrogenesis rate of each organic matter relative to the sodium acetate.
Wherein the relative power generation rate of the organic wastewater is obtained by adding products of relative power generation rates of different organic substances and the amount of the substances.
The present invention uses a dual-chamber reaction configuration to assemble a bioelectrochemical reactor that can be used for the culture of bioelectrodes required for a bioelectrochemical sensor and as a bioelectrochemical sensor. Carbon-based materials (including carbon brushes, carbon cloth,graphite flake, etc.) as a bioelectrode, a nickel foam air electrode as a non-bioelectrode, and silver/silver chloride as a reference electrode. Operating the bioelectrochemical reactor in an MFC mode in a closed loop, inoculating with sewage containing an electrogenic functional microorganism, and culturing a bioelectrode in the bioelectrochemical reactor. And testing the growth condition of the electrode biomembrane, and connecting the electrode biomembrane into a constant potential instrument in a three-electrode system after the growth of the biomembrane is determined to be mature, namely taking the bioelectrode as a working electrode, taking a foam nickel air electrode as a counter electrode and taking an Ag/AgCl electrode as a reference electrode. And (3) placing the electrode biomembrane in sodium acetate solutions with different BOD concentrations, performing linear voltammetry scanning analysis, selecting scanning currents at different potentials to perform linear fitting, determining the optimal signal output potential and obtaining a linear equation between the output current signal and the sodium acetate (BOD meter) concentration. The electrode biomembrane is placed in other organic matter solutions with different BOD concentrations to obtain a linear equation of the output current signal of the bioelectrochemical sensor and the concentrations of other organic matters (BOD meter). According to the slope of the linear equation corresponding to each type of organic matter and sodium acetate, the relative electrogenesis rate (eta) of each organic matter relative to sodium acetate is calculatedx). Estimating the relative power generation rate of the organic wastewater according to the components of the organic wastewater, and converting according to the output electric signals of the bioelectrochemical sensor in the organic wastewater to obtain the BOD concentration of the organic wastewater.
The double-chamber reactor structure in the invention refers to a reactor adopting a cubic two-chamber structure with a classical structure, wherein the anode chamber has the inner diameter of 35mm, the length of 40mm and the volume of 40mL, and the cathode chamber has the inner diameter of 35mm, the length of 20mm and the volume of 20 mL. The two chambers are separated by a cation exchange membrane.
The control of the potential of the biological electrode in the invention means that the potential of the biological electrode is controlled by applying a voltage between the biological electrode and the reference electrode when the reactor is used for detecting the BOD of the organic wastewater by utilizing the characteristic that the potential of the reference electrode in a solution is relatively stable (+197mVvs.
In the invention, the operation in the MFC mode means that the biological electrode and the non-biological electrode are connected with each other through a copper wire and an external resistor, in the mode, electrochemical half-reactions can be spontaneously carried out on the biological electrode and the non-biological electrode, and electrons in a circuit are transferred from the biological electrode (anode) to the non-biological electrode (cathode).
The electricity-generating functional microorganism in the invention refers to an electroactive microorganism with the capacity of generating electricity by oxidizing organic matters, and comprises microorganisms of Geobacter and the like.
The sewage containing the microorganisms with the electricity generating function in the invention refers to the sewage containing the microorganisms with the electricity generating function in natural environment or after artificial domestication, and comprises the sewage of an anoxic section of an urban sewage treatment plant, the wastewater of a slaughterhouse, the effluent of a laboratory stable bioelectrochemical reactor and the like.
The inoculation in the invention means that sewage containing electricity-generating functional microorganisms is added into a bioelectrochemical reactor to provide an initial source of the electricity-generating functional microorganisms for the bioelectrochemical enrichment process. The inoculum solution was a mixture of 50% (v/v) inoculum and 50% (v/v) matrix solution. The base solution was 50mM phosphate buffer (PBS; 11.466g L)-1Disodium hydrogen phosphate dodecahydrate, 2.75g L-1Sodium dihydrogen phosphate dihydrate) containing 12.5mL of L-1Trace minerals, 5mL L-1Vitamins and 1.50gBODL-1Biologically utilizable organic substance (sodium acetate, lactic acid, glucose, etc. can be selected). The inoculation process continued for five days with daily changes of the inoculation solution.
In the invention, the step of culturing the bioelectrode refers to that the bioelectrode is cultured in a matrix solution in a sequential batch mode after the inoculation process is finished, and the matrix solution is changed every day. During the incubation and inoculation, the cathode compartment solution was 50mM PBS containing 12.5mL L-1Trace minerals, 5mL L-1Vitamins, changed every 7 days.
In the invention, the growth maturity of the biological membrane means that the maximum voltage of the MFC constructed by the biological electrode can be repeatedly cycled for more than three periods, so that the cultured biological membrane can be considered to be mature in growth and the bioelectrochemical property is relatively stable.
The linear volt-ampere scanning analysis in the invention refers to that the potentiostat applies voltage between the bioelectrode and the reference electrode to control the potential of the bioelectrode and carry out the linear volt-ampere scanning test, and the scanning range is from-0.6V to-0.1V (vsAgCl), scanning speed of 4mV s-1。
The scanning current under different potentials is subjected to linear fitting, namely, the scanning current values of the bioelectrode in the sodium acetate solution with gradient BOD concentration under different potentials are selected for fitting, the linearity of the fitting of the current values under different potentials is observed, and the potential value corresponding to the result with the highest linearity is selected and used as the best electric signal output potential of the bioelectrochemical sensor.
In the invention, the calculation of the relative electrogenesis rate of each organic matter relative to sodium acetate means that the ratio of the slope of a linear equation of the output current signal of the bioelectrochemical sensor and the concentration of a certain organic matter (BOD meter) and the slope of a linear equation of the output signal of the bioelectrochemical sensor and the concentration of the sodium acetate (BOD meter) is taken as the relative electrogenesis rate of each organic matter relative to the sodium acetate.
The estimation of the relative power generation rate of the organic wastewater based on the components of the organic wastewater in the present invention means that the product of the relative power generation rates of different organic substances and the amount of the substance is added as the relative power generation rate of the organic wastewater.
The relation between the relative electricity generating rate of the specific substance or the organic wastewater and the slope of the detection marking line is that the product of the relative electricity generating rate and the slope of the detection marking line in the sodium acetate solution is the slope of the marking line when the substance (corresponding to the specific substance or the organic wastewater, the organic wastewater refers to the wastewater containing organic pollutants) is detected by a bioelectrochemical BOD sensor.
Description of the inventive principles:
the invention provides a bioelectrochemical method for detecting BOD in organic wastewater in situ in real time based on the bioelectrochemical oxidation capability of an electrode biomembrane on organic pollutants. The method comprises a bioelectrochemical sensor test method, test parameter selection and a signal correction method according to organic pollutant components of the organic wastewater.
We utilize a bioelectrochemical reactor to rapidly culture a bioelectrode having stable bioelectrochemical oxidation activity in an MFC mode. And by changing the wiring mode of the device, the bioelectrode is used as a working electrode of an electrochemical system, namely a detector of the bioelectrochemical sensor, and the electric response signal obtained in the bioelectrochemical test method is used for detecting the BOD of the organic wastewater.
In the method for testing the bioelectrochemical sensor and the method for selecting the test parameters, 4mV s is utilized-1The bioelectrochemical response of the electrode biomembrane to a single organic matter solution with different BOD concentrations is rapidly obtained by linear voltammetric scanning at the scanning speed. And selecting the scanning current values of the bioelectrode in the sodium acetate solution with gradient BOD concentration at different potentials for fitting, observing the fitting linearity of the current values at each potential, and selecting the potential value corresponding to the result with the highest linearity as the optimal electric signal output potential of the bioelectrochemical sensor.
After selecting proper electric signal output potential. The bioelectrode is tested in different organic matter solutions with different BOD concentrations to obtain a linear equation of the output current signal of the bioelectrochemical sensor and the concentrations of different organic matters (BOD meter), and the relative power generation rates of the different organic matters are calculated. And calculating the relative power generation rate of the organic wastewater according to the type of the organic matters in the organic wastewater and the ratio of the amount of different organic matters. And correcting the electrical response of the bioelectrochemical sensor in the organic wastewater according to the relative electrogenesis rate of the organic wastewater to obtain the accurate BOD concentration of the organic wastewater.
Compared with the prior art, the invention has the following beneficial effects:
1. and (3) representing the BOD content of the organic wastewater by selecting the current value of the diffusion section in the linear voltammetry scanning process. The method can quickly establish the relationship between the bioelectrochemical sensor electric signal and the BOD concentration of the organic wastewater, shorten the testing time and have high testing precision.
2. The method provides a concept of the relative power generation rate of organic matters and a method for calculating the relative power generation rate of wastewater containing various organic matters.
3. The test result of the bioelectrochemical sensor can be corrected according to the relative power generation rate of the organic wastewater, so that the bioelectrochemical sensor can be applied to BOD detection of actual organic wastewater with complex components.
Drawings
FIG. 1 is a voltage curve during the course of operating a bioelectrode in a MFC mode for the inoculation and cultivation of a bioelectrode in a bioelectrochemical reactor,
FIG. 2 is a linear relationship between the output current signal of the bioelectrochemical sensor and the concentration of different organic substances (BOD),
FIG. 3 shows the result of the bioelectrochemical sensor in the organic waste water with fixed phase to power generation rate,
FIG. 4 is a schematic view of a structure in which a bioelectrochemical reactor is constructed in different modes (in which FIG. 4-1 is a schematic view of a structure in which a bioelectrochemical reactor is constructed as an MFC reactor, and FIG. 4-2 is a schematic view of a structure in which a bioelectrochemical reactor is constructed as a bioelectrochemical sensor)
Reference numerals: 11-silver/silver chloride reference electrode, 12-bioelectrode, 13-foamed nickel air electrode, 14-anode chamber, 15-cathode chamber, 16-MFC reactor, 17-bioelectrochemical sensor, 18-resistor and 19-potentiostat.
Detailed Description
The invention is further described with reference to the following figures and specific examples, which are intended to better illustrate the invention and not to limit it.
Example 1
Using sludge water in an anoxic section of a sewage treatment plant as an inoculum, culturing the biological electrode for the detector in an MFC mode:
an external resistor 18 is connected between the anode and the cathode of the bioelectrochemical reactor, and the circuit is connected by copper wires to construct a microbial dye cell reactor (i.e., an MFC reactor) 16, as shown in fig. 4-1. The MFC reactor is inoculated with the anoxic sludge water, the inoculation process lasts for five days, then the culture is transferred into a sequential batch mode, and the substrate solution is changed every day. The voltage of the MFC was recorded by a digital data collection instrument (keygage model 34970 a).
Specifically, the method comprises the following steps:
the configuration of the reactor having a cubic two-chamber structure was constructed as a bioelectrochemical reactor having an anode chamber 14 of 35mm in inner diameter, 40mm in length and 40mL in volume and a cathode chamber 15 of 35mm in inner diameter, 20mm in length and 20mL in volume. The two chambers are separated by a cation exchange membrane.
With bioelectrode12 as an anode and a non-biological electrode 13 (a foam nickel air electrode is used as a non-biological electrode) as a cathode, the bioelectrochemical reactor is operated in a closed circuit by an MFC mode, and an inoculation solution is added into an anode chamber of the bioelectrochemical reactor for inoculation, wherein the inoculation solution is a mixture of 50 percent of inoculum and 50 percent of matrix solution, the inoculation process lasts for five days, and the inoculation solution is replaced every day; the matrix solution was 50mM phosphate buffer containing 12.5mL L-1Trace minerals, 5mL L-1Vitamins and 1.50gBODL-1A bioavailable organic material; the inoculum is sludge water in an anoxic section of a sewage plant;
after inoculation is completed, the bioelectrode is cultured in a matrix solution in a sequential batch mode, and the matrix solution is changed every day until the electrode biofilm grows mature. Wherein the cathode chamber solution is 50mM PBS solution containing 12.5mL L during inoculation and bioelectrode culture-1Trace minerals, 5mL L-1Vitamins, changed every 7 days.
The voltage profile of the MFC reactor during the seed culture in this example is shown in fig. 1.
According to the voltage of the MFC reactor, the culture condition of the bioelectrode for the detector can be judged. Typically, the voltage profile of the MFC reactor is stable and repeatable for more than 3 cycles after inoculation, i.e., the bioelectrode is considered to have grown relatively stable and can be used as a detector of a bioelectrochemical sensor for detection of contaminants. As in fig. 1, the bioelectrode satisfies the stable and repeatable cycle of voltage curve more than 3 at day 6, when it can be used as a detector of bioelectrochemical BOD sensor. The electrode culture process usually requires 4-9 days, and the performance of the bioelectrode is kept relatively stable after the bioelectrode is cultured to be mature (as shown in MFC voltage data of 6-9 days in the figure), so that the bioelectrode can be cultured in advance to ensure that the mature bioelectrode can be used when the pollutant detection requirement exists.
Example 2
The bioelectrode is a response current curve which is generated by LSV (namely linear sweep voltammetry) scanning in a solution (sodium acetate solution is taken as an example) containing fixed organic matter components with different BOD concentrations and changes along with the potential, and the most appropriate BOD detection process signal output potential is selected according to curve data.
After the electrode biofilm is matured, the external resistor of the MFC reactor is removed, and the bioelectrochemical reactor (including the matured bioelectrode and the reference electrode placed in the anode chamber and the counter electrode placed in the cathode chamber) is connected with a potentiostat, thereby constructing the bioelectrochemical sensor 17, as shown in fig. 4-2.
The bioelectrochemical reactor is connected with a potentiostat by a three-electrode system, and a graphite electrode (bioelectrode) 12, a foam nickel air electrode 13 and a silver/silver chloride electrode 11 are respectively used as a working electrode, a counter electrode and a reference electrode. By adding 12.5mL of sodium chloride-1Trace minerals and 5mL.L-1Sodium acetate is added into 50mMPBS of vitamin to prepare standard BOD-containing solution, and the concentration of the standard BOD solution is 20mgBOD L-1,40mgBOD L-1,80mgBOD L-1,100mgBOD L-1,120mgBOD L-1And 160mgBOD L-1. In the LSV scanning process, the bioelectrode potential is controlled by a constant potential rectifier to change from-0.6V (vs. Ag/AgCl) to-0.1V (vs. Ag/AgCl), and the scanning speed is set to be 4mV s-1. Wherein, during the operation of the bioelectrochemical sensor, the solution in the cathode chamber of the bioelectrochemical reactor is the same as that in the bioelectrode culturing and inoculating stage.
The current values at the potential positions of LSV scanning curve-0.4V, -0.3V, -0.2V and-0.1V are selected for fitting, and the linearity is respectively 0.923, 0.988, 0.990 and 0.992. Therefore, the-0.1V is selected as the optimal signal output potential of the bioelectrochemical sensor when BOD detection is carried out.
Example 3
The detection marked line of the bioelectrochemical sensor taking the invention as the detection method in a fixed organic component BOD solution (taking a sodium acetate solution as an example) is measured:
the bioelectrochemical reactor is connected with a potentiostat by a three-electrode system, and a graphite electrode (bioelectrode), a foam nickel air electrode and a silver/silver chloride electrode are respectively used as a working electrode, a counter electrode and a reference electrode. By adding 12.5mL of L-1Trace minerals and 5mL L-1Sodium acetate was added to 50mM PBS of vitamins to prepare a standard BOD-containing solution, and the concentrations of the standard BOD solutions were set to be 0.5mgBOD L, respectively-1，1mgBOD L-1，2mgBOD L-1，4mgBOD L-1，10mgBOD L-1，20mgBOD L-1,40mgBOD L-1,80mgBOD L-1,100mgBOD L-1,120mgBOD L-1，160mgBOD L-1，200mgBOD L-1，240mgBOD L-1And 320mgBOD L-1. And (3) selecting the current at-0.1V potential of each LSV scanning curve to perform linear fitting, determining the maximum linear detection range with the fitting degree linearity higher than 0.990, and obtaining a detection marking line corresponding to the organic component solution.
The detection line of the bioelectrode in different sodium acetate solutions is shown in figure 2.
The experimental result shows that the maximum linear detection range of the bioelectrode in the sodium acetate solution is 4-160 mgBOD L-1The detection linearity is higher than 0.997, and the detection marked line is that I is 0.00743 xcBOD+0.08, where I denotes current, cBODRefers to the BOD concentration.
Example 4
Measuring the relative electrogenesis rate (eta) of the specific organic matter solution and calculating the relative electrogenesis rate of the complex organic matter component solution:
the bioelectrochemical reactor is connected with a potentiostat by a three-electrode system, and a graphite electrode (bioelectrode), a foam nickel air electrode and a silver/silver chloride electrode are respectively used as a working electrode, a counter electrode and a reference electrode. By adding different types of organic matters (including sodium acetate, lactic acid, glucose and the like) into 50mMPBS, BOD solutions with different concentrations are prepared, and the concentration value comprises 20mgBOD L-1,40mgBOD L-1,80mgBOD L-1,100mgBOD L-1,120mgBOD L-1. And (3) selecting the current at-0.1V potential of each LSV scanning curve to perform linear fitting to obtain a detection marking line for the organic component solution.
Relative electrogenesis rate of a particular organic matter is calculated using glucose as an example, where the slope of the detection plot of the bioelectrode in a glucose solution is 0.0033, which is 44.4% of the slope (0.00743) of the detection plot of the bioelectrode in a sodium acetate solution, the relative electrogenesis rate of glucose is 0.444.
According to the relative power generation rate of different organic matters and the ratio of the amount of the different organic matters in the organic wastewater, the relative power generation rate of the organic wastewater with the mixed organic matters can be calculated. The output signal of the bioelectrochemical sensor can be quickly corrected by utilizing the relative electrogenesis rate of the organic wastewater, and the detection precision of the bioelectrode in the organic wastewater with different organic components is improved.
Example 5
The effectiveness of the method for correcting the detection result of the bioelectrochemical sensor by using the relative electrogenesis rate method in the actual wastewater test is as follows:
the bioelectrochemical reactor is connected with a potentiostat by a three-electrode system, and a graphite electrode (bioelectrode), a foam nickel air electrode and a silver/silver chloride electrode are respectively used as a working electrode, a counter electrode and a reference electrode. Seasoning plant wastewater was diluted with deionized water at different dilution ratios (organic wastewater volume/organic wastewater volume + dilution water volume) for testing. And (3) selecting the current at-0.1V potential of each LSV scanning curve to perform linear fitting.
The results of the test of the bioelectrochemical sensor on the wastewater of the seasoning factory with different dilution ratios are shown in fig. 3.
The results show that the current generated by the bioelectrochemical sensor shows a good linear relationship with the dilution ratio in the linear detection range of the bioelectrochemical sensor. The result shows that when the organic components of the organic wastewater are fixed, the relative electrogenesis rate is fixed, so that the bioelectrochemical sensor can correct the detection result by utilizing the relative electrogenesis rate to accurately detect the BOD concentration in the organic wastewater with different organic components.
Example 6
The bioelectrochemical sensor utilizes the actual detection effect of the BOD test method of the invention on the organic wastewater with different components
The bioelectrochemical reactor is connected with a potentiostat by a three-electrode system, and a graphite electrode (bioelectrode), a foam nickel air electrode and a silver/silver chloride electrode are respectively used as a working electrode, a counter electrode and a reference electrode. The components of the solution to be tested, the BOD concentration and other parameters are shown in Table 1.
TABLE 1 test results of bioelectrochemical sensors in organic wastewaters of different organic compositions
The result shows that the bioelectrochemical sensor accurately tests the BOD concentration in the organic wastewater with different components, and the maximum relative error in the test process is only 5.4%. As the detection time of the bioelectrochemical sensor using the detection method of the invention is less than 2.1 minutes and is far shorter than the test time (5 days) of the standard dilution method, the method is considered to be a new technology which is expected to replace the standard dilution method and realize the BOD detection in the real-time in-situ organic wastewater.
Claims (8)
1. A bioelectrochemical method for detecting BOD in organic wastewater in situ in real time comprises the following steps:
step 1): operating a bioelectrochemical reactor in a closed circuit by taking a biological electrode as an anode and taking a non-biological electrode as a cathode through an MFC (micro-fuel cell) mode, adding an inoculation solution into an anode chamber of the bioelectrochemical reactor for inoculation, wherein the inoculation solution is a mixture of 50% of inoculum and 50% of matrix solution, the inoculation process lasts for five days, and the inoculation solution is replaced every day; the matrix solution was 50mM phosphate buffer containing 12.5mL L-1Trace minerals, 5mL L-1Vitamins and 1.50gBODL-1A bioavailable organic material; the inoculum is sewage containing microorganisms with electricity generation function;
step 2): after inoculation, culturing the bioelectrode in the matrix solution, and replacing the matrix solution every day until the electrode biofilm grows mature;
step 3): connecting a bioelectrochemical reactor with a potentiostat by a three-electrode system to construct a bioelectrochemical sensor and carrying out linear voltammetry scanning analysis, wherein a bioelectrode is placed in a single organic matter solution containing different BOD concentrations, scanning currents at different potentials are selected for linear fitting, the optimal signal output potential is determined, and a linear equation between the output current signal and the single organic matter concentration is obtained;
step 4): obtaining a linear equation of an output current signal and the concentration of each organic matter according to the optimal signal output potential, and calculating the relative power generation rate of each organic matter relative to the single organic matter; wherein, the calculating the relative power generation rate of each organic matter relative to the single organic matter in the step 4) refers to: taking the ratio of the slope of the linear equation of the output current signal of the bioelectrochemical sensor and the concentration of each organic matter to the slope of the linear equation of the output signal of the bioelectrochemical sensor and the concentration of the single organic matter as the relative power generation rate of each organic matter relative to the single organic matter;
step 5): calculating the relative power generation rate of the organic wastewater and the output electric signal of the bioelectrochemical sensor in the organic wastewater according to the organic components of the organic wastewater, thereby obtaining the BOD concentration of the organic wastewater; wherein, in the step 5): calculating the relative power generation rate of the organic wastewater according to the components of the organic wastewater refers to that: the product of the relative power generation rate of different organic matters and the quantity of the matters is added to be used as the relative power generation rate of the organic wastewater.
2. The bioelectrochemical method according to claim 1, characterized in that: the sewage containing the microorganisms with the electricity generating function in the step 1) is sewage containing the microorganisms with the electricity generating function in a natural environment or after artificial domestication, and comprises sewage of an anoxic section of an urban sewage treatment plant, slaughterhouse wastewater and effluent of a laboratory stable bioelectrochemical system.
3. The bioelectrochemical method according to claim 2, characterized in that: the electricity generating functional microorganism in the step 1) refers to an electroactive microorganism with the capacity of generating electricity by oxidizing organic matters, and comprisesGeobacterA microorganism belonging to genus Haplodia.
4. The bioelectrochemical method according to claim 1, characterized in that: the bioelectrochemical reactor in the step 1) is a reactor with a cubic two-chamber structure, the inner diameter of an anode chamber is 35mm, the length of the anode chamber is 40mm, the volume of the anode chamber is 40mL, the inner diameter of a cathode chamber is 35mm, the length of the cathode chamber is 20mm, and the volume of the cathode chamber is 20 mL; the two chambers are separated by a cation exchange membrane.
5. The bioelectrochemical method according to claim 1, characterized in that: the step 1) is operated in an MFC closed circuit mode, which means that a biological electrode and a non-biological electrode are connected with an external resistor through a copper wire, electrochemical half-reactions can be spontaneously carried out on the biological electrode and the non-biological electrode in the mode, and electrons in a circuit are transferred from the biological electrode to the non-biological electrode.
6. The bioelectrochemical method according to claim 1, characterized in that: the step 2) of culturing the bioelectrode comprises the following steps: after the inoculation process is finished, sequentially culturing the bioelectrode in a matrix solution in a batch mode, and replacing the matrix solution every day; wherein the cathode chamber solution contains 12.5mL L of 50mM PBS solution during the inoculation and cultivation-1Trace minerals, 5mL L-1Vitamins, which are replaced every 7 days; the mature growth of the electrode biological membrane means that the maximum voltage of the MFC constructed by the biological electrode can be repeatedly cycled for more than three periods, the cultured biological membrane can be considered to be mature, and the bioelectrochemical performance is relatively stable.
7. The bioelectrochemical method according to claim 1, characterized in that: the three-electrode system in the step 3) is characterized in that a carbon-based material is used as a biological electrode, a foamed nickel air electrode is used as a non-biological electrode, and silver/silver chloride is used as a reference electrode, wherein the carbon-based material comprises a carbon brush, carbon cloth and a graphite sheet;
the linear voltammetric scanning analysis comprises the following steps: controlling the potential of the bioelectrode by applying voltage between the bioelectrode and the reference electrode through a constant potential rectifier, and carrying out linear volt-ampere scanning test, wherein the scanning range is from-0.6V to-0.1V, and the scanning speed is 4mV s-1；
The linear fitting of the scanning currents at different potentials means that: and selecting the scanning current values of the bioelectrode in the single organic matter solution with gradient BOD concentration at different potentials for fitting, observing the fitting linearity of the current values at each potential, and selecting the potential value corresponding to the result with the highest linearity as the optimal electric signal output potential of the bioelectrochemical sensor.
8. The bioelectrochemical method according to claim 1, characterized in that: the single organic matter in the step 3) and the step 4) is sodium acetate, each organic matter in the step 4) comprises sodium acetate, lactic acid and glucose, and the different organic matters in the step 5) comprise sodium acetate, lactic acid and glucose.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1360677A (en) * | 1999-07-07 | 2002-07-24 | 韩国科学技术研究院 | Electrochemical method for enrichment of microorganism, biosensor for analyzing organic substance and BOD |
| CN103326053A (en) * | 2013-05-23 | 2013-09-25 | 中国农业大学 | Multi-electrode microbial fuel cell system for researching microbial electrochemistry |
| CN103364469A (en) * | 2013-05-31 | 2013-10-23 | 内蒙古科技大学 | Device and method for quickly measuring BOD (biochemical oxygen demand) based on microbial electrolysis cell technology |
| WO2014082989A1 (en) * | 2012-11-28 | 2014-06-05 | Universitat De Girona | Bioelectrochemical water treatment and apparatus |
-
2021
- 2021-06-11 CN CN202110656570.6A patent/CN113484397B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1360677A (en) * | 1999-07-07 | 2002-07-24 | 韩国科学技术研究院 | Electrochemical method for enrichment of microorganism, biosensor for analyzing organic substance and BOD |
| WO2014082989A1 (en) * | 2012-11-28 | 2014-06-05 | Universitat De Girona | Bioelectrochemical water treatment and apparatus |
| CN103326053A (en) * | 2013-05-23 | 2013-09-25 | 中国农业大学 | Multi-electrode microbial fuel cell system for researching microbial electrochemistry |
| CN103364469A (en) * | 2013-05-31 | 2013-10-23 | 内蒙古科技大学 | Device and method for quickly measuring BOD (biochemical oxygen demand) based on microbial electrolysis cell technology |
Non-Patent Citations (2)
| Title |
|---|
| Effect of nitrate on electricity generation in single-chamber air cathode microbial fuel cells;Haobin Huang等;《Chemical Engineering Journal》;20171229;第327卷;第661-670页 * |
| 单室空气阴极微生物燃料电池硝酸根去除系统的建立和性能研究;黄浩斌等;《环境科学学报》;20190630;第39卷(第6期);第1739-1746页 * |
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