CN114894863A - Organic wastewater BOD detection device and application and method thereof - Google Patents
Organic wastewater BOD detection device and application and method thereof Download PDFInfo
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- G—PHYSICS
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- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses an organic wastewater BOD detection device and application and a method thereof. The device comprises a microbial fuel cell reactor, wherein the microbial fuel cell reactor comprises an anode chamber, a cathode chamber and a lead; wherein a cathode material and a cathode electron acceptor are arranged in the cathode chamber, and the cathode electron acceptor comprises potassium ferricyanide; an anode material, microorganisms enriched on the anode material and an anode nutrient solution are arranged in the anode chamber, and the anode nutrient solution contains glucose, glutamic acid, a pH buffer system, mineral elements and vitamins; the anode material and the cathode material are both carbon felts, and the pretreatment step of the carbon felts comprises the following steps: modifying the carbon felt by using strong oxidizing acid; then washing and neutralizing until the water washing liquid is neutral, and burning. The device can stably run for several months, the measured data has better reproducibility, and the stability is obviously superior to that of the traditional microbial electrode method and BOD 5 And (4) measuring.
Description
Technical Field
The invention belongs to the technical field of water quality monitoring, and particularly relates to an organic wastewater BOD detection device and application and a method thereof.
Background
Organic pollutants are a main aspect of water body pollution, and Biochemical Oxygen Demand (BOD) is a comprehensive index reflecting the content of the organic pollutants in water and is also a key index for measuring water quality to ensure environmental safety and human health. The current national standard method is the traditional five-day biochemical method, however, the method is a time-consuming and labor-consuming technology, and a great deal of time is consumed in the response process. In addition, the limitation factor is the complicated operation, low reproducibility, high maintenance cost, generation of a large amount of waste, and the like. Therefore, the method is not suitable for process control and real-time monitoring of the water environment in daily wastewater (such as urban wastewater, domestic sewage and underground water) treatment, and the method is greatly developed, can be directly applied to water environment sites and real-time biochemical oxygen demand monitoring technology, promotes the current wastewater treatment method, and is of great significance in contributing to the protection of water resources.
The automatic on-line monitoring based on the real-time biochemical oxygen demand value developed in recent years can effectively reflect the water quality change process and measure the water quality condition, and is more ideal compared with the traditional BOD detection process. Many biochemical oxygen demand biosensors aimed at shortening the measurement time have been developed, including biosensors based on bacterial respiration, fixed bacterial oxygen consumption, enzymatic reactions in dead cells, and bioluminescence. These biosensors measure the biochemical oxygen demand in a short time, about 15 minutes to 1 hour, and show a high correlation with the biochemical oxygen demand. However, most of these methods are complicated and the measurements are performed ex situ and do not reflect real-time changes in water quality. Therefore, it is very urgent to develop a new technique with simple operation, time saving and strong universality to monitor BOD in a water sample in real time. Among them, the research of BOD sensors based on the operating principle of Microbial Fuel Cells (MFCs) has also been focused on by researchers in recent years.
Microbial Fuel Cells (MFCs) are devices that convert chemical energy directly into electrical energy using microorganisms as anode catalysts. The MFCs can directly degrade organic matters in water or sludge while converting electrons generated from the organic matters in a microbial metabolism process into electric signals, thereby obtaining electric energy. MFCs biosensors have significant advantages over other different types of biosensors; the device has the advantages of small volume, quick response, high accuracy, better repeatability, capability of realizing continuous on-line monitoring, no need of sample pretreatment and the like, simple and quick whole determination process, realization of automatic analysis, and realization of the advantages in the MFCs biosensing technology. Meanwhile, the MFCs biosensor can perform biosensing by utilizing an electric signal, fully utilizes weak electric energy generated by the MFCs, realizes real-time online monitoring of organic wastewater, and has certain practical application value. Therefore, the MFCs biosensing technology has good comprehensiveness, stability and energy recovery and wide application prospect.
Various researches in the related art show that the BOD concentration in the wastewater is in a linear relationship with the electrical signals output by the MFCs within a certain range. However, the BOD detection device in the related art has many defects of poor stability, low accuracy and the like, so that it cannot meet the requirement of rapid and accurate BOD detection in the actual wastewater monitoring and treatment process.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. For this reason, the present invention proposes an organic wastewater BOD detection apparatus having excellent stability and high accuracy.
The invention also provides an application of the device.
The invention also provides a method for detecting by using the device.
According to one aspect of the invention, an organic wastewater BOD detection device is provided, which comprises a microbial fuel cell reactor, wherein the microbial fuel cell reactor comprises an anode chamber, a cathode chamber and a lead, and the anode chamber and the cathode chamber are connected through the lead;
wherein a cathode material and a cathode electron acceptor are arranged in the cathode chamber, and the cathode electron acceptor comprises potassium ferricyanide;
an anode material, microorganisms enriched on the anode material and an anode nutrient solution are arranged in the anode chamber, the anode nutrient solution contains glucose, glutamic acid, a pH buffer system, mineral elements and vitamins, and the pH buffer system is used for adjusting the pH of the anode nutrient solution to 6.0-8.0;
the anode material and the cathode material are both carbon felts, and the pretreatment step of the carbon felts comprises the following steps: modifying the carbon felt by using strong oxidizing acid; then washing and neutralizing until the washing liquid is neutral, and burning.
According to a preferred embodiment of the present invention, at least the following advantages are provided: aiming at the defects of high cost, low performance and the like of the existing BOD sensor based on the microbial fuel cell, the invention provides a novel low-cost BOD rapid detection device for organic wastewater of a mediator-free double-chamber microbial fuel cell. The device takes potassium ferricyanide as a cathode electron acceptor, fully utilizes the characteristics of high oxidation-reduction potential, strong stability, no by-product in reaction and the like of the potassium ferricyanide, improves the performance of the BOD sensor, can realize the rapid detection of wastewater with high BOD concentration, simultaneously reduces electrons of the potassium ferricyanide into potassium ferrocyanide, changes cathode solution from yellow green into colorless, has less pollution to a diaphragm by the solution, and can ensure that the device can stably run for a longer time. The carbon felt is modified by soaking in strong oxidizing acid, so that the hydrophilicity of the surface of the electrode is improved, the electrochemical activity is further improved, and meanwhile, the wettability of the surface of the carbon felt can be obviously improved after the strong oxidizing acid is subjected to acidification treatment; the carbon felt pretreated by the scheme of the invention increases the specific surface area, porosity and oxygen-containing functional groups on the surface of the carbon felt, has good stability, excellent conductivity, high specific surface area and excellent electrochemical activity, and the surface can be subjected to pre-oxidation treatment; the carbon felt is adopted as the electrode material, so that the cost can be reduced, and meanwhile, the carbon felt pretreated by the scheme of the invention has a loose and porous structure and has a relatively large internal areaThe electrode has a plurality of gaps, the specific surface area of the electrode is increased to a certain extent, more microorganisms can be attached to the electrode for growth, the electrochemical activity is higher, the response time is shortened, the BOD real-time online detection can be realized, the accuracy of the detection result is improved (the error of the actual life wastewater detection result is less than 5 percent compared with the traditional five-day biochemical method), and the structure is more stable, so that the detection effect is more stable and reliable. The starting time of the BOD detection device adopting the scheme of the invention is not more than 192 h; not only has higher detection upper limit, but also has wider linear range, can accurately measure the organic wastewater with BOD concentration below 500mg/L without dilution, and has good linear relation (linear correlation coefficient R) between BOD concentration and voltage in the range of 50-500 mg/LBOD 2 0.9967), accurate quantification can be achieved; response is realized within 5min to 3h, and the method has good application prospect in actual online monitoring, and breaks through the defect that the traditional BOD detection device can only stay in the experimental stage; the device can stably run for months, the measured data has better reproducibility, and the stability is obviously superior to that of the traditional microbial electrode method and BOD 5 And (4) measuring.
In some preferred embodiments of the present invention, the strong oxidizing acid modification treatment is a soaking treatment with a strong oxidizing acid, and the soaking time is 3-6 hours; preferably about 4 hours.
In some preferred embodiments of the invention, the strong oxidizing acid is nitric acid.
In some preferred embodiments of the present invention, the nitric acid has a mass concentration of 30 to 40%.
In some preferred embodiments of the present invention, the nitric acid has a concentration of about 34% by mass.
In some preferred embodiments of the invention, the nitric acid is prepared by diluting commercially available concentrated nitric acid in a volume ratio of about 1: 1.
In some preferred embodiments of the present invention, the carbon felt is dried and then fired.
In some preferred embodiments of the present invention, the drying treatment is constant temperature vacuum drying.
In some preferred embodiments of the present invention, the drying temperature is 75 to 85 ℃.
In some preferred embodiments of the present invention, the drying temperature is about 80 ℃.
In some preferred embodiments of the present invention, the drying time is 10 to 14 hours.
In some preferred embodiments of the present invention, the drying time is about 12 hours.
In some preferred embodiments of the present invention, the burning temperature is 580 to 620 ℃ and the burning time is 1.5 to 2.5 hours.
In some more preferred embodiments of the present invention, the firing temperature is about 600 ℃ and the firing time is about 2 hours.
In some preferred embodiments of the present invention, the temperature increase rate of the burning is 1 to 3 ℃/min.
In some preferred embodiments of the present invention, the temperature increase rate of the burning is about 2 ℃/min.
In some preferred embodiments of the invention, the carbon felt has a porosity of no less than 90%.
In some more preferred embodiments of the present invention, the carbon felt has a porosity of between 90% and 98%.
In some more preferred embodiments of the invention, the carbon felt has a porosity of about 95%.
In some preferred embodiments of the invention, the length, width and thickness of the carbon felt are 1.5-2.5 cm, 1.5-2.5 cm and 0.5-1.5 cm in sequence.
In some more preferred embodiments of the present invention, the length, width and thickness of the carbon felt are 2cm, 2cm and 1cm in sequence.
In some preferred embodiments of the invention, the working area of the carbon felt is 10-15 cm 2 。
In some preferred embodiments of the invention, the working area of the carbon felt is about 12cm 2 。
In some preferred embodiments of the present invention, the carbon felt has a thickness of 8 to 12 mm.
In some preferred embodiments of the invention, the carbon felt has a thickness of about 10 mm.
In some preferred embodiments of the present invention, the distance between the carbon felts as the cathode and the anode is 1-3 cm.
In some preferred embodiments of the invention, the carbon felt spacing between the cathode and anode is about 2 cm.
In some preferred embodiments of the present invention, during the start-up phase, the microorganisms are inoculated on the anode material by an inoculum solution, and the inoculum solution is prepared by a process comprising the following steps: mixing anaerobic activated sludge with pretreatment liquid, sealing, oscillating at constant temperature for 20-28 h, and deoxidizing; the pretreatment solution contains glucose, glutamic acid, a pH buffer system, a mineral solution and a vitamin solution. The start-up time of the device can be as low as 96 hours by inoculation with the pretreated inoculum. The mixed strain in the anaerobic activated sludge is taken as an inoculation source of the electrochemical active microorganism, and compared with a microbial electrode using a single strain, the method has wider application range and linear range and can be used for measuring various samples or complex component samples in a larger concentration range.
In some preferred embodiments of the present invention, the constant temperature oscillation is performed at 34 to 36 ℃ and at a speed of 80 to 120 rpm.
In some more preferred embodiments of the invention, the constant temperature shaking is shaking at a speed of about 100rpm at about 35 ℃.
In some preferred embodiments of the present invention, the BOD value of the pretreatment solution is about 500 mg/L.
In some preferred embodiments of the present invention, the wire is externally connected with a resistor, and the resistance of the resistor is about 1000 Ω. The output power density increases with the increase of the resistance, and when the external resistance reaches 1000 omega, 68mW/m of the maximum power density is reached 2 Then the power density starts to decrease with further increase of the external resistance. This may be because the high external resistance limits the electron absorption through the circuit. Accordingly, the present invention has selectedThe external resistance is 1000 Ω to ensure the maximum output power density of the MFCs. The external resistor when the output power of the MFCs is maximum can improve the accuracy of BOD detection.
In some preferred embodiments of the present invention, the pH buffer system in the anode nutrient solution is used for adjusting the pH of the anode nutrient solution to 6.5-7.5.
In some preferred embodiments of the invention, a pH buffer system in the anode nutrient solution is used to adjust the pH of the anode nutrient solution to about 7.0.
In some preferred embodiments of the present invention, the concentration of glucose in the anode nutrient solution is 0.3 to 0.4 g/L.
In some preferred embodiments of the invention, the concentration of glucose in the anode nutrient solution is about 0.375 g/L.
In some preferred embodiments of the present invention, the concentration of glutamic acid in the anode nutrient solution is 0.3 to 0.4 g/L.
In some preferred embodiments of the present invention, the concentration of glutamic acid in the anode nutrient solution is about 0.375 g/L.
In some preferred embodiments of the present invention, the pH buffering system is a phosphate buffering system.
In some preferred embodiments of the present invention, the concentration of phosphate in the phosphate buffer system is 0.08 to 0.12 mol/L.
In some preferred embodiments of the present invention, the phosphate buffer system has a phosphate concentration of about 0.1 mol/L.
In some preferred embodiments of the invention, the mineral elements are added to the anode nutrient solution by a mixed solution containing the following components in a volume ratio of 1: 70-90:
in some preferred embodiments of the invention, the mineral elements are added to the anode nutrient solution by a mixed solution containing the following components in a volume ratio of 1: 70-90:
in some preferred embodiments of the invention, the vitamins are added into the anode nutrient solution through a mixed solution containing the following components in a volume ratio of 1: 100-300:
in some preferred embodiments of the invention, the vitamins are added into the anode nutrient solution through a mixed solution containing the following components in a volume ratio of 1: 100-300:
in some preferred embodiments of the present invention, the concentration of the potassium ferricyanide is 40 to 60 mmol/L.
In some preferred embodiments of the invention, the concentration of potassium ferricyanide is about 50 mmol/L.
In some preferred embodiments of the invention, the wire is a titanium wire. The titanium wire is used as a lead of a part contacting with the solution, the corrosion resistance of the titanium wire is better, the titanium wire is not easy to be corroded by the solution in the running process of the MFCs, the titanium wire cannot enter the solution, and the toxic action on microorganisms cannot be generated, so that the stability of the MFCs can be ensured.
In some preferred embodiments of the present invention, the diameter of the titanium wire is 0.5 to 1.5 mm.
In some preferred embodiments of the invention, the titanium wire has a diameter of about 1 mm. The titanium wire with the diameter of 1mm is selected as the lead of the part contacting the solution, the corrosion resistance of the titanium wire is better, the titanium wire is not easy to be corroded by the solution in the running process of the MFCs, the titanium wire cannot enter the solution, and the toxic effect on microorganisms cannot be generated, so that the stability of the MFCs can be ensured.
In some preferred embodiments of the invention, the microbial fuel cell reactor further comprises a Cation Exchange Membrane (CEM) for separating the cathode chamber from the anode chamber. The cation exchange membrane is adopted to replace an expensive proton exchange membrane, so that the production cost is greatly reduced, simultaneously, the interference between the two reaction chambers is effectively guaranteed, the device performance is more stable, the data result reproducibility is higher, and the real-time detection of the BOD of the wastewater is more favorable.
In some preferred embodiments of the invention, the cation exchange membrane is selected from the group consisting of CMI-7000 cation exchange membranes.
In some preferred embodiments of the invention, the cation exchange membrane is pretreated by:
soaking in hydrogen peroxide;
soaking in water at high temperature;
soaking in nitric acid at high temperature;
soaking in water at high temperature;
storing in moisture state for use.
In some preferred embodiments of the present invention, the temperature of the high-temperature soaking treatment is 75 to 85 ℃.
In some preferred embodiments of the present invention, the temperature of the high temperature soaking treatment is about 80 ℃.
In some preferred embodiments of the present invention, the time of the high temperature soaking treatment is 0.5 to 1.5 hours.
In some preferred embodiments of the present invention, the high temperature soaking treatment is performed for about 1 hour.
In some preferred embodiments of the present invention, in the pretreatment process of the cation exchange membrane, the mass concentration of hydrogen peroxide is 4-8%.
In some preferred embodiments of the present invention, during the pretreatment of the cation exchange membrane, the hydrogen peroxide solution has a mass concentration of about 5%.
In some preferred embodiments of the present invention, the mass concentration of the nitric acid in the pretreatment process of the cation exchange membrane is 8 to 12%.
In some preferred embodiments of the present invention, during the pretreatment of the cation exchange membrane, the hydrogen peroxide solution has a mass concentration of about 10%.
In some preferred embodiments of the present invention, the working area of the cation exchange membrane is 6-10 cm 2 。
In some preferred embodiments of the invention, the working area of the cation exchange membrane is about 7cm 2 。
In some preferred embodiments of the present invention, the volume of the microbial fuel cell reactor is 24 to 32ml, wherein the anode chamber and the cathode chamber are each 12 to 16 ml. The volume of the reactor of the scheme of the invention is only 28ml, and the carrying and the use are convenient.
In some preferred embodiments of the invention, the microbial fuel cell reactor has a volume of 28ml, wherein the anode and cathode compartments are each 14 ml. The volume of the reactor of the scheme of the invention is only 28ml, and the carrying and the use are convenient.
According to another aspect of the invention, the device is applied to the BOD online monitoring of the organic wastewater.
The application according to a preferred embodiment of the invention has at least the following advantageous effects: the scheme of the invention has good application prospect in the BOD on-line monitoring of the organic wastewater.
According to another aspect of the invention, a BOD detection method for organic wastewater is provided, which comprises the following steps:
and adding the water sample to be detected into the detection device, measuring the output voltage generated by the detection device, and substituting the voltage value into a linear equation to calculate the BOD value.
The method according to a preferred embodiment of the invention has at least the following advantageous effects: the BOD is directly calculated according to the voltage value, and compared with the traditional method which needs to convert the voltage into the electric quantity, the detection method is simpler and more convenient.
Drawings
The invention is further described with reference to the following figures and examples, in which:
FIG. 1 is a schematic structural view of an apparatus according to example 1 of the present invention;
FIG. 2 is a schematic diagram of a microbial fuel cell reactor according to example 1 of the present invention;
FIG. 3 is a side view of a microbial fuel cell reactor of example 1 of the present invention;
FIG. 4 is a diagram showing the result of the start-up time test of the apparatus according to embodiment 1 of the present invention;
FIG. 5 is a graph showing the open circuit voltage test results of the device in embodiment 1 of the present invention;
FIG. 6 is a schematic view showing the operation of a microbial fuel cell reactor according to example 1 of the present invention;
FIG. 7 is a graph of a standard curve measured in example 2 of the present invention;
FIG. 8 is a graph showing the linear relationship between test data of a simulation sample in example 2 of the present invention;
FIG. 9 is a graph showing the results of the microbial activity test at different BOD concentrations in example 2 of the present invention;
FIG. 10 is a graph showing the voltage and power output at different external resistors in example 2 of the present invention;
FIG. 11 is a graph of voltage and power output results at different pH's in example 2 of the present invention;
FIG. 12 is a graph showing the results of the stability test in example 3 of the present invention;
FIG. 13 is a graph showing the results of the stability test in comparative example 2 of the present invention.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention. The test methods used in the examples are all conventional methods unless otherwise specified; the materials, reagents and the like used are commercially available reagents and materials unless otherwise specified.
In the description of the present invention, unless otherwise explicitly defined, terms such as connected should be understood in a broad sense, and those skilled in the art can reasonably determine the specific meanings of the above terms in the present invention by combining the specific contents of the technical solutions.
In the description of the present invention, reference to the description of the terms "one embodiment," "some embodiments," "an illustrative embodiment," "an example," "a specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
In the description of the present invention, the meaning of "about" means plus or minus 2%, unless otherwise specified.
Example 1
The embodiment provides an organic wastewater BOD detection device and application thereof, as shown in figure 1, the device comprises a microbial fuel cell reactor, a liquid supply system, a liquid discharge system and a signal acquisition device (a computer provided with KickSart software), wherein the microbial fuel cell reactor (as shown in figures 2 and 3) comprises a shell (which is made of organic glass and has a volume of 28ml), an anode chamber (in a cylindrical configuration with a diameter of 3cm and a height of 2cm and a volume of 14 ml) positioned inside the shell, a cathode chamber (in a cylindrical configuration with a diameter of 3cm and a height of 2cm and a volume of 14 ml), and a cation exchange membrane (in a working area of 7cm and a working area of 14 ml) separating the anode chamber and the cathode chamber 2 ) A lead wire connecting the cathode chamber and the anode chamber and a resistance-changing box externally connected on the lead wire; wherein, cathode material (carbon fiber felt, 10mm (thickness) × 20mm × 20mm, working area 12 cm) is arranged in the cathode chamber 2 ) And a 50mmol/L potassium ferricyanide solution as an electron acceptor; anode material (carbon fiber felt, carbon for short) is arranged in the anode chamberFelt, 10mm (thickness) 20mm x 20mm, working area 12cm 2 ) Microorganisms (electrogenesis bacteria) enriched on the anode material and anode nutrient solution.
The anode nutrient solution is also called as an anolyte or Artificial sewage (AWW). It is used as a nutrient for microorganisms at the start-up stage of MFCs and as a solution to be tested at the BOD detection stage.
In the embodiment, artificial sewage is used as an anode nutrient solution, and each liter of artificial sewage contains: 0.375g/L glucose, 0.375g/L glutamic acid, 0.1mol/L phosphate buffered saline (0.1M PBS, pH 7.0), 12.5mL/L trace mineral solution, and 5mL/L vitamin solution (formulations of phosphate buffered saline, trace mineral solution, and vitamin solution are shown in tables 1-3).
TABLE 1 formulation of phosphate buffer solution
TABLE 2 formulation of the trace mineral solution
TABLE 3 formulation of vitamin solutions
The prepared anode nutrient solution is packaged in a conical flask, sealed by aluminum foil paper and then placed in an autoclave for sterilization for 30min, wherein the sterilization temperature is 121 ℃. And (4) refrigerating the sterilized anode nutrient solution in a refrigerator at the temperature of-4 ℃ for later use.
The total volume of the MFCs reactor was 28mL, the volumes of the anode and cathode chambers were 14mL, and the separator used CMI7000 Cation Exchange Membrane (CEM), 7cm membrane working area 2 . The cathode and anode electrode materials are both processed carbon felts with the thickness of 10mm, the porosity of 95 percent and the working area of 12cm 2 . The lead adopts a titanium wire with the diameter of 1mm, the electrode carbon felt is connected through the titanium wire, and the electrode distance between the anode and the cathode is 2 cm. The upper end of the cathode (anode) chamber is respectively provided with two circular hole channels with the diameter of 10mm, and the circular hole channels are connected by a silicone tube and used for adding and discharging fuel. The wire is connected with a resistance box (the measuring range is 0-9999 omega) and a Keithley universal meter to form a complete circuit, wherein the Keithley universal meter is connected with a computer, and data are continuously recorded through KickSart software. All reactors were operated in a thermostatted water bath at 35 ℃.
The electrode material adopts carbon felt which is pretreated by the following steps:
firstly, soaking a carbon felt of 10mm multiplied by 20mm in a 1+1 nitric acid solution (commercially available concentrated nitric acid solution is diluted with water by 1:1 (vol/vol)) for 4 hours, and modifying the carbon felt by soaking the carbon felt in strong oxidizing acid to improve the hydrophilicity of the surface of an electrode and further improve the electrochemical activity, and meanwhile, the wettability of the surface of the carbon felt can be obviously improved after the nitric acid acidification treatment.
Then taking out the carbon felt soaked in the acid, cleaning the carbon felt by using deionized water, soaking the carbon felt in l.0mol/L NaOH solution for 4h to neutralize the acid adsorbed by the carbon felt, and finally thoroughly washing the carbon felt by using the deionized water until the pH value is neutral. And drying the cleaned carbon felt in a constant-temperature vacuum drying oven at 80 ℃ for 12 h.
Finally, the crucible is sealed and placed in a muffle furnace to be burnt for 2 hours at the temperature rise speed of 2 ℃/min at the temperature of 600 ℃. After cooling, the electrode material is used as an MFCs electrode material for standby.
The carbon felt pretreated by the operation has excellent conductivity, high specific surface area and excellent electrochemical activity, and the surface can be subjected to preoxidation treatment; this not only increases the specific surface area, porosity and surface oxygen-containing functional groups of the carbon felt, but also provides the carbon felt with good stability in the electrolyte.
The cation exchange membrane used in the above operation is pretreated by the following steps:
two MFCsThe cell membrane was a CMI-7000 cation exchange membrane. First, the cation exchange membrane was placed in 5 wt% H 2 O 2 Soaking in water at 80 deg.c in constant temperature water bath for 1 hr to oxidize and clean the surface impurity of the cationic film; taking out the film, placing the film in deionized water, and carrying out water bath at the constant temperature of 80 ℃ for 1 h; then taking out the film, putting the film into a 10 wt% nitric acid solution, and carrying out constant-temperature water bath for 1h at the same temperature of 80 ℃; finally, putting the mixture into deionized water, and carrying out water bath at the constant temperature of 80 ℃ for 1 h; and placing the treated cation exchange membrane in ultrapure water for storage and standby.
The sludge inoculated by the electrogenic microorganisms is sludge in an anaerobic section of a secondary sedimentation tank of a certain sewage treatment plant in Jiangmen (the anaerobic sludge is in a black particle state, and the sludge taken back by a plastic barrel is placed in a 105 laboratory of the continuing education college for sealed preservation). In the starting stage of the MFCs, artificial wastewater with the BOD concentration of 500mg/L and containing the anode nutrient solution is used as inoculation liquid. Anaerobic sludge and inoculation liquid are put into a conical flask according to the volume ratio of 1:1 and sealed by a preservative film. And the pretreatment comprises the following steps: placing the mixed solution in a constant-temperature shaking table with the speed of 100rpm and the temperature of 35 ℃ for oscillation for 24h, introducing nitrogen to remove redundant dissolved oxygen before injecting the mixed solution into the anode chamber of the MFCs, intermittently injecting the inoculation solution into the anode chamber of the MFCs by adopting a peristaltic pump, suspending sample injection after the anode chamber is filled with the inoculation solution, and re-injecting the sample after the organic matters in the anode chamber are consumed by the microorganisms (namely, the voltage is firstly increased to reach the maximum value, then the voltage is slowly reduced to the reference value, and then the anode nutrient solution is replaced again to perform second period measurement). The electron acceptor used by the cathode of the MFCs during start-up is K 3 [Fe(CN) 6 ]The cathode potassium ferricyanide solution is replaced by one day in a period, and the potassium ferricyanide solution is prepared and used each time. The external resistor is 1000 omega, the voltage generated by the MFCs and the maximum value and the average value of the voltage every day are continuously recorded, and when the maximum value and the average value of the voltage in each period are stable, the starting voltage curve has no obvious change, so that the MFC is proved to be in a state of being in a stable state S The start-up was successful, i.e. the anode carbon felt had been enriched with sufficient electrogenic microorganisms. The specific test process is as follows:
inoculating anaerobic active granular sludge into the MFCs and feeding the MFCs by taking artificial wastewater as nutrient solution, wherein after the anode inoculation of the MFCs is replaced each time, chemical energy is converted into electric energy in the process of degrading organic matters by electrogenic microorganisms due to sufficient nutrient substances in the early stage, and the voltage of the MFCs gradually rises to a peak value; with the gradual reduction of nutrients and the continuous accumulation of metabolites, the voltage of the MFCs has a tendency of sharp drop; eventually the nutrients slowly deplete and the voltage slowly drops to baseline. The voltage peaks per cycle of MFCs are shown in fig. 4. As can be seen from fig. 4, as the start-up time increases, the voltage peaks of the MFCs gradually increase and gradually stabilize, and the start-up voltage peaks are about 550 mV. And at 96h, the starting voltage of the MFCs basically reaches a stable value, which indicates that enough electrogenesis microbial communities are enriched on the carbon felt of the anode chamber, and the MFCs device is successfully started. Because the nutrients in the artificial sewage are sufficient, the anaerobic sludge is injected into the artificial sewage, the artificial sewage is fully and uniformly mixed with the anaerobic sludge after oscillation at constant temperature, and the inoculation liquid is replaced in time in each period, the device can be started successfully within 96h (192 h is required if the inoculation of the non-pretreated microorganisms is adopted)
The open circuit voltage of MFCs is one of the important indicators for measuring the performance of batteries. And when the MFCs reactor is successfully started, disconnecting the external resistor to change the device from a closed loop to an open circuit state and keeping the device in the open circuit state for 1h, then using an electrochemical workstation to measure the open circuit voltage, wherein in the measuring process, the working electrode clamps the anode, the reference electrode and the auxiliary electrode clamps the cathode, the time is set to 3600s, the sampling interval is 10s, and the open circuit voltage of the MFCs at the time of starting for 96h is measured, and the result is shown in FIG. 5. As can be seen from fig. 5, the open circuit voltage of the MFCs reactor tends to be stable around 20min, and is about 624mV, which indicates that the MFCs is successfully started and the device has good stability.
In the above-mentioned apparatus, the operating principle of the microbial fuel reactor is as shown in fig. 6:
the MFCs are devices which take microorganisms as anode catalysts and can directly convert chemical energy of degradable organic matters in wastewater into electric energy. The device consists of load microorganisms (mainly electrogenesis bacteria), an anode and a cathode, and the working process can be summarized as follows: the anode organic matter generates proton and electron under the action of the oxidation decomposition of microbe, and the electron passes throughRespiratory enzymes (NADH) and NAD + Transferring in cell, and transferring to anode via wire, membrane protein contact or electron mediator and other extracellular electron transfer mechanism, transferring to cathode via external circuit, transferring proton in electrolyte from anode chamber to cathode chamber driven by electric field force and concentration difference, and transferring electron and proton to electron acceptor [ Fe (CN) 6 ] 3- A reduction reaction takes place.
The theoretical potential of the microbial fuel cell is as follows:
anode: c 6 H 12 O 6 +6H 2 O＝24e - +24H + +6CO 2 E 0 0.428V (formula 1-1)
Cathode: [ Fe (CN) 6 ] 3- +e - ＝[Fe(CN) 6 ] 4- E 0 0.361V (formula 1-2)
The invention reduces the volume of the reactor to 14ml, shortens the electrode spacing to 2cm, adopts carbon felt as an electrode material to replace expensive metal catalyst, adopts titanium wire with better corrosion resistance as a lead, reduces the influence on the activity of the microorganism, thereby obtaining the MFCs type BOD detection device with high sensitivity, high stability and wide monitoring range, being used for on-line or off-line determination of BOD value in organic wastewater, and greatly improving the monitoring level.
The embodiment also provides the application of the device in online or offline BOD monitoring of the organic wastewater. In the online or offline BOD monitoring of the organic wastewater, the device with the structure of the embodiment of the invention has good application effect. By optimizing the configuration of the device, selecting low-cost electrode materials and membrane materials, reducing the use of noble metal catalysts, reasonably processing the electrode materials and the membrane materials, adopting potassium ferricyanide as a cathode electron acceptor, and utilizing anaerobic granular sludge as an inoculation liquid to enrich electroactive microorganisms, the start-up time of MFCs is shortened, the high stability and wide applicability of the MFCs type BOD detection device are realized, and the BOD real-time online monitoring of organic wastewater is realized.
Example 2
The embodiment provides a method for detecting BOD of organic wastewater, which adopts the device constructed by the embodiment to detect, and the specific process is as follows: and adding a water sample to be detected into the anode chamber of the detection device, measuring the output voltage generated by the detection device, and substituting the voltage value into a linear equation to calculate the BOD value.
The linear equation (BOD standard curve) is plotted as follows:
GGA solutions (commercially available, diluted with 0.1MPBS (pH 7.0) solution) with different standard BOD concentrations (50, 100, 200, 300, 500mg/L) are prepared, the BOD concentrations are detected by an MFCs reactor, output voltage (U) and response time (T) are respectively recorded, and linear fitting is carried out on the voltage peak value and the BOD concentrations of artificial sewage to obtain a corresponding linear equation, namely a BOD standard curve, as shown in FIG. 7. As can be seen from fig. 7, the linear equation is y ═ 0.9635x +52.1914, R 2 ＝0.9967。
The water sample to be tested is a simulated sample, and specifically is artificial sewage with different BOD concentrations (50, 100, 200, 300, 500, 1000mg/L) (prepared according to the concentrations in the above, wherein each liter of artificial sewage contains 0.375g/L glucose, 0.375g/L glutamic acid, 0.1mol/L phosphate buffer solution (0.1M PBS, pH 7.0), 12.5mL/L trace mineral solution and 5mL/L vitamin solution (the formulas of the phosphate buffer solution, the trace mineral solution and the vitamin solution are shown in tables 1-3).
The detection result of the analog sample of 50-500 mg/L BOD is shown in FIG. 8, and it can be seen from FIG. 8 that after AWW with different BOD concentrations is injected into the anode chamber, the electrogenic microorganisms on the anode electrode rapidly start to degrade organic matters to generate voltage, and the voltage value rises to the maximum value in a short time; as the BOD concentration increases, more organic matter can be degraded by the microorganisms, resulting in a larger voltage value. When the BOD concentration is >500mg/L, the voltage maximum gradually deviates from the linear relationship and is lower than the theoretical value. When the concentration of organic matters exceeds the requirement of microorganisms, the proton transfer efficiency is not increased linearly any more due to the limitation of the number of the microorganisms on the anode carbon felt and the area of the cation exchange membrane; meanwhile, the continuous increase of the BOD concentration may cause the accumulation of metabolic products such as organic acid in the system, leading to the acidification of the anode chamber, causing a great concentration difference, leading the electron acceptor of the cathode to reach the anode through the cation exchange membrane, thereby influencing the activity of electrogenesis microorganisms on the anode carbon felt, reducing the electron transfer rate between the cathode and the anode, and leading to the gradual decrease of the maximum voltage value. Therefore, when the BOD concentration of the wastewater is 50-500 mg/L, the BOD concentration of the wastewater can be detected by using the maximum voltage generated by the MFCs. Aiming at organic wastewater with the BOD concentration of below 500mg/L, the BOD mass concentration of a sample to be measured can be accurately measured without dilution, only simple sample introduction operation is needed, the output voltage signal value of the device is directly read through program control software connected with a universal meter, and the BOD mass concentration of the sample to be measured can be calculated according to the obtained BOD standard curve linear equation.
To verify the detection conditions, different detection conditions were verified:
1) effect of BOD concentration of anode nutrient solution on microbial activity: the electrogenic bacteria cultured anaerobically are subjected to curve scanning by Cyclic Voltammetry (CV) in a voltage stabilization period to evaluate the electrochemical activity of the electrode biofilm. The study performed CV curve scanning on anode solutions to be tested with different concentrations. Tests show that the oxidation peak and the reduction peak obtained by scanning the CV curve are more obvious along with the increase of the concentration of the liquid to be detected, and the peak value does not obviously change after the concentration exceeds a certain concentration. The test results of 50-500 mg/LBOD are shown in FIG. 9, and it can be seen from FIG. 9 that the solutions to be tested with different concentrations have a greater influence on the activity of the anode electrogenic bacteria, the higher the solution concentration is, the larger the area of the CV curve is, the greater the electron transfer amount is, the stronger the electron transfer capability of the electrode is, and the stronger the microbial activity is. And the obtained curve shows that the electrogenic bacteria enriched on the anode carbon felt have good electrochemical activity and can be used for carrying out the next experiment when the concentration of the anolyte is within the range of the scheme of the invention.
2) The influence of different external resistances on the detection effect:
the external resistor when the output power of the MFCs is maximum can improve the BOD detection accuracy. Measuring the output voltage (U) of the MFCs under the condition of connecting different external resistors (Rext), taking GGA solution with BOD concentration of 300mg/L as MFCs anolyte, and calculating the power density (P) of the MFCs under different external resistors (external resistance values are respectively 100, 200, 330, 510, 680, 1000, 1200 and 1500 omega) according to the following formula:
P＝U 2 /Rext*A
in the formula: and A is the surface area of the anode carbon felt electrode.
The test results are shown in fig. 10. As can be seen from FIG. 10, the power density increased first with the increase of the resistance, and 68mW/m of the maximum power density was reached when the external resistance reached 1000. omega 2 Then the power density starts to decrease with further increase of the external resistance. This may be because the high external resistance limits the electron absorption through the circuit. Therefore, the external resistance is preferably 1000 Ω to ensure the maximum output power density of the MFCs.
3) Influence of different pH on the detection effect:
the BOD concentration of the anode nutrient solution and the pH value of the anode nutrient solution are changed, the influence of the anode nutrient solution on the performance of the MFCs is researched, and the optimal BOD detection condition and detection range are determined.
pH is an important factor in biochemical reactions, and either too high or too low can affect anode chamber microbial activity, resulting in failure of MFCs reactors. Meanwhile, in the process of decomposing organic matters by microorganisms, substances such as organic acid and the like can be generated, and the pH value of the solution is reduced. Therefore, a buffer solution of a certain concentration should be added to the water sample to control the pH of the solution. The GGA solution with BOD of 300mg/L is used as anolyte, an external resistor is connected with the anolyte by 1000 omega, the influence of the GGA solution with the pH value of 3.0-10.0 on the output voltage and the power density of the MFCs reactor is examined, and the test result is shown in figure 11. As can be seen from fig. 11, the output voltage of the MFCs is the highest at pH 7.0, the power density is also the highest, and the signal stabilization time is the longest, which is most beneficial for the detection result. Therefore, the pH value of the solution should be adjusted to about 7.0 during the later detection process, which is most beneficial to the growth of microorganisms.
4) And (3) testing the stability:
stability is one of the essential factors that must be considered in the long-term operation of MFCs type BOD detection devices. As shown in fig. 12, the stability of the MFCs type BOD detection device was achieved by continuously operating 50, 100, 200, 300, 500mg/L BOD for more than 15 days, respectively. As can be seen from FIG. 12, the voltage output signal values of the MFCs type BOD detection device during the test are stable for BODs of different concentrations, and the average voltages corresponding to BODs of different concentrations are 101.27mV (50mg/L), 168.93mV (100mg/L), 241.67mV (200mg/L), 346.87mV (300mg/L) and 544.67mV (500mg/L), with standard deviations of + -5.31% (50mg/L), + -4.61% (100mg/L), + -4.80% (200mg/L), + -5.11% (300mg/L) and + -5.40% (500mg/L), respectively. The test results still maintained high stability for months thereafter. Therefore, the scheme device and the detection condition have stable and reliable detection results.
In the test process, the response speed of the electric signal of the device in the embodiment of the invention to the BOD concentration (50-500 mg/L) of the organic wastewater is higher, the shortest response time is 5min, the longest response time is not more than 180min, and the detection result of the actual domestic wastewater and the BOD are found 5 And the relative error is within 5.0 percent. This result provides the possibility of practical application of MFCs type BOD biosensors in real-time measurement.
Example 3
This example provides a method for detecting BOD of organic wastewater, which is different from example 2 in that: the water sample to be tested is actual organic wastewater (taken from four domestic sewage outlets around a certain university in Jiangmen City).
The MFCs type BOD detection apparatus obtained based on the above steps tests the output voltage signal value of the artificial sewage, and detects the BOD concentration of the actual organic wastewater according to the standard curve drawn in example 2.
Comparative example 1
The comparative example provides an organic wastewater BOD detection method, which adopts the traditional five-day biochemical method to detect and compare domestic wastewater from the same source.
The results of the tests of example 3 of the present invention and comparative example 1 are summarized in the following table 4:
TABLE 4
As can be seen from the above table, the detection results of the detection device constructed by the traditional five-day biochemical method and the invention have relative deviation less than 5%, which shows that the detection results of the two methods are basically consistent, the requirement of BOD analysis precision can be met, and the device of the embodiment of the invention has higher reliability and stronger applicability.
Comparative example 2
This comparative example provides an organic wastewater BOD detection device, which differs from example 1 in that: the anode chamber and the cathode chamber are respectively hexahedron, and the volume of the anode chamber and the volume of the cathode chamber are respectively 30 mL; the anode nutrient solution does not contain glutamic acid, 10mmol/L potassium permanganate is used as a cathode electron acceptor, the two electrodes are graphite felts, and a proton exchange membrane (commercially available Nafion 117) is used as a separation membrane. The start-up time was 240 hours and the response time was 10 hours or more, and the stability data measured with reference to example 2 is shown in fig. 13, and it can be seen from fig. 13 that the operation stability of the apparatus was poor.
The device provided by the embodiment of the invention takes the basic starting points of improving the power generation capacity of the MFCs and reducing the huge electric energy consumed during wastewater treatment, shortens the BOD detection time and improves the BOD detection range. The method is characterized in that active granular sludge at an anaerobic section is used as an inoculation source, potassium ferricyanide solution is used as a cathode electron acceptor, a cation exchange membrane replaces an expensive proton exchange membrane to serve as a partition of a cathode chamber and an anode chamber to construct a double-chamber mediator-free MFCs type BOD detection device, meanwhile, the measurement conditions of the MFCs type BOD detection device are selected and optimized, and the measurement results of the MFCs type BOD detection device are more accurate and reliable by optimizing the conditions such as the pH value of anode nutrient solution, the size of an external resistor, the concentration of the cathode potassium ferricyanide solution and the like. Drawing a BOD standard curve and carrying out BOD real-time online monitoring on the actual organic wastewater, and comparing the monitoring result of the MFCs type BOD detection device with the traditional BOD 5 The results obtained by the method are compared, and the reproducibility and the accuracy of the measurement result of the MFCs type BOD detection device are tested. Compared with the prior art, the scheme of the invention at least has the following advantages:
(1) the invention reduces the volume of the reactor to 14ml by optimizing the microorganism species and the configuration of the reactor in the MFCs type BOD detection device, shortens the electrode spacing to 2cm, adopts carbon felts as electrode materials to replace expensive metal catalysts, adopts cation exchange membranes as diaphragm materials to replace expensive proton exchange membranes, adopts potassium ferricyanide solution as a catalyst and an electron acceptor as a cathode, does not cause diaphragm pollution in the operation process, has the real-time online continuous measurement function, is simple to operate, has long continuous and stable working time, and has relatively lower use and maintenance cost. The lead adopts a titanium wire, has better corrosion resistance, reduces the influence on the activity of microorganisms, thereby obtaining the MFCs BOD detection device with high sensitivity, high stability and wide monitoring range, being used for measuring the BOD value in the organic wastewater on line or off line and greatly improving the monitoring level.
(2) The redox reaction of the double-chamber MFCs type BOD detection device adopted by the invention is usually carried out in solution, the reaction resistance is small, and the output power is high; the double-chamber MFCs are simple in structure, electricity production conditions are convenient to adjust, no interference exists between the two reaction chambers, the device performance is more stable, the data result reproducibility is higher, and the real-time detection of wastewater BOD is more favorable.
(3) The MFCs type BOD detection device takes potassium ferricyanide as a cathode electron acceptor, fully utilizes the characteristics of high oxidation-reduction potential, strong stability, no by-product in reaction and the like of the potassium ferricyanide, improves the performance of the BOD sensor, can realize the rapid detection of the wastewater with high BOD concentration, reduces electrons obtained from the potassium ferricyanide into potassium ferrocyanide, changes cathode solution from yellow green into colorless, and has less pollution to a diaphragm, thereby ensuring that the device can stably run for a longer time.
(4) The MFCs type BOD detection device provided by the invention expands the detection upper limit of wastewater BOD to 500mg/L, the detection range is obviously improved compared with that of other BOD sensors of the same type, the accuracy and repeatability of the monitoring result of the device are ensured, the error of the monitoring data is less than 5% compared with that of the traditional five-day biochemical method, and the device has good stability and can be used for detecting the BOD concentration in wastewater in real time.
(5) MFCs type BOD detection of the present inventionThe response time of the device is short, the starting voltage reaches about 545mV of a stable value within one week, the treated anode carbon felt can enrich enough electrogenesis microorganisms within a short time, the successfully started device has stable performance in later operation, and the real-time BOD online detection can be realized. Compared with the conventional BOD 5 The response time of the device is short compared to the assay, the assay can usually be completed within a few minutes to a few hours, and the response time of the reactor is proportional to the BOD mass concentration of the sample. Meanwhile, the signal response value of the MFCs type BOD detection device can be directly transmitted through program control software connected with a Keithley universal meter, so that the real-time online detection of the BOD of the wastewater is realized.
(6) The MFCs type BOD detection device has a wide application range. The device uses the mixed strain in anaerobic section granular sludge of a sewage treatment plant as an inoculation source of electrochemical active microorganisms, has wider application range and linear range compared with a microbial electrode using a single strain, and can determine various samples or complex component samples within a larger concentration range.
(7) The MFCs type BOD detection device has good stability. Potassium ferricyanide is used as a cathode electron acceptor, a cation exchange membrane is used as a middle diaphragm of a cathode chamber and an anode chamber, a double-chamber microbial fuel cell is used as a reaction core component, the device can stably run for months, and measured data have good reproducibility and are compatible with a microbial electrode method and BOD 5 The assay has better stability than the other.
(8) The MFCs type BOD detection device is simple to operate. By using the MFCs type BOD detection device, the organic wastewater with the BOD concentration of below 500mg/L can be accurately measured without dilution, only simple sample introduction operation is needed, the output voltage signal value of the device is directly read through the program control software connected with the universal meter, and the BOD mass concentration of a sample to be detected can be calculated according to the obtained BOD standard curve linear equation.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (10)
1. The utility model provides an organic waste water BOD detection device which characterized in that: the microbial fuel cell reactor comprises an anode chamber, a cathode chamber and a lead, wherein the anode chamber and the cathode chamber are connected through the lead;
wherein a cathode material and a cathode electron acceptor are arranged in the cathode chamber, and the cathode electron acceptor comprises potassium ferricyanide;
an anode material, microorganisms enriched on the anode material and an anode nutrient solution are arranged in the anode chamber, the anode nutrient solution contains glucose, glutamic acid, a pH buffer system, mineral elements and vitamins, and the pH buffer system is used for adjusting the pH of the anode nutrient solution to 6.0-8.0;
the anode material and the cathode material are both carbon felts, and the pretreatment step of the carbon felts comprises the following steps: modifying the carbon felt by using strong oxidizing acid; then washing and neutralizing until the washing liquid is neutral, and burning.
2. The BOD detection device for organic wastewater according to claim 1, characterized in that: drying the carbon felt and then firing the carbon felt; preferably, the drying treatment is constant-temperature vacuum drying; preferably, the drying treatment temperature is 75-85 ℃; preferably, the drying treatment time is 10-14 h; preferably, the ignition temperature is 580-620 ℃, and the ignition time is 1.5-2.5 h; preferably, the temperature rise speed of the firing is 1-3 ℃/min.
3. The BOD detection device for organic wastewater according to claim 1, characterized in that: in the starting stage, the microorganism is inoculated on the anode material through an inoculation liquid, and the preparation process of the inoculation liquid comprises the following steps: mixing anaerobic activated sludge with pretreatment liquid, sealing, oscillating at constant temperature for 20-28 h, and deoxidizing; the pretreatment solution contains glucose, glutamic acid, a pH buffer system, a mineral solution and a vitamin solution; preferably, the constant-temperature oscillation is carried out at 34-36 ℃ and at the speed of 80-120 rpm; preferably, the shaking at constant temperature is at about 35 ℃ at a speed of about 100 rpm; preferably, the BOD value of the pretreatment solution is about 500 mg/L.
4. The BOD detection device for organic wastewater according to claim 1, characterized in that: the wire is externally connected with a resistor; preferably, the resistance of the resistor is about 1000 Ω.
5. The BOD detection device for organic wastewater according to claim 1, characterized in that: the pH buffer system in the anode nutrient solution is used for adjusting the pH of the anode nutrient solution to 6.5-7.5; preferably, the pH buffer system in the anode nutrient solution is used to adjust the pH of the anode nutrient solution to about 7.0; preferably, the concentration of glucose in the anode nutrient solution is 0.3-0.4 g/L; preferably, the concentration of glucose in the anode nutrient solution is about 0.375 g/L; preferably, the concentration of the glutamic acid in the anode nutrient solution is 0.3-0.4 g/L; preferably, the concentration of glutamic acid in the anode nutrient solution is about 0.375 g/L; preferably, the pH buffering system is a phosphate buffering system; preferably, the concentration of phosphate in the phosphate buffer system is 0.08-0.12 mol/L; preferably, the concentration of phosphate in the phosphate buffer system is about 0.1 mol/L; preferably, the mineral elements are added into the anode nutrient solution through a mixed solution containing the following components in a volume ratio of 1: 70-90:
preferably, the vitamins are added into the anode nutrient solution through a mixed solution containing the following components in a volume ratio of 1: 100-300:
6. the BOD detection device for organic wastewater according to claim 1, characterized in that: the concentration of the potassium ferricyanide is 40-60 mmol/L; preferably, the concentration of the potassium ferricyanide is about 50 mmol/L; preferably, the wire is a titanium wire.
7. The BOD detection device for organic wastewater according to claim 1, characterized in that: the microbial fuel cell reactor further comprises a cation exchange membrane for separating the cathode chamber from the anode chamber; preferably, the cation exchange membrane is selected from the group consisting of CMI-7000 cation exchange membranes; preferably, the cation exchange membrane is pretreated by:
soaking in hydrogen peroxide;
soaking in water at high temperature;
soaking in nitric acid at high temperature;
soaking in water at high temperature;
storing in moisture state for use.
8. The BOD detection apparatus for organic wastewater according to any one of claims 1 to 7, characterized in that: the volume of the microbial fuel cell reactor is 24-32 ml, wherein the anode chamber and the cathode chamber are 12-16 ml respectively; preferably, the microbial fuel cell reactor has a volume of 28ml, wherein the anode and cathode compartments are each 14 ml; preferably, the distance between the carbon felts used as the cathode and the anode is 1-3 cm.
9. Use of the device according to any one of claims 1 to 8 for on-line BOD monitoring of organic wastewater.
10. A BOD detection method for organic wastewater is characterized by comprising the following steps: the method comprises the following steps:
a water sample to be tested is added into the detection device according to any one of claims 1 to 8, the output voltage generated by the detection device is measured, and the voltage value is substituted into a linear equation to calculate the BOD value.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115340969A (en) * | 2022-09-20 | 2022-11-15 | 中国科学院重庆绿色智能技术研究院 | Flora domestication method and application of BOD (biochemical oxygen demand) microbial electrochemical sensor |
| WO2023207134A1 (en) * | 2022-04-25 | 2023-11-02 | 五邑大学 | Organic wastewater bod test device and method, and application |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006077343A (en) * | 2004-09-08 | 2006-03-23 | Toray Ind Inc | Carbon fiber mat, method for producing the same, substrate for forming by using the same |
| CN101620201A (en) * | 2009-08-03 | 2010-01-06 | 广东省生态环境与土壤研究所 | Measuring method of biochemical oxygen demand and BOD sensor and applications |
| US20110097605A1 (en) * | 2009-10-26 | 2011-04-28 | Teledyne Scientific & Imaging, Llc | Yeast biofilm based fuel cell |
| CN103207230A (en) * | 2013-04-02 | 2013-07-17 | 北京林业大学 | Method for constructing dual-chamber microbial fuel cell-type BOD (biochemical oxygen demand) sensor by using potassium permanganate as cathode electron acceptor |
| 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 |
| JP2016091805A (en) * | 2014-11-05 | 2016-05-23 | 国立研究開発法人農業・食品産業技術総合研究機構 | Microbial fuel cell |
| CN107045012A (en) * | 2016-11-24 | 2017-08-15 | 北京化工大学 | A kind of microbiological fuel cell toxic sensors and operation method |
| CN111579618A (en) * | 2020-05-25 | 2020-08-25 | 广州中国科学院沈阳自动化研究所分所 | Biochemical oxygen demand online automatic detection system and method based on microbial fuel cell |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109160616B (en) * | 2018-09-13 | 2021-03-02 | 太原理工大学 | Method for treating sulfadiazine in sewage by adopting nickel-manganese ion modified electrode material |
| CN114894863A (en) * | 2022-04-25 | 2022-08-12 | 五邑大学 | Organic wastewater BOD detection device and application and method thereof |
-
2022
- 2022-04-25 CN CN202210441499.4A patent/CN114894863A/en active Pending
- 2022-12-14 WO PCT/CN2022/139061 patent/WO2023207134A1/en unknown
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006077343A (en) * | 2004-09-08 | 2006-03-23 | Toray Ind Inc | Carbon fiber mat, method for producing the same, substrate for forming by using the same |
| CN101620201A (en) * | 2009-08-03 | 2010-01-06 | 广东省生态环境与土壤研究所 | Measuring method of biochemical oxygen demand and BOD sensor and applications |
| US20110097605A1 (en) * | 2009-10-26 | 2011-04-28 | Teledyne Scientific & Imaging, Llc | Yeast biofilm based fuel cell |
| CN103207230A (en) * | 2013-04-02 | 2013-07-17 | 北京林业大学 | Method for constructing dual-chamber microbial fuel cell-type BOD (biochemical oxygen demand) sensor by using potassium permanganate as cathode electron acceptor |
| 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 |
| JP2016091805A (en) * | 2014-11-05 | 2016-05-23 | 国立研究開発法人農業・食品産業技術総合研究機構 | Microbial fuel cell |
| CN107045012A (en) * | 2016-11-24 | 2017-08-15 | 北京化工大学 | A kind of microbiological fuel cell toxic sensors and operation method |
| CN111579618A (en) * | 2020-05-25 | 2020-08-25 | 广州中国科学院沈阳自动化研究所分所 | Biochemical oxygen demand online automatic detection system and method based on microbial fuel cell |
Non-Patent Citations (2)
| Title |
|---|
| 吴锋;刘志;周顺桂;王跃强;黄赛花;: "低成本单室微生物燃料电池型BOD传感器的研制", 环境科学, no. 10, pages 3099 - 3103 * |
| 李学萍 等: "碳毡电极的表面改性 II.碳毡表面HNO3化学改性对电极性能影响", 《分子催化》, vol. 6, no. 4, pages 297 - 302 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023207134A1 (en) * | 2022-04-25 | 2023-11-02 | 五邑大学 | Organic wastewater bod test device and method, and application |
| CN115340969A (en) * | 2022-09-20 | 2022-11-15 | 中国科学院重庆绿色智能技术研究院 | Flora domestication method and application of BOD (biochemical oxygen demand) microbial electrochemical sensor |
| CN115340969B (en) * | 2022-09-20 | 2024-01-30 | 中国科学院重庆绿色智能技术研究院 | Flora domestication method and application of BOD microbial electrochemical sensor |
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|---|---|
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