CN202710505U - Device for detecting electron transfer in electrically facilitated biological denitrification process - Google Patents

Device for detecting electron transfer in electrically facilitated biological denitrification process Download PDF

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Publication number
CN202710505U
CN202710505U CN 201220338046 CN201220338046U CN202710505U CN 202710505 U CN202710505 U CN 202710505U CN 201220338046 CN201220338046 CN 201220338046 CN 201220338046 U CN201220338046 U CN 201220338046U CN 202710505 U CN202710505 U CN 202710505U
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microorganism
cathode electrode
hole
reaction
electron transfer
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CN 201220338046
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丛燕青
徐谦
冯华军
沈东升
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Zhejiang Gongshang University
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Zhejiang Gongshang University
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Abstract

The utility model discloses a device for detecting electron transfer in an electrically facilitated biological denitrification process. The device comprises a base, a cathode electrode plate, and a reactive tank which are orderly laminated from bottom to top; an injection cavity is arranged inside the reactive tank; a cathode electrode rod is inserted into the injection cavity; a through hole is arranged at the bottom surface of the injection cavity, and the bottom part of the through hole is sealed by the cathode electrode plate. A power supply is connected in work; wastewater is injected into the injection cavity; microorganism is injected and falls off on the cathode electrode plate to form a biological film when a current value is stable; the electrically facilitated biological denitrification reaction is carried out; the change of the current is monitored in real time; the reaction is terminated after the current value is stabilized; a water body index in the wastewater is detected, and the electron transfer process and the velocity in a reaction process are determined through the change of the current value and the final water body index. According to the device disclosed by the utility model, the electron transfer process and the velocity between the microorganism and an electrode in an electrically facilitated biofortification system can be effectively researched.

Description

A kind of device that detects electronics transfer in the short biological denitrification denitrification process of electricity
Technical field
The utility model relates to the short biological denitrification denitrification treatment technology field of electricity, is specifically related to a kind of device that electronics shifts in the short biological denitrification denitrification process of electricity that detects.
Background technology
In recent years, the short biological reinforcing technology of electricity as a new type water treatment technology at the focus that has become domestic and international research aspect the denitrification denitrogenation.The at present research of this technology mainly concentrates on based in the investigation that improves the reaction unit design of removing efficient and different factor affecting denitrification effects, how to affect microbial activity and microbiological analysis etc. about microorganism and interelectrode electron transport mechanism, electric microfield and studies relative less.
Existing research is found: on the one hand, electrode can provide electronics for the breathing of some microorganisms, NO 3 -As final electron accepter by micro-reduction; On the other hand, microorganism can pass to electrode with the electronics that self produces, thereby generate watt current by respiratory metabolism oxidative degradation organic compound.But electronics is transferred to microorganism from electrode and is transferred to these two processes of electrode with the electronics the microbial cell and can not realize simple reverse, has great importance so microorganisms and electrode electronics each other shifts.
At present, Chinese scholars finds that to the research of microbiological fuel cell electron transport mechanism mainly comprises following three approach: the Direct electron transfer that utilizes the C-type cytochrome of cell membrane outside surface, additionally add the indirect electronics that electron medium occurs and shift, the electronics of " nm-class conducting wire " that produces by microorganism self shifts.But have now and mainly concentrate on microbiological fuel cell this part about microorganism and interelectrode mutual electron transport mechanism, seldom relevant for electron transport mechanism and the electronics and the NO that come from electrode in the short biological reinforced system (continuing to provide power supply) of electricity 3 -The research of terminal electronic acceptor Relations Among lacks effective mechanism research device and method.
Common biofilm reactor has parallel plate type reactor, negative and positive cellular-type reactor and drum type brake reactor, negative and positive the two poles of the earth of parallel plate type reactor are parallel to each other, the negative electrode of negative and positive cellular-type reactor is inserted respectively in the reactor that links to each other with anode, the cylinder of drum type brake reactor is negative electrode, biological membrane is fixed on its inside surface, and anode is inserted flexible center.These several reactors are reactors commonly used in the wastewater treatment, all can carry out effective denitrogenation to waste water, but in its course of reaction, biological membrane all too disperses, and can not the transfer of electronics in the anti-process effectively be detected.
The utility model content
The utility model provides a kind of device that electronics shifts in the short biological denitrification denitrification process of electricity that detects, and can effectively study microorganism and interelectrode electronics transfer case in the short biological reinforced system of electricity by controlling biomembranous biofilm area.
A kind of device that detects electronics transfer in the short biological denitrification denitrification process of electricity comprises:
Stacked base, cathode electrode sheet and reactive tank successively from the bottom to top, described reactive tank is with the fluid injection chamber, and described fluid injection is inserted with the anode electrode rod in the chamber, and bottom surface, described fluid injection chamber is provided with through hole, and described via bottoms is sealed by described cathode electrode sheet.
Described anode electrode rod is preferably graphite rod, described cathode electrode sheet is preferably graphite flake, during work, described graphite rod is connected with the output terminal of power supply with graphite flake, and the current detecting instrument or be connected to electrochemical workstation of connecting, first in the fluid injection chamber, inject nitrogenous effluent, determine reference current, namely when detected current value is stablized in the current detecting instrument, in nitrogenous effluent, inject microorganism, microorganism falls on the graphite flake of via bottoms owing to action of gravitation, curent change in the course of reaction is by the current detecting instrument Real-Time Monitoring, cessation reaction after current value is stable detects the water body index in the waste water, changes with final water body index by current value and determines that the electronics in the course of reaction shifts.
The cross-sectional area of through hole is less than the cross-sectional area in fluid injection chamber, preferably, described fluid injection chamber is 1.5~5: 1 with the cross-sectional area ratio of through hole, the little cross-sectional area of through hole is conducive to microorganism and forms the biological membrane of small size at graphite flake, the fluid injection chamber be conducive to the interpolation of fixing and nutrient solution and the microorganism of graphite rod than large space.
Negative electrode level, anode are vertical, negative and positive the two poles of the earth quadrature arranges, the microorganism that injection is entered utilizes Action of Gravity Field just to drop on the horizontal graphite flake, like this microorganism and cathode electrode close contact, form electrode biomembrane at negative electrode easilier, shorten widely the biofilm time of negative electrode, and can solve the problems such as biofilm detachment.Because area definition and the area of via bottoms are very little, can make biomembranous area definition and very little, the background current value that whole like this electrode biomembrane produces is less, the electronics transfer case that electrode and biological membrane interphase interaction are caused can obviously reflect on current detecting instrument or electrochemical workstation, and can not exist Weak current to change situation about being covered by background current greatly.Last analysis result in conjunction with water-quality guideline, effectively detected electrons transfer case.Device of the present utility model lightly makes things convenient for, is convenient to install and unloading, be not subjected to site influence, and structural design makes microorganism and electrode close contact cleverly, and rapid biofilm in the short time is beneficial to the carrying out of experiment.
Preferably, described via bottoms and described cathode electrode sheet contact position are provided with the packing washer around described through hole.Packing washer prevents that with via bottoms and the sealing of graphite flake contact position reactant liquor from spilling.
Described negative and positive two-stage electrode intersects setting, and preferably, described anode electrode rod is perpendicular to described cathode electrode sheet.
Preferably, the distance between described anode electrode rod bottom and the described cathode electrode sheet is 5~30mm, more preferably, is 8~20mm.
The beneficial effects of the utility model:
(1) apparatus and method of the present utility model can be effective, easy, electronic transfer process and the speed in the short biological denitrification denitrification process of online study electricity rapidly;
(2) the Promethean negative electrode level of the utility model device, anode vertically, the structure of negative and positive two electrode quadratures, having broken conventional electrochemical appliance Anodic and negative electrode all is the convention of vertically placing, the microorganism that injection is entered utilizes Action of Gravity Field just to drop on the horizontal graphite working electrode, like this microorganism and electrode close contact, form electrode biomembrane at negative electrode easilier, shortened widely the biofilm time of negative electrode, and can solve the problems such as biofilm detachment, for the design of electrode biomembrane reactor provides a kind of new approaches;
(3) design of whole device is ingenious, makes meticulously, provides powerful guarantee for studying electric microfield to mechanism of action, Real-Time Monitoring microorganism and the interelectrode electronic transfer process of microbial activity.
The short biological denitrification denitrogenation electronics transfer case research of electricity is for the short biological reinforcing technology of electricity is applied in the Practical Project better, realizes cleaning, efficient denitrification provides certain foundation at low cost, has important theory value and Research Significance.
Description of drawings
Fig. 1 is structural representation of the present utility model;
Fig. 2 a is respectively the curent change curve of the utility model device under different voltages and corresponding water-quality guideline synoptic diagram with Fig. 2 b;
Fig. 3 a and Fig. 3 b are respectively the utility model device curent change curve and corresponding water-quality guideline synoptic diagram under different microorganisms concentration;
Fig. 4 a and Fig. 4 b are respectively the utility model device curent change curve and corresponding water-quality guideline synoptic diagram under the dissimilar microorganisms of injection.
Embodiment
As shown in Figure 1, a kind of device that detects electronics transfer in the short biological denitrification denitrification process of electricity, comprise base 9, base 9 is columniform solid construction, cylindrical reactive tank 3 in base 9 end face settings and base 9 same diameter, the center of reactive tank 3 is provided with vertical fluid injection chamber 2, fluid injection chamber 2 is cylindrical cavity, the bottom in fluid injection chamber 2 arranges diameter less than the through hole 5 in fluid injection chamber 2, fluid injection chamber 2 forms ring-shaped step with the internal face intersection of through hole 5, fluid injection chamber 2 is 1.5~5: 1 with the diameter ratio of through hole 5, and in the present embodiment, fluid injection chamber 2 is 3: 1 with the diameter ratio of through hole 5.
Cathode electrode sheet 8 (selecting graphite flake in the present embodiment) is arranged between the bottom surface of the end face of base 9 and reactive tank 3, solid section correspondence position with reactive tank 3 on the base 9 is equipped with screw hole 4, fixing by long screw nail 10 between base 9 and the reactive tank 3, graphite flake is clamped between base 9 and reactive tank 3 bottoms, base seal with through hole 5, through hole 5 arranges packing washer 6 with the contact position setting of graphite flake around through hole 2, prevents that reactant liquor spills in the course of reaction.
Anode electrode rod 1 (selecting graphite rod in the present embodiment) vertically inserts in the fluid injection chamber 2, the bottom is stretched in the through hole 5, and the spacing between the graphite flake can be set to 5~30mm, is set to 10mm in the present embodiment, and the top is fixed on the reactive tank 3 by stationary installation.
During work, graphite flake and graphite rod are respectively connected negative pole and the positive pole of dc current regulator power supply, and the intelligent digital volometer of connecting, inject nutrient solution in the fluid injection chamber 2 and (contain NO 3 -Simulated wastewater), determine reference current, namely the current value in the intelligent digital volometer is stablized in the backward simulation waste water and is injected microorganism, microorganism forms biological membrane 6 because Action of Gravity Field falls to through hole 5 bottoms at graphite flake, carries out the short biological denitrification denitrification reaction of electricity, pass through the variation of intelligent digital volometer Real-Time Monitoring electric current in the course of reaction, cessation reaction after electric current is again stable is poured out the simulated wastewater in the fluid injection chamber 2, with the NO in the standard method measure analog waste water 3 --N and NO 2 --N concentration.By the curent change situation in the course of reaction and the NO in the simulated wastewater 3 --N and NO 2 -Electronics transfer case and speed in-the N Analysis of concentrations course of reaction.
Detect respectively the electronics transfer case under differential responses voltage, different microorganisms kind and the different microorganisms final concentration, the impact that analytical work voltage, microbe species and microorganism final concentration shift the short biological denitrification denitrogenation electronics of electricity.
Embodiment 1
Short biological electronic transfer process or speed and denitrification denitrogenation effect of electricity in different voltage lower devices.
Setting respectively different magnitudes of voltage is 1V, 2V, 3V and 3.5V, the nutrient solution (constituent of nutrient solution: 30mg/L NO of injection 6mL in the reaction unit 3 --N, 80mg/L NaHCO 3, 5g/L K 2HPO 4, 1.5g/L KH 2PO 4), after current stabilization, injection 4ml concentration is the microorganism that the energising of 10mg/ml is tamed in the device again, the final concentration of microorganism is 4mg/ml in the reaction system, microorganism is taken from the electrode biomembrane reactor of stable operation, the curent change value of observation and recording device, until the electric current rear end reaction that substantially tends towards stability, total reaction time is about 2.5 hours.Nutrient solution in will installing is at last poured out, and utilizes the water-quality guideline in the standard method measurement nutrient solution, wherein NO 3 -The mensuration of-N adopts ultraviolet spectrophotometry, NO 2 -The mensuration of-N adopts N-(1-naphthyl)-ethylenediamine-hydrochloride spectrophotometric method.
The energy (ATP) that microorganism obtains in the metabolic process under specified conditions is directly proportional with energy difference Δ E (V) between electron donor and the electron accepter.Shown in Fig. 2 a, under (1V and 2V), interelectrode electric current diminishes along with the injection of microorganism under low voltage, and under high voltage slightly (3V and 3.5V), electric current is along with increase tendency has appearred in the adding of microorganism.Hence one can see that, and the electron transfer rate of low-voltage lower electrode surface is rate-limiting step, do not have enough electronics for the growth of microorganism metabolism, and the activity of microorganism can't be excited, and has reduced on the contrary the electron transfer rate of system.In addition, can find under low voltage NO from Fig. 2 b 2 --N growing amount is 0, NO 3 -Almost be not reduced, microorganism self does not produce electronics yet, so the device electric current diminishes.And the high electric current that high voltage produces (>0.2mA) can provide enough electronics to utilize for microorganism, promote its growth and metabolism, microorganism is at reductive NO 3 -Simultaneously itself also can produce electronics, and and electrode between electronic transfer process occurs, therefore after high voltage condition is made a bet microorganism in the device electric current increase tendency has appearred, NO 2 -The growing amount of-N and NO 3 -The clearance of-N is also higher.
Embodiment 2
Short biological electronic transfer process and speed and denitrification denitrogenation situation of electricity in the different microorganisms final concentration lower device.Setting voltage value is constant to be 3V, the nutrient solution (constituent of nutrient solution: 30mg/L NO of injection 6mL in the reaction unit 3 --N, 80mg/L NaHCO 3, 5g/L K 2HPO 4, 1.5g/L KH 2PO 4), after current stabilization, injecting respectively 1mL, 2mL, 3mL, 4mL and 5mL concentration in the device again is the microorganism that the energising of 10mg/ml is tamed, and the microorganism final concentration is respectively 1.4mg/ml, 2.5mg/ml, 3.3mg/ml, 4mg/ml and 4.5mg/ml after the injection.Microorganism is taken from the electrode biomembrane reactor of stable operation, the curent change value of observation and recording device, until the electric current rear end reaction that substantially tends towards stability, total reaction time is about 2.5 hours, wherein the nutrient solution time of putting down is 0.5 hour, and the reaction time behind the adding microorganism is 2 hours.
Nutrient solution in will installing is at last poured out, and utilizes the water-quality guideline in the standard method measurement nutrient solution, wherein NO 3 -The mensuration of-N adopts ultraviolet spectrophotometry, NO 2 -The mensuration of-N adopts N-(1-naphthyl)-ethylenediamine-hydrochloride spectrophotometric method.
Can find out from Fig. 3 a, when the voltage of setting is 3V, add the immediate current generation rapid fluctuation of microorganism, because system resistance changes with the after-current fast-descending.Along with micro-reduction NO 3 -, itself has produced electronics microorganism, then the electronics that produces is transferred to electrode, so increase tendency slowly appears in the electric current in the device, the microbial body accumulated amount of injecting is larger, and the electric current increase tendency is faster.It is larger to find simultaneously to work as the microbial body accumulated amount of injecting from Fig. 3 b, NO 2 -The growing amount of-N and NO 3 -The clearance of-N is also higher.
Embodiment 3
Short biological electronic transfer process and speed and denitrification denitrogenation situation of electricity in the different types of microorganisms lower device.Setting voltage value is constant to be 3V, the nutrient solution (constituent of nutrient solution: 30mg/L NO of injection 6mL in the reaction unit 3 --N, 80mg/L NaHCO 3, 5g/L K 2HPO 4, 1.5g/L KH 2PO 4), after current stabilization, again respectively in the device injection 5mL concentration be the microorganism tamed of the energising of 10mg/ml and without the energising acclimated microorganism, the final concentration of microorganism in the injection afterreaction system is 4.5mg/ml, wherein microorganism is taken from respectively the electrode biomembrane reactor (energising domestication) of stable operation and only has the control reactor (energising is tamed) of microorganism, curent change value in the observation and recording device, until the electric current rear end reaction that substantially tends towards stability, total reaction time is about 2.5 hours, wherein the nutrient solution time of putting down is 0.5 hour, and the reaction time behind the adding microorganism is 2 hours.
Nutrient solution in will installing is at last poured out, and utilizes the water-quality guideline in the standard method measurement nutrient solution, and wherein the nutrient solution time of putting down is 0.5 hour, and the reaction time behind the adding microorganism is 2 hours.
Increase tendency has appearred in the electric current injection along with the energising acclimated microorganism that can find working electrode from Fig. 4 a, and when having injected the nothing energising acclimated microorganism of same volume accumulated amount, increase tendency does not but appear in the electric current in the device.Variation has all occured in energising acclimated microorganism growth and morphology metabolic way under the stimulation of electric current, the electronics that can effectively accept electrode provides carries out anaerobic respiration, when removing nitrate, itself produce electronics, produced watt current thereby electronics is transferred to electrode; And can not accept very soon the electronics that electrode provides without the energising acclimated microorganism, can not produce watt current.Fig. 4 b shows the NO that has injected the energising acclimated microorganism in the device 2 -The growing amount of-N and NO 3 -The clearance of-N has all been injected the effluent index without the energising acclimated microorganism in the device, the phenomenon that occurs in can well explain Fig. 4 a.

Claims (6)

1. one kind is detected the device that electronics shifts in the short biological denitrification denitrification process of electricity, it is characterized in that, comprising:
Stacked base (9), cathode electrode sheet (8) and reactive tank (3) successively from the bottom to top,
Described reactive tank (3) is with fluid injection chamber (2), be inserted with anode electrode rod (1) in the described fluid injection chamber (2), bottom surface, described fluid injection chamber (2) is provided with through hole (5), and described through hole (5) bottom is sealed by described cathode electrode sheet (8).
2. device according to claim 1 is characterized in that, described fluid injection chamber (2) is 1.5~5: 1 with the cross-sectional area ratio of through hole (5).
3. device according to claim 2 is characterized in that, described through hole (5) bottom and described cathode electrode sheet (8) contact position are provided with the packing washer (7) around described through hole (5).
4. device according to claim 3 is characterized in that, described anode electrode rod (1) is perpendicular to described cathode electrode sheet (8).
5. device according to claim 4 is characterized in that, the distance between described anode electrode rod (1) bottom and the described cathode electrode sheet (8) is 5~30mm.
6. device according to claim 5 is characterized in that, the distance between described anode electrode rod (1) bottom and the described cathode electrode sheet (8) is 8~20mm.
CN 201220338046 2012-07-13 2012-07-13 Device for detecting electron transfer in electrically facilitated biological denitrification process Expired - Fee Related CN202710505U (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102735715A (en) * 2012-07-13 2012-10-17 浙江工商大学 Device and method for detecting electron transfer in process of electrically promoted microorganism denitrification
CN114216808A (en) * 2021-11-18 2022-03-22 中国人民解放军军事科学院国防工程研究院工程防护研究所 Gas impurity detection device and detection method

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102735715A (en) * 2012-07-13 2012-10-17 浙江工商大学 Device and method for detecting electron transfer in process of electrically promoted microorganism denitrification
CN114216808A (en) * 2021-11-18 2022-03-22 中国人民解放军军事科学院国防工程研究院工程防护研究所 Gas impurity detection device and detection method

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