CN111505068B - Biosensor method and device for monitoring COD concentration in constructed wetland in real time - Google Patents
Biosensor method and device for monitoring COD concentration in constructed wetland in real time Download PDFInfo
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Abstract
The invention discloses a biosensor method and a device for monitoring COD concentration in an artificial wetland in real time, which comprises the following steps: A. an anode conductive filler layer is arranged in the middle or at the bottom of the wetland, and a collector is arranged in the anode filler layer; B. arranging a cathode conductive filler layer on the surface layer of the wetland filler, and arranging a cathode collector in the layer; C. the anode and cathode packing layers are separated by a non-conductive isolating packing layer; D. the output electric quantity signal is displayed by an electric signal detector; E. sewage enters the wetland from the bottom and is discharged from a water outlet of the upper cathode conductive packing layer; F. and in the process of flowing through the system, the real-time sewage concentration is obtained through the displayed electric quantity signal. The device is paved with a bottom non-conductive, anode conductive, non-conductive and cathode conductive filler layer from bottom to top. The method is simple, convenient to operate, short in response time, high in sensitivity and good in stability, and can feed back the COD concentration and the organic load of the sewage efficiently in real time, so that the stable operation and the purification effect of the system are guaranteed.
Description
Technical Field
The invention belongs to the field of environmental protection, and particularly relates to a method for monitoring and feeding back a biosensor of an influent organic impact load in real time, and also relates to a device for monitoring and feeding back the biosensor of the influent organic impact load in real time. The method is suitable for monitoring the water inflow COD and predicting the impact organic load in real time, and adjusting the corresponding operation management mode to ensure the stability of the system and the water outflow.
Background
Microbial Fuel Cells (MFC) are bioelectrochemical devices which have attracted attention in recent decades, and degrade organic substances and transfer electrons by means of metabolism of microorganisms, so that chemical energy is directly converted into electric energy. The miniaturization and real-time online monitoring of MFC lead to wider research and application in the field of biosensors. However, MFC biosensors have a higher proton exchange membrane cost, and require maintenance of an anodic anaerobic environment and frequent replacement of catholyte to provide a suitable electron acceptor, so that their application and spread in practical sewage Monitoring are limited (Chouerer, J., Lorenzo, M., Water Quality Monitoring in Developing Countries; Can Microbial Fuel Cells be the answer biosensors 2015,5, 450-.
The electrode is embedded into the artificial wetland by virtue of a natural redox gradient formed from bottom to top of the vertical flow artificial wetland to form an artificial wetland-Microbial fuel cell (CW-MFC) coupled system, which shows a better voltage signal response effect to COD concentration (Doherty, L., ZHao, Y., ZHao, X., Hu, Y., Hao, X., Xu, L.and Liu, R.A review of a recording based engineered technology: constrained wet and-Microbial fuels. Water Research,2015,85, 38-45), and the system does not need a proton exchange membrane or a specific electrode chamber environment, greatly reduces the cost, and makes the realization of the real-time monitoring of COD by adopting the CW-MFC biosensor feasible.
However, the method of feeding back the COD concentration in real time by the response of the voltage has certain drawbacks. For example, when the sewage contains refractory organic matters and has complex composition, the voltage signal is often delayed and unstable in response, so that the COD concentration cannot be truly and accurately reflected. Moreover, the anaerobic environment of the anode region is beneficial to the growth of nitrate reducing bacteria and sulfate reducing bacteria, and the growth of the bacteria can directly utilize electrons generated by the anode to carry out nitrate and sulfate reduction, so that interference can be generated on an output voltage signal.
In addition, for biological treatment processes, the impact load of sewage often has disastrous consequences, and even biofilm processes with strong impact load can only be passively dealt with. In the process of sewage purification of the artificial wetland, because the biofilm formation of the filler is closer to the biofilm process, the hydraulic impact load caused by sudden increase of water quantity and the organic impact load caused by increase of pollutant concentration can be passively borne, and the effects of water blocking, biofilm falling, water quality deterioration and the like are caused.
How to actively measure the organic load or COD concentration in the feedback sewage by adopting an economic and effective method and adjust corresponding operation parameters according to the impact organic load to ensure the stable operation of the artificial wetland and the effluent quality effect is a problem to be solved urgently in practical engineering.
Disclosure of Invention
The invention aims to provide a biosensor method for monitoring COD concentration in real time in the process of purifying sewage by using a vertical flow artificial wetland, which is simple and easy to implement, convenient to operate, short in response time, high in sensitivity and good in stability, can feed back organic load of a system in real time and high efficiency, can adjust the water inflow amount according to the organic impact load, and ensures the stable operation and purification effect of the system.
The invention also aims to provide a biosensor device for monitoring the COD concentration in real time in the process of purifying sewage by using the vertical flow artificial wetland. The device is simple, the operation is convenient, and the cost is low; the COD concentration is converted into an electric quantity signal for feedback, the electric quantity signal changes stably and directly along with time, the occurrence of organic impact load can be fed back quickly, the operation parameters can be guided and adjusted in time, and the quality deterioration of effluent water caused by sudden concentration increase is avoided; meanwhile, the electric quantity signal is more stable than the voltage signal, and the problem of signal fluctuation caused by the instability of the biological membrane due to hydraulic flushing can be avoided.
In order to achieve the purpose, the invention adopts the following technical measures:
the technical conception is as follows: cathode and anode electrode layers are embedded in different packing layers of the vertical flow artificial wetland, the anode electrogenesis flora is enriched by utilizing the vertical natural oxidation-reduction potential difference in the vertical flow artificial wetland and anaerobic, anoxic and aerobic microenvironments of the packing layers at different depths, the electrogenesis flora generates electrons by taking organic matters in sewage as substrates and forms a circuit through an external lead, and the generated electric signal can be used as the indication of the sewage COD concentration. The anode conductive filler layer and the cathode conductive filler layer are arranged at different positions in the vertical direction of the vertical flow artificial wetland and are connected through an external lead to form a current loop to form a CW-MFC sensor, the COD concentration in sewage is indicated through an electric quantity signal, and the fluctuation of a voltage signal caused by the hydraulic impact of a conventional voltage signal and the instability of a microbial flora is avoided.
A method for monitoring a biosensor for COD concentration in an artificial wetland in real time comprises the following steps:
A. an anode conductive filler layer is arranged in the middle or at the bottom of the vertical flow artificial wetland, and a collector is arranged in the anode filler layer;
B. arranging a cathode conductive filler layer on the surface layer of the vertical flow artificial wetland filler, arranging a cathode collector in the layer, exposing one half of the layer to the air, and keeping the other half of the layer to be soaked by sewage; the root system of the wetland plant is planted below the layer;
C. the anode filler layer and the cathode filler layer are separated by a non-conductive isolation filler layer;
D. one end of the anode collector and one end of the cathode collector are connected with a load through an outer lead to form a circuit;
E. the output electric quantity signal is displayed by an electric signal detector;
F. sewage enters the artificial wetland from the bottom and is discharged from a water outlet of the upper cathode conductive packing layer;
G. and in the process of flowing through the system, the real-time sewage concentration is obtained through the electric quantity signal displayed immediately, and the adjustment of the operation parameters of the artificial wetland is guided.
The key points in the seven steps are the arrangement of the anode packing layer in the step A and the exposure of half of the cathode packing layer in the step B to the air, and the soaking of half of the cathode packing layer in the sewage. The arrangement of the anode filler layer determines the enrichment degree and stability of the electrogenic flora and whether certain specific electron-consuming nitrogen and phosphorus removal functional flora appears, which influences the stability of the electric signal. The cathode filler layer needs to fully utilize oxygen in the air as an electron acceptor, so that the electron transfer is facilitated.
By adopting the method, the sewage can generate stable electric quantity signals in the process of flowing through the artificial wetland, the COD concentration in the sewage is fed back in real time, and the sensitivity can reach 52.92C/(mg.L)-1)。
A biosensor device for monitoring COD concentration in constructed wetland in real time is provided with a bottom non-conductive filler layer, an anode conductive filler layer, a non-conductive filler isolating layer and a cathode conductive filler layer from bottom to top; the method is characterized in that: the anode conductive filler layer is respectively connected with the bottom non-conductive filler layer and the non-conductive filler isolation layer, the cathode conductive filler layer is connected with the non-conductive filler isolation layer, wetland plants are planted in the non-conductive filler isolation layer, the anode collector electrode and the cathode collector electrode are connected through an outer lead load, and the anode collector electrode and the cathode collector electrode are respectively placed in the anode conductive filler layer and the cathode conductive filler layer.
The biosensor device for monitoring the COD concentration in the constructed wetland in real time is characterized in that:
the fillers in the anode filler layer and the cathode conductive filler layer are granular activated carbon or graphite granules; the particle diameter of the granular active carbon and the graphite particles is 1-5 mm.
The anode collector and the cathode collector are made of graphite felt, graphite rods or stainless steel nets.
The non-conductive filler isolation layer in the device is one or any one of one to four of gravel, sandstone, anthracite and biological ceramsite;
the wetland plant is one or any combination of one to six of canna, bamboo reed, windmill grass, reed, sweet grass and cord grass;
through the technical measures: the most critical components of the present invention are the anode filler layer, the cathode filler layer and their effective connections. The material and the property of the conductive filler of the anode filler layer, the position and the thickness of the anode filler layer and other parameters directly influence the growth and enrichment of the anode electrogenesis flora. The cathode filler layer is arranged to contact with air and keep the sewage wet so as to ensure sufficient electron acceptors and accelerate the electron transfer efficiency. The anode filler layer and the cathode filler layer are connected through an anode collector and a cathode collector through external leads respectively, the anode collector and the cathode collector realize efficient electron collection and form a communication circuit through the external leads, and output of electric signals is ensured. Meanwhile, the electric signal is represented by the output electric quantity, the COD concentration can be fed back in real time, and the problems of fluctuation of the voltage signal, non-full-time response and the like in the prior art are solved. By adopting the technical measures of the invention, the sewage with COD in the range of 0-1000mg/L can be monitored in real time, and the electric quantity signals and the COD concentration all present good linear relation within 0-40 h.
Compared with the prior art, the invention has the following advantages and effects:
1. the invention adopts the output electric quantity as the sensor signal, which is more stable than the voltage signal, and the signal has a good linear relation with the measured sewage concentration at any time, and the response time is quicker than that of the voltage signal.
2. The CW-MFC integrated sensor formed by the invention can realize the electric quantity signal conversion of the sewage COD concentration only by burying the anode filler layer and the cathode filler layer and connecting the anode filler layer and the cathode filler layer with a simple lead, does not need to add a chemical electrode, does not need to replace the electrode, does not need to update the electrode liquid of the conventional microbial fuel cell, and has simple and convenient maintenance and low cost.
Drawings
Fig. 1 is a schematic diagram of a device for monitoring COD concentration in an artificial wetland in real time.
Wherein: 1-bottom non-conductive filler layer; 2-anode conductive filler layer; 3-a non-conductive filler isolation layer; 4-a cathode conductive filler layer; 5-wetland plants; 6-anode collector; 7-a cathode collector; 8-wire (plain); 9-external line load (commercially available, common); 10-electric signal collector (commercially available, common).
FIG. 2A is a graph of response voltage (U) versus time (t) for different COD concentrations using a biosensor formed using the device of the present invention and using the voltage as the response signal.
FIG. 2B is a graph of the response of the biosensor formed using the method and apparatus of the present invention to different COD concentrations in the amount of electricity (Q) as a function of time (t).
FIG. 3A is a graph showing the change of voltage signal (U) with time (t) for sewage having COD of 400mg/L using three sensor devices MS1, MS2, and MS3 of the present invention.
FIG. 3B is a graph showing the time (t) of the signal (Q) of the electric quantity of wastewater with COD of 400mg/L for three sensors MS1, MS2 and MS3 formed by the method and apparatus of the present invention.
Detailed Description
The following description and drawings of the present invention are made with reference to fig. 1, fig. 2A, fig. 2B, fig. 3A, and fig. 3B, and are not intended to limit the present invention.
Example 1:
a biosensor method for monitoring the COD concentration of an artificial wetland in real time comprises the following steps:
A. an anode conductive filler layer 2 is arranged above a non-conductive filler layer 1 at the bottom of the vertical flow constructed wetland, and an anode collector 6 rolled into a cylinder shape is inserted into the anode conductive filler layer 2;
B. a non-conductive filler isolation layer 3 is arranged above the anode conductive filler layer 2;
C. a cathode conductive filler layer 4 is arranged above the non-conductive filler isolation layer 3, and an annular cathode collector electrode 7 is inserted into the cathode conductive filler layer 4;
D. the wetland plants 5 penetrate through the annular cathode collector 7, and the root systems of the wetland plants 5 are mainly distributed at the middle upper part of the non-conductive filler isolation layer 3;
E. one end of the anode collector 6 and one end of the cathode collector 7 are connected with an external line load 9 through a lead 8 to form a circuit, and two ends of the electric signal collector 10 are connected with the external line load 9;
F. sewage continuously enters from the bottom of the system and sequentially rises in a plug-flow manner along the bottom non-conductive filler layer 1 and the anode conductive filler layer 2, is fully utilized by the electrogenic flora in the anode conductive filler layer 2, and organic matters are used as substrates and are converted into electrons by the electrogenic flora in the self-metabolism process;
G. then the sewage flows into a non-conductive filler isolation layer 3 which mainly functions as a separator between an anode conductive filler layer 2 and a cathode conductive filler layer 4;
H. then the sewage flows into the cathode conductive filler layer 4 and is discharged from the layer;
I. finally, in the process that the sewage flows through the system, the electric quantity signal converted from the COD is displayed immediately through the electric signal collector 10;
J. and the real-time displayed electric quantity signal obtains the concentration of the real-time sewage through a linear relation equation of the COD concentration and the electric quantity signal.
The experimental results show that: after the method is adopted, the COD concentration of the sewage can be converted and indicated in real time through the displayed electric quantity signal, the electric signal is stable, and the reflected COD concentration of the sewage is accurate and efficient. When the voltage is taken as a response signal, the duration of the stable voltage signal is 11.7 hours, and the voltage signal is stable only when the voltage signal enters the system from the 5 th hour of sewage. When the electric quantity is taken as the response signal, the electric quantity signal responds and tends to be stable from the moment when the sewage enters the system, and the duration time of the electric quantity signal is 17.8 hours until the COD in the sewage is consumed. Therefore, the advantages and effects of the electric quantity response signal are adopted.
Example 2:
the utility model provides a biosensor device of real-time supervision constructed wetland COD concentration, the device has laid bottom non-conductive filler layer 1, positive pole conductive filler layer 2, non-conductive filler isolation layer 3, negative pole conductive filler layer 4 from bottom to top, its characterized in that: the anode conductive filler layer 2 is respectively connected with the bottom non-conductive filler layer 1 and the non-conductive filler isolation layer 3, the cathode conductive filler layer 4 is connected with the non-conductive filler isolation layer 3, wetland plants 5 are planted in the non-conductive filler isolation layer 3, the anode collector 6 and the cathode collector 7 are connected through a lead 8, the anode collector 6 and the cathode collector 7 are respectively placed in the anode conductive filler layer 2 and the cathode conductive filler layer 4, one end of the anode collector 6 and one end of the cathode collector 7 are respectively connected with the lead 8 and an external line load 9, and two sides of the external line load 9 are respectively connected with two ends of the electric signal collector 10.
The biosensor device for monitoring the COD concentration in the constructed wetland in real time is characterized in that: the fillers in the anode filler layer 2 and the cathode conductive filler layer 4 are granular activated carbon or graphite granules; the particle diameters of the granular activated carbon and the graphite particles are 1 or 2 or 3 or 4 or 5 mm.
The bottom non-conductive packing layer 1 and the non-conductive packing isolation layer 3 are one or any one of one to four of gravel, sandstone, anthracite and biological ceramsite.
The wetland plant 5 is one or any combination of one to five of canna, bamboo reed, windmill grass, reed, sweet grass and rice grass.
The anode conductive filler layer 2 is embedded with an anode collector 6, and the anode collector 6 can be a graphite felt, a graphite rod or a stainless steel net, wherein one (sheet) or a plurality (2-6) of the graphite felt, the graphite rod or the stainless steel net is connected in series.
The anode collector 6 and the cathode collector 7 are made of graphite felt, graphite rods or stainless steel nets.
The lead 8 is common and commercially available.
The external line load 9 has a resistance of 500-.
The electric signal collector 10 can collect and display real-time voltage, current, electric quantity signals and the like on a terminal.
The treated sewage has a residence time in the apparatus of 2.2 to 138 hours.
The experimental results show that: after the device is adopted, the dynamic COD concentration of the inlet water can be truly indicated in real time through an electric quantity signal in the sewage purification process. The relative abundances of anode-enriched Geobacter and Geothrix were 3.36% and 3.17%, respectively. The anode also enriches certain abundance of denitrifying bacteria, namely thermoeutta (3.65%), Gemmobacter (2.92%), Thauera (2.91%), Hydrogenophaga (1.12%), arinibacter (1.69%) and hygropbium (2.18%), which can directly utilize electrons generated by the electrogenic bacteria for nitrate reduction, thereby reducing the voltage transmitted through a lead and making the voltage signal appear unstable (fig. 2A). However, the electric quantity signal still presents a better straight line trend, which is enough to prove the reliability of the electric quantity signal.
Example 3:
a biosensor method for monitoring the COD concentration of an artificial wetland in real time comprises the following implementation processes: the procedure was as in steps A-J of example 1.
The COD in the sewage is monitored in real time by adopting the method and the device, and the experimental result shows that:
1. compared with the output voltage, the output electric quantity is adopted as a response signal of the COD concentration, and the stability of the device is greatly enhanced. As shown in fig. 2A, when the voltage signal is used, the output voltage shows a fast rise in a short time, then stabilizes at a high value for a longer time, and then slowly falls until there is no signal, so that it is necessary to take a stable voltage value to reflect the real concentration value. And the real-time concentration can be truly represented from the time when the signal appears to the time when the signal disappears by adopting the electric quantity signal (figure 2B), so that the method is more scientific and more convenient.
2. The real-time electricity generated has a good linear relationship with the COD concentration (see MS1 sensor in Table 1).
When the measured sewage COD concentration is 0-400mg/L, the real-time linear relation equation of the electric quantity signal and the sewage COD is as follows: cCOD(t)＝0.019Q(t)+37.69(1),R2＝0.993；
When the measured sewage COD concentration is 400-1000mg/L, the linear relation equation of the real-time electric quantity signal and the sewage COD is as follows: cCOD(t)＝0.0053Q(t)+264.82(2),R2＝0.980；
(1) And (2) wherein Q(t)The unit is coulomb C, CCOD(t)The COD concentration value of the sewage measured at the time t is in mg/L.
The COD concentration range of the sewage is 0-1000 mg.L-1. (when the electric signal is 0 or the electric signal is no response after the sewage flows through the system, the COD concentration can be approximately considered to be 0)
The depth of the anode filler layer is 15cm, and the anode filler layer is positioned at 1/5-1/2 of the total height of the bottom device.
The top surface of the anode filler layer is 20cm away from the bottom surface of the cathode filler layer.
The other implementation steps are the same as in example 1.
Example 4:
by adopting the method, the difference of the time for starting the voltage signal to be stable caused by the different configurations of the device is avoided, three groups of sensor devices with different configurations are arranged and named as MS1, MS2 and MS3 respectively (the structural parameters of each group are shown in Table 1), the COD concentration in the sewage is monitored in real time, and the experimental result shows that:
1. the voltage signals of the three devices are shown in fig. 3(a), and the output voltage signals all show a rapid rise in time firstly for a short time, then stabilize at a high value for a longer time, and finally slowly fall until there is no signal. However, the three devices have inconsistent time for voltage stabilization, and the time for voltage stabilization duration is also different. The MS1, the MS2 and the MS3 enter a stable period after 2h, 3h and 5h respectively, and the duration of the stable voltage signal is 40.67h, 21.00h and 11.17h respectively. The output power signals of the three devices are shown in fig. 3(B), and the power changes with time from zero to show uniform linear growth. When the signal appears, the COD concentration in the sewage can be truly reflected at each moment.
2. The total relative abundance of the anodically enriched denitrifying bacteria Thermoguta, Gemmobacter, Thauera, Hydrogenophaga, Aridibacter, Hyphosphoribium, Ralstonia, Ornatilinea, Longilinea and Exiguobacterium in MS1, MS2 and MS3 is 9.58%, 9.04% and 15.37%, respectively. These denitrifying bacteria, enriched at the anode, compete for the electrons produced by the anode and affect the stability of the voltage in the output voltage (FIG. 3 (A)). However, the electric signals (fig. 3(B)) output by the three devices are not affected, and the linear correlation coefficients of the electric signals and the sewage COD concentration respectively reach 0.993, 0.980 and 0.999.
3. The sensitivities of the sensors MS1, MS2 and MS3 are 52.92, 65.78 and 23.78C/(mg.L) respectively-1) (ii) a The response time of the electric quantity signal is 43.2h, 31h and 17.8h respectively.
The COD concentration range of the sewage is 400 mg.L-1。
The other implementation steps are the same as in example 1.
TABLE 1
Claims (7)
1. The utility model provides a method for using COD concentration in biosensor device real-time supervision constructed wetland which characterized in that buries negative pole, anode electrode layer in the different packing layers of vertical flow constructed wetland, utilizes the perpendicular natural redox potential difference and the anaerobism of different degree of depth packing layers, oxygen deficiency, good oxygen microenvironment in the vertical flow constructed wetland, enrichment positive pole electrogenesis fungus crowd, electrogenesis fungus crowd uses the organic matter in the sewage as the substrate and produces electron and forms the circuit through the external conductor, the signal of telecommunication of production can be as the instruction of sewage COD concentration, its step is:
A. an anode conductive filler layer is arranged in the middle or at the bottom of the vertical flow artificial wetland, and an anode collector is arranged in the anode conductive filler layer;
B. arranging a cathode conductive filler layer on the surface layer of the vertical flow artificial wetland filler, arranging a cathode collector in the layer, exposing one half of the layer to the air, keeping the other half of the layer soaked by sewage, and implanting plant roots of the wetland below the layer;
C. the anode conductive filler layer and the cathode conductive filler layer are separated by a non-conductive filler isolation layer;
D. one end of the anode collector and one end of the cathode collector are connected with a load through an outer lead to form a circuit;
E. the output electric quantity signal is displayed by an electric signal detector;
F. sewage enters the artificial wetland from the bottom and is discharged from a water outlet of the upper cathode conductive packing layer;
G. and in the process of flowing through the system, the COD concentration of the sewage is obtained in real time through the electric quantity signal displayed immediately, and the adjustment of the operation parameters of the artificial wetland is guided.
2. The biosensor device for monitoring the COD concentration of the constructed wetland in real time according to the method of claim 1, which is paved with a bottom non-conductive filler layer (1), an anode conductive filler layer (2), a non-conductive filler isolation layer (3) and a cathode conductive filler layer (4) from bottom to top, and is characterized in that: the anode conductive packing layer (2) is respectively connected with the bottom non-conductive packing layer (1) and the non-conductive packing isolation layer (3), the cathode conductive packing layer (4) is connected with the non-conductive packing isolation layer (3), wetland plants (5) are planted in the non-conductive packing isolation layer (3), the anode collector electrode (6) and the cathode collector electrode (7) are connected through a lead (8), the anode collector electrode (6) and the cathode collector electrode (7) are respectively placed in the anode conductive packing layer (2) and the cathode conductive packing layer (4), one end of the anode collector electrode (6) and one end of the cathode collector electrode (7) are respectively connected with the lead (8) and an external line load (9), and two sides of the external line load (9) are respectively connected with two ends of the electric signal collector (10).
3. The biosensor device for monitoring the COD concentration of the constructed wetland in real time according to the method of claim 1, is characterized in that: an anode collector electrode (6) is embedded in the anode conductive filler layer (2), and the anode collector electrode (6) is one or 2-6 graphite felts, graphite rods or stainless steel nets which are connected in series.
4. The biosensor device for monitoring the COD concentration of the constructed wetland in real time according to the method of claim 1, is characterized in that: the fillers in the anode conductive filler layer (2) and the cathode conductive filler layer (4) are granular activated carbon or graphite granules; the particle diameters of the granular activated carbon and the graphite particles are 1-5 mm.
5. The biosensor device for monitoring the COD concentration of the constructed wetland in real time according to the method of claim 2, is characterized in that: the bottom non-conductive packing layer (1) and the non-conductive packing isolation layer (3) are any one of gravel, sandstone, anthracite and biological ceramsite.
6. The biosensor device for monitoring the COD concentration of the constructed wetland in real time according to the method of claim 1, is characterized in that: the wetland plant (5) is one or any combination of two to five of canna, arundo donax linn, pinus avicularis, reed, sweet citronella and cord grass.
7. The biosensor device for monitoring the COD concentration of the constructed wetland in real time according to the method of claim 1, is characterized in that: the anode collector (6) and the cathode collector (7) are made of graphite felt, graphite rods or stainless steel nets.
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