CN113540542B - Microbial battery for constructed wetland - Google Patents
Microbial battery for constructed wetland Download PDFInfo
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- CN113540542B CN113540542B CN202110853334.3A CN202110853334A CN113540542B CN 113540542 B CN113540542 B CN 113540542B CN 202110853334 A CN202110853334 A CN 202110853334A CN 113540542 B CN113540542 B CN 113540542B
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- 229910002804 graphite Inorganic materials 0.000 claims abstract description 33
- 239000010439 graphite Substances 0.000 claims abstract description 33
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 27
- 239000010935 stainless steel Substances 0.000 claims abstract description 25
- 239000010802 sludge Substances 0.000 claims abstract description 13
- 229920000742 Cotton Polymers 0.000 claims abstract description 11
- 239000003365 glass fiber Substances 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 20
- 239000001632 sodium acetate Substances 0.000 claims description 20
- 235000017281 sodium acetate Nutrition 0.000 claims description 20
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- 239000008103 glucose Substances 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 230000002572 peristaltic effect Effects 0.000 claims description 5
- 239000010963 304 stainless steel Substances 0.000 claims description 4
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 claims description 4
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims description 3
- 230000008093 supporting effect Effects 0.000 abstract description 3
- 235000001727 glucose Nutrition 0.000 description 17
- 239000000758 substrate Substances 0.000 description 14
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- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- 238000001075 voltammogram Methods 0.000 description 2
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- 238000004519 manufacturing process Methods 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
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- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention relates to an artificial wetland microbial battery, which comprises: a down-flow reactor, an anode and an air cathode; a glass fiber cotton separation layer is arranged in the downflow reactor and divides an inner cavity of the downflow reactor into an upper cavity and a lower cavity; gravel and anaerobic sludge are filled in the upper cavity and the lower cavity; the anode and the air cathode are respectively arranged at the bottom and the top of the downflow reactor; the anode comprises a first stainless steel net and a first graphite felt, and the first graphite felt is arranged outside the first stainless steel net; the air cathode comprises a second stainless steel net and a second graphite felt, and the second stainless steel net is wrapped outside the second graphite felt. The constructed wetland microbial battery provided by the invention does not need to plant plants, and is provided with gravels for supporting, so that the sludge blockage is reduced.
Description
Technical Field
The invention relates to the technical field of electricity generation in environmental engineering, in particular to an artificial wetland microbial battery.
Background
The constructed wetland microbial fuel cell (CW-MFC) is a new technology combining the Constructed Wetland (CW) and the Microbial Fuel Cell (MFC), can purify sewage and generate electricity, has wide prospect and practical application value, and has attracted extensive attention in recent years. At present, the CW-MFC in the up-flow mode is mostly adopted by researchers, but the maximum power density is not high, and is usually only 10-30mW m -2 . However, much research is focused on the upflow structure, but the upflow may cause the internal resistance of the system to become large due to the sludge clogging effect caused by the long-time operation, further affecting the transfer of the electron amount to cause the decrease of the electricity generation performance. How to enhance the electricity generation performance of the down-flow reactor is also one of the concerns of the society of today.
Glucose or sodium acetate is generally used as a substrate which is one of the important factors that CW-MFC can generate electricity. Glucose is a fermentation-type substance that is easily absorbed and decomposed by microorganisms, but produces volatile fatty acids (e.g., acetic acid, propionic acid, and lactic acid) and carbon dioxide, etc., during its metabolism. Sodium acetate is a micromolecule substance of a non-fermentation substance and is easy to be completely decomposed and utilized by the electrogenesis microorganisms. Different substrates (such as sodium acetate, glucose and propionic acid) have different influences on the formation of anode biomembranes, and the internal resistance of the system is limited by the used substrates and products formed after metabolism, thereby influencing the electricity generation performance of the system. However, the time required to initiate acclimation and the effect on the electrochemical performance of the system for the downflow CW-MFC system using the two classical substrates glucose and sodium acetate have been further investigated.
Disclosure of Invention
The invention aims to provide an artificial wetland microbial battery, so as to overcome the influence of the blocking effect of plants and sludge on the electrogenesis performance and improve the output power density.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides an artificial wetland microbial battery, which comprises: a down-flow reactor, an anode and an air cathode;
a glass fiber cotton separation layer is arranged inside the downflow reactor and divides an inner cavity of the downflow reactor into an upper cavity and a lower cavity;
gravel and anaerobic sludge are filled in the upper cavity and the lower cavity;
the anode and the air cathode are respectively arranged at the bottom and the top of the downflow reactor;
the anode comprises a first stainless steel mesh and a first graphite felt, and the first graphite felt is arranged outside the first stainless steel mesh;
the air cathode comprises a second stainless steel net and a second graphite felt, and the second stainless steel net is wrapped outside the second graphite felt.
Optionally, the top and the bottom of the sidewall of the downflow reactor are respectively provided with a water inlet and a water outlet.
Optionally, the constructed wetland microbial cell further comprises a peristaltic pump;
the peristaltic pump is arranged at the water outlet of the downflow reactor.
Optionally, the anode and the air cathode are led out from the side wall of the downflow reactor through a wire.
Optionally, the constructed wetland microbial battery further comprises an external circuit.
Optionally, the external circuit includes an external resistor and a data collector;
the external resistor is connected with the anode and the air cathode through a lead, and the data collector is connected with the external resistor in parallel.
Optionally, the inlet water carbon source of the constructed wetland microbial cell is as follows: sodium acetate and/or glucose.
Optionally, the COD concentration of the inlet water carbon source of the constructed wetland microbial cell is 250-350mgCOD/L, and the ammonia nitrogen concentration is 20-50mg/L.
According to the specific embodiment provided by the invention, the invention discloses the following technical effects:
the invention discloses an artificial wetland microbial battery, which comprises: a down-flow reactor, an anode and an air cathode; a glass fiber cotton separation layer is arranged inside the downflow reactor and divides an inner cavity of the downflow reactor into an upper cavity and a lower cavity; gravel and anaerobic sludge are filled in the upper cavity and the lower cavity; the anode and the air cathode are respectively arranged at the bottom and the top of the downflow reactor; the anode comprises a first stainless steel mesh and a first graphite felt, the first graphite felt being disposed outside the first stainless steel mesh; the air cathode comprises a second stainless steel net and a second graphite felt, and the second stainless steel net is wrapped outside the second graphite felt. The constructed wetland microbial battery provided by the invention does not need to plant plants, and is provided with gravels for supporting, so that the sludge blockage is reduced.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without inventive exercise.
FIG. 1 is a schematic structural diagram of an artificial wetland microbial cell provided by the invention;
fig. 2 is a diagram of the COD content at the water outlet of the constructed wetland microbial cell based on glucose (s.g.) and sodium acetate (s.s.) respectively according to the embodiment of the present invention;
fig. 3 is a graph comparing the electricity generation performance of constructed wetland microbial cells based on glucose (s.g.) and sodium acetate (s.s.) respectively according to the embodiment of the present invention; fig. 3a is a graph showing the voltage change of the microbial cell of the artificial wetland with the substrate of glucose (s.g.) and sodium acetate (s.s.), respectively, and fig. 3b is a graph showing the power density and polarization of the microbial cell of the artificial wetland with the substrate of glucose (s.g.) and sodium acetate (s.s.), respectively;
fig. 4 is a voltammogram of an artificial wetland microbial cell with glucose (s.g.) and sodium acetate (s.s.) as substrates according to an embodiment of the present invention, fig. 4a is a cyclic voltammogram, and fig. 4b is a linear sweep voltammogram;
fig. 5 is a Tafel plot of constructed wetland microbial cells with glucose (s.g.) and sodium acetate (s.s.) as substrates, respectively, according to an embodiment of the present invention;
fig. 6 is an electrochemical impedance nyquist diagram of an artificial wetland microbial cell with a substrate of glucose (s.g.) and sodium acetate (s.s.), respectively, according to an embodiment of the present invention, fig. 6a is an electrochemical impedance nyquist diagram of an artificial wetland microbial cell with a substrate of glucose (s.g.), and fig. 6b is an electrochemical impedance nyquist diagram of an artificial wetland microbial cell with a substrate of sodium acetate (s.s.);
fig. 7 is an equivalent circuit diagram for measuring electrochemical impedance of an artificial wetland microbial cell according to an embodiment of the invention, fig. 7a is an equivalent circuit diagram for measuring electrochemical impedance of an artificial wetland microbial cell with glucose (s.g.) as a matrix, and fig. 7b is an equivalent circuit diagram for measuring electrochemical impedance of an artificial wetland microbial cell with sodium acetate (s.s.) as a matrix.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention aims to provide a constructed wetland microbial battery to overcome the influence of plant and sludge blocking effect on the electricity production performance and improve the output power density.
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in further detail below.
As shown in fig. 1, the present invention provides an artificial wetland microbial cell comprising: a down-flow reactor, an anode 1 and an air cathode 5.
A glass fiber cotton separation layer 4 is arranged inside the downflow reactor, and the glass fiber cotton separation layer 4 divides the inner cavity of the downflow reactor into an upper cavity and a lower cavity; and a shading black ribbon is wrapped outside the downflow reactor. The top and the bottom of the side wall of the downflow reactor are respectively provided with a water inlet 6 and a water outlet 2. The anode 1 and the air cathode 5 are led out through the side wall of the downflow reactor through a lead 9 and are connected with an external resistor 7, and a data collector 8 is connected in parallel with two ends of the external resistor 7 through leads for voltage data collection. The water outlet 2 realizes the consistency of the water outlet flow rate and the water inlet flow rate through a peristaltic pump, and the water level balance is ensured.
Gravel and anaerobic sludge 3 are filled in the upper cavity and the lower cavity. The gravel is arranged in the down-flow reactor to ensure uniform water distribution and supporting effect.
The anode and the air cathode are respectively arranged at the bottom and the top of the down flow reactor.
The anode includes a first stainless steel mesh and a first graphite felt disposed exterior to the first stainless steel mesh. That is, the anode has a structure in which a stainless steel mesh (first stainless steel mesh) serving as a current collector is inserted between graphite felts (first graphite felts). The anode takes the pretreated graphite felt as a substrate, and the treated stainless steel wire mesh is embedded in the middle of the graphite felt.
The air cathode comprises a second stainless steel net and a second graphite felt, and the second stainless steel net is wrapped outside the second graphite felt. That is, the air cathode is a structure in which the outer surface of the graphite felt (second graphite felt) is wrapped by the stainless steel net (second stainless steel net). The air cathode takes the pretreated graphite felt as a substrate, and the outer surface of the graphite felt is coated with the treated stainless steel wire mesh to form the air cathode.
In the operation process, the temperature of the system is controlled to be 28-32 ℃, and the pH =6-7; the influent carbon source is sodium acetate and glucose respectively, and the COD concentration is 250-350mgCOD/L; the ammonia nitrogen concentration is 20-50mg/L; the hydraulic retention time is 1-2d.
The carbon source is used as anode fuel to be oxidized to generate electrons, the electrons are transmitted to the anode 1 through solution, sludge, bacteria and the like, and then transmitted to the air cathode through the lead 9 and the external resistor 7, and form a loop with the internal components of the constructed wetland microbial cell to generate current, so that the output power density is improved.
The anode and the air cathode are connected to an external circuit and then connected to a data collector for voltage data collection. The whole downflow reactor adopts a continuous operation mode, and the integrated device is simple to operate, high in controllability and capable of finally obtaining higher electric energy.
The present invention also provides the following specific embodiments to explain the technical effects of the present invention.
The constructed wetland microbial fuel cell device has total COD of 300mg/L and hydraulic retention time of 1.5 days. The bottom anode region is filled with anaerobic sludge and coated on the gravel and is separated from the upper cathode region by glass fiber cotton, the vertical distance between the glass fiber cotton and the bottom of the device is 17cm, and the thickness of the glass fiber cotton is 1cm. The anode is arranged at the bottom, the cathode is arranged at the top of the downflow reactor and is used as an air cathode, and the vertical distance between the lower surface of the cathode and the upper surface of the anode is 24cm. The anode was a graphite felt having a size of 8cm (length) by 8cm (width) by 2cm (thickness), and a 5 mesh 304 stainless steel wire mesh having a wire thickness of 0.6mm and a side length of 8cm was inserted into the middle thereof. The air cathode is a graphite felt with the diameter of 21cm and the thickness of 2cmBoth sides were vertically cut to make 256cm as a surface 2 The outer surface of the cathode is coated with a 5-mesh 304 stainless steel wire mesh with the wire thickness of 0.6 mm.
Concentration of main influent substrate: sodium acetate (s.s.) and glucose (s.g.) were fed into water at a concentration of 300 mgCOD/L.
Simulated wastewater enters the down-flow reactor from the top through the water inlet 6, enters the anode region through the air cathode 5, gravel, anaerobic sludge 3 and a glass fiber cotton separation layer 4, microorganisms coated on the gravel in the anode region are oxidized by matrix organic matters to generate electrons, the electrons are transferred to the surface of the anode 1 and transferred to the air cathode 5 through the current collector stainless steel in the anode 1, and a closed loop is formed to generate current through the lead 9 and the external resistor 7. Along with continuous water inflow, the voltage generated by the external resistor begins to increase and begins to stabilize, COD is removed while high output power density is realized, and continuous controllable water outflow is realized through the water outlet 2.
As shown in fig. 2-7, the device constructed by the present invention effectively improves the problem of output power density. Meanwhile, the obtained carbon source sodium acetate has the advantage of more excellent electricity generation performance. As shown in FIG. 3, the device with sodium acetate (S.S.) as the matrix produced a maximum output power density of 48.14mW m -2 Glucose (S.G.) (42.61 mWm) -2 ) High, and increased by 100% -187% compared with other studies. As shown in fig. 2, the s.s. has a stronger COD removing ability than the s.g. does. The electrochemical characterization as shown in fig. 4 and 5 shows that the anode of s.s. Exhibits higher current response and electron transfer capacity than s.g. Fig. 7 shows the equivalent circuit R (Q (RW)) of the electrochemical impedances measured (fig. 7 a) s.g. and (fig. 7 b) s.s. as shown in fig. 7, which is a combination of polarization resistance (charge transfer resistance, rp), solution resistance (ohmic resistance, rs), weber impedance diffusion element (W) and a constant phase angle element (CPE), and the results show that the sodium acetate based device of the present invention has a lower internal resistance.
Based on the above analysis, the effects and benefits of the present invention are: in the anode region of the integrated downflow system, the anode microorganisms can transfer electrons generated by carbon source oxidation to the surface of the anode and then transfer the electrons to the air cathode through an external circuit, so that the COD in the water body can be removed while high output power is achieved. The water inlet mode is continuous water inlet, and the water outlet mode is continuous water outlet. The down-flow reactor is integrated, the support layer and the filler adopt gravels to reduce the cost, and the middle part of the down-flow reactor is made of glass fiber cotton to reduce the oxygen mass transfer coefficient and relieve the reverse flow of electrons. The down-flow form has a stronger power density output than the conventional up-flow form, and can improve by 100% -187%. In addition, the used cathode construction mode is also one of the cores, and compared with a single noble metal electrode, the economic cost and the high efficiency of the operation result can be greatly ensured. The size of the final anode, 6-15cm (length) 6-15cm (width) 1-4cm (thickness), is also one of the main cores of the invention. The method is beneficial to promoting the electricity generation performance of the device to be improved and can purify the COD of the water body.
The air cathode integrated down-flow type non-plant artificial wetland-microbial fuel cell device has the advantages of small occupied area, low construction cost and simple and convenient operation, is suitable for the design of integrated devices, and has wide application prospect in the construction of sponge cities and the treatment of urban water.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The principles and embodiments of the present invention have been described herein using specific examples, which are provided only to help understand the method and the core concept of the present invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, the specific embodiments and the application range may be changed. In view of the above, the present disclosure should not be construed as limiting the invention.
Claims (6)
1. An artificial wetland microbial cell, characterized in that the artificial wetland microbial cell comprises: a down-flow reactor, an anode and an air cathode;
a glass fiber cotton separation layer is arranged inside the downflow reactor and divides an inner cavity of the downflow reactor into an upper cavity and a lower cavity;
gravel and anaerobic sludge are filled in the upper cavity and the lower cavity;
the anode and the air cathode are respectively arranged at the bottom and the top of the downflow reactor;
the anode comprises a first stainless steel mesh and a first graphite felt, the first graphite felt being disposed outside the first stainless steel mesh;
the air cathode comprises a second stainless steel net and a second graphite felt, and the second stainless steel net is wrapped outside the second graphite felt;
the top and the bottom of the side wall of the downflow reactor are respectively provided with a water inlet and a water outlet; the constructed wetland microbial cell also comprises a peristaltic pump; the peristaltic pump is connected with the water inlet and the water outlet of the downflow reactor;
the anode is a graphite felt with the size of 8cm (length) 8cm (width) 2cm (thickness), and a 5-mesh 304 stainless steel wire mesh with the wire thickness of 0.6mm and the side length of 8cm is inserted in the middle of the graphite felt; an air cathode is a graphite felt with a diameter of 21cm and a thickness of 2cm, and is vertically cut at both sides to obtain a graphite felt with a surface of 256cm 2 The outer surface of the cathode is coated with a 5-mesh 304 stainless steel wire mesh with the wire thickness of 0.6 mm.
2. The constructed wetland microbial cell of claim 1, wherein the anode and the air cathode are led out from the side wall of the downflow reactor through a wire.
3. The microbial cell of claim 1, wherein the microbial cell further comprises an external circuit.
4. The constructed wetland microbial battery of claim 3, wherein the external circuit comprises an external resistor and a data collector;
the external resistor is connected with the anode and the air cathode through a lead, and the data collector is connected with the external resistor in parallel.
5. The constructed wetland microbial cell of claim 1, wherein the carbon source of the inlet water of the constructed wetland microbial cell is: sodium acetate and/or glucose.
6. The constructed wetland microbial cell of claim 1, wherein the COD concentration of the inlet water carbon source of the constructed wetland microbial cell is 250-350mgCOD/L, and the ammonia nitrogen concentration is 20-50mg/L.
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| AU2020103245A4 (en) * | 2020-11-05 | 2021-01-14 | Sichuan Agricultural University | A device for enhancing denitrification by combining a horizontal subsurface flow with a vertical flow CW-MFC system in series and an operation method thereof |
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| CN105858902B (en) * | 2016-05-25 | 2018-09-07 | 哈尔滨工业大学 | Plant compound bio cathode wetland type biological fuel cell and water purification produce electricity method |
| CN108383232B (en) * | 2018-04-03 | 2020-04-10 | 中国科学院水生生物研究所 | Method and device for improving nitrate nitrogen removal efficiency of downward vertical flow constructed wetland |
| CN109081426B (en) * | 2018-08-29 | 2021-07-09 | 东华大学 | Microbial fuel cell type composite artificial wetland with low internal resistance |
| CN112174293A (en) * | 2020-08-25 | 2021-01-05 | 兰州理工大学 | Electric-enhanced bioretention system for removing low-concentration antibiotics |
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| CN205662370U (en) * | 2015-11-20 | 2016-10-26 | 中国水利水电科学研究院 | But electric installation is produced to aeration and layering measuring constructed wetland |
| AU2020103245A4 (en) * | 2020-11-05 | 2021-01-14 | Sichuan Agricultural University | A device for enhancing denitrification by combining a horizontal subsurface flow with a vertical flow CW-MFC system in series and an operation method thereof |
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Application publication date: 20211022 Assignee: Guangxi Dinglian Environmental Protection Technology Co.,Ltd. Assignor: GUILIN University OF TECHNOLOGY Contract record no.: X2023980044425 Denomination of invention: A Kind of Artificial Wetland Microbial Battery Granted publication date: 20230324 License type: Common License Record date: 20231026 |