CN111816902B - Capacitive microbial desalination cell device and method applied to chemical tail water treatment - Google Patents
Capacitive microbial desalination cell device and method applied to chemical tail water treatment Download PDFInfo
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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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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- 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 a capacitive microbial desalination cell device and method applied to chemical tail water treatment, and belongs to the technical field of water resource treatment. The cell device comprises an anode chamber, a desalting chamber and a cathode chamber which are respectively separated by an anion-cation exchange membrane and a cation-exchange membrane; the anode adopts a carbon material, and the cathode adopts a hollow carbon fiber-carbon film capacitor electrode formed by a hollow carbon fiber-carbon film capacitor layer, a titanium substrate, a waterproof layer and a catalytic layer which are sequentially arranged; the anode and the cathode are connected by an external circuit. The desalting method includes the steps of circulating chemical tail water inside the anode chamber, serial connecting the anode chamber and desalting chamber of the cell unit after certain residence time, and circulating the water treated in the anode chamber to the desalting chamber for desalting and/or COD. The invention can integrally and efficiently remove organic matters and salt in the chemical tail water, efficiently recover the salt, has stable electrode structure and long service life, and can be widely applied to the treatment of various chemical tail water.
Description
Technical Field
The invention belongs to the field of water resource treatment, and particularly relates to a microbial desalination cell device and a microbial desalination cell method which are applied to chemical tail water treatment and are provided with hollow carbon fiber-carbon film capacitive electrodes.
Background
The chemical tail water refers to the discharged wastewater which is treated by a centralized sewage plant in a chemical park and reaches the first-level discharge standard B of urban sewage or the discharge standard of local chemical enterprises, and the residual salt is an important reason for inhibiting the recycling and resource utilization of the wastewater. At present, the cost of tail water treatment is limited to high, and the reuse water in China is mainly used for low-end reuse sections such as cooling circulation and the like, so that the method has significance of practical research and application in effectively removing salt in part of water at low cost and low energy consumption, and also conforms to the sustainable water-saving concept advocated by the state at present. The traditional desalting methods mainly include three major categories, namely thermal separation, membrane separation and electrochemical separation, and technologies such as multi-stage flash evaporation, multi-effect distillation, electrodialysis, reverse osmosis and the like have been widely applied in the market.
A Microbial Desalination Cell (MDC) is a device that converts biomass energy into electrical energy and synchronously carries out Desalination. Based on a microbial fuel cell, an anion-cation exchange membrane is added between an anode chamber and a cathode chamber to form a middle desalting chamber, and the brine in the middle desalting chamber is desalted under the condition of no external pressure and no electric energy; meanwhile, the wastewater in the MDC anode chamber is purified, and electric energy is generated. The desalting can be completed under the condition of no external energy input, secondary pollution is avoided, and organic matters in water can be integrally removed.
In fact, the chemical tail water still contains a certain amount of salt with use value for recycling. In addition, the Microbial Capacitance Desalination Cell (MCDC) is greatly limited by the service life of a capacitance electrode, the water quality condition of chemical tail water is complex, the electrode is easily influenced by the fluctuation of pH, temperature and conductivity of wastewater, and in addition, the adsorption pollution of organic pollutants on the surface of an electrode material and the scouring corrosion of the shearing force of the wastewater containing suspended particles on the surface of the electrode exist. Therefore, the conventional tabletting preparation method is difficult to ensure the adhesion strength of the capacitor material on the conductive substrate, easily causes the falling of the capacitor material, and is difficult to effectively deal with the variable and complex industrial wastewater quality.
Based on this, need for the special electric capacity electrode of microbial desalination battery configuration, can wholly improve electric capacity material's adhesion strength and electrode structural stability to the desalination demand of all kinds of waste water is adapted, and long-time operation is in order to retrieve the salinity that has use value, optimizes the mode of intaking simultaneously, makes it can get rid of organic matter and salinity in same system, will possess extensive application and market prospect.
Disclosure of Invention
1. Problems to be solved
Aiming at the problems that the added-value salt is difficult to recover and the service life of a cathode electrode is short in the chemical tail water treatment process of the existing microbial desalination battery, the invention provides the microbial desalination battery device and the method which are applied to the chemical tail water treatment and are provided with the hollow carbon fiber-carbon film capacitive cathode.
Another object of the present invention is to remove COD and salt from chemical tail water efficiently by the above method for operating a microbial desalination cell apparatus.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a capacitive microbial desalination cell device applied to chemical engineering tail water treatment comprises an anode chamber, a desalination chamber and a cathode chamber, wherein the anode chamber and the desalination chamber are separated by an anion exchange membrane, and the cathode chamber and the desalination chamber are separated by a cation exchange membrane; the anode of the battery device adopts a carbon material to load microorganisms and transfer electrons, and the cathode of the battery device adopts a hollow carbon fiber-carbon film capacitor electrode which comprises a hollow carbon fiber-carbon film capacitor layer, a titanium-based layer, a waterproof layer and a catalyst layer which are sequentially arranged; the anode and the cathode are connected by an external circuit with a resistor. The anode is loaded with domesticated electrogenesis microorganisms, can generate stable voltage while treating organic matters in water, is provided with a hollow carbon fiber-carbon film capacitive electrode as a cathode, can collect high-added-value metal ions separated from tail water while achieving an electronic effect, and has the advantages of high capacitance and long service life compared with the traditional capacitive electrode; the assembled cathode catalyzes oxygen molecules in air to be used as an electron acceptor to carry out reduction reaction through a platinum-carbon catalyst layer, electrons are unloaded from a waterproof layer formed by PTFE to complete electron transfer, and meanwhile, electrons of a circuit in the battery move to form an electric field, so that wastewater in a desalting chamber directionally moves to complete desalting through membrane separation, cations after passing through a membrane are adsorbed in a capacitor layer of the cathode.
Preferably, the hollow carbon fiber-carbon film capacitor layer structure is formed by covering a carbon film layer formed by carbonized microspheres on a titanium dioxide nanotube array embedded with hollow carbon fibers. The titanium dioxide nano array enhances the binding force between the capacitor layer and the titanium substrate, and effectively prolongs the service life of the capacitor; in addition, the carbon fibers are uniformly distributed on the titanium substrate under the condition that nickel exists in the precursor, and the formed hollow structure can greatly increase the capacitance of the capacitor layer, adsorb more renewable ions and prolong the regeneration period of the electrode.
Preferably, the area of the hollow carbon fiber-carbon film capacitor electrode is 1/2-3/4 of the cross section area of the cathode chamber, so that transferred electrons can be discharged into the cathode chamber through the waterproof layer, the electricity generation efficiency is improved while the electron transfer is not influenced, and higher desalting rate and adsorption rate are obtained.
Preferably, the anode carbon material of the battery device includes carbon felt, carbon brush, activated carbon particles, or the like. Similar to the traditional microbial fuel cell, the microbial fuel cell mainly has the functions of attaching and enriching the electrogenic microbes, and receiving and transmitting electrons transmitted by extracellular electrons of the electrogenic microbes.
Preferably, the anion exchange membrane and the cation exchange membrane of the microbial desalination cell device are heterogeneous electrodialysis ion exchange membranes, the thickness is preferably 0.5-1.0mm, the independent transmittance is not less than 90%, and the bursting strength is more than 0.3 Mpa.
Preferably, a resistor is connected between the cathode and the anode in series in the battery device, and the resistance value is 10-1500 omega.
Preferably, the preparation method of the hollow carbon fiber-carbon film capacitor electrode comprises the step of obtaining the integrated hollow carbon fiber-carbon film capacitor layer with the embedded structure by taking a titanium-based titanium dioxide nanotube array as a conductive matrix (current collector) and taking a mixed solution of glucose and nickel acetate as a precursor through vacuum induction, anaerobic pyrolysis and hydrophilic modification, wherein the temperature in the anaerobic pyrolysis step is 800-850 ℃. The temperature in the oxygen-free pyrolysis step is controlled to be 800-850 ℃ to promote TiO2The structure of the titanium suboxide is converted, the current collection efficiency of the capacitor electrode is improved, the electron conduction of the system is enhanced, and the ion enrichment and release process of the MDC-capacitor system is promoted.
Preferably, the specific preparation steps of the hollow carbon fiber-carbon film capacitor electrode are as follows:
preparation of S1 precursor: preparing glucose (C) with a certain concentration at room temperature6H12O6) Weighing nickel acetate (Ni (CH) tetrahydrate in the water solution)3COO)2·4H2O) solid is added into the glucose water solution, and a precursor is obtained after stirring and dissolving;
s2, placing a titanium-based titanium dioxide nanotube array (current collector) in a flask with two or more openings with a plug, ensuring that one opening of the flask is connected with a vacuum pump and the other opening is connected with a dropping funnel with a plug and a constant pressure, wherein a precursor is filled in the funnel; vacuumizing to a certain vacuum degree, then opening a constant-pressure dropping funnel, dropping the precursor into the two bottles until the liquid level is higher than the horizontal plane of the current collector, closing the funnel and the vacuum pump, and slowly releasing the air pressure in the bottles to atmospheric pressure;
s3, taking out the current collector processed in the step S2, placing the current collector on a horizontal table top, ensuring that one surface of pure titanium faces downwards, dropwise adding the precursor on the upper surface of the current collector and uniformly smearing the precursor to form a film, aging the film in air at room temperature, preheating and decomposing the film through a vacuum resistance box, and taking out the film for later use; this step is repeated several times to obtain the desired film thickness;
s4, placing the electrode dried in vacuum in the step S3 in a muffle furnace, pyrolyzing the electrode in air, placing the electrode in a nitrogen protective furnace for high-temperature carbonization and oxygen-free pyrolysis, and taking out the electrode to obtain the capacitor electrode with the formed hydrophobic capacitor layer;
s5, placing the capacitance electrode obtained in the step S4 in a nitric acid solution, heating and acidifying at a constant temperature, and washing with deionized water until the capacitance electrode is neutral to obtain a capacitance electrode of a hydrophilic capacitance layer;
s6, brushing a waterproof layer three times on the titanium base layer on one side of the capacitor layer obtained in the step S5 by adopting PTFE and nafion solution, and then uniformly coating a Pt-C catalyst on the side of the waterproof layer to obtain the hollow carbon fiber-carbon film capacitor electrode.
Preferably, the concentration of glucose in step S1 is 80-120g/L, and the concentration of nickel acetate is 10-40 g/L.
Preferably, the vacuum degree in the step S2 is 0.01-0.03 MPa.
Preferably, the aging time in the step S3 is 12-24h, the vacuum heating temperature is 55-65 ℃, and the heating time is 12 h.
Preferably, the muffle furnace temperature rising/reducing speed of the air-in-gas pyrolysis process in the step S4 is 1 ℃/min, and the heat preservation time at 200 ℃ and 250 ℃ is 2 h; in the oxygen-free pyrolysis process, the temperature rising/reducing speed of the nitrogen protection furnace is 1 ℃/min, and the temperature is kept for 1h at the temperature of 850 ℃ plus 800 ℃.
Preferably, the concentration of the nitric acid in the step S5 is 4.5-5.5mol/L, the constant-temperature heating temperature is 50-55 ℃, and the heating time is 18-24 h.
Preferably, the PTFE in the step S6 is a PTFE solution with a mass fraction of 60%, the Nafion solution is coated with 500. mu.L of Nafion solution with a mass fraction of 5% per 5mg of Pt-C catalyst according to the coating amount of the Pt-C catalyst, and the coating amount of the Pt-C catalyst is 0.2-0.6mg/cm2。
Preferably, the adding amount of the dropwise added precursor in the step S3 is less than or equal to 0.03 mu L; and/or the thickness of the titanium matrix in the titanium-based titanium dioxide nanotube array in the step S2 is less than or equal to 0.02mm, so that the internal resistance of the system is reduced, and a higher desalting rate can be achieved.
The invention also provides a capacitive microbial desalination method applied to chemical tail water treatment, which adopts the cell device, firstly, chemical tail water is internally circulated in the anode chamber, after a specific retention time, the anode chamber of the cell device is connected with the desalination chamber in series, so that water treated by the anode chamber enters the desalination chamber, and is circularly treated with desalination and/or COD in the desalination chamber and the anode chamber;
or firstly, nutrient solution is adopted to carry out internal circulation in the anode chamber, after specific retention time, chemical tail water is introduced into a desalting chamber to carry out circular treatment for desalting, and meanwhile, the salt in the tail water is recovered;
or firstly, nutrient solution is adopted to carry out internal circulation in the anode chamber, after specific retention time, chemical tail water is introduced into the desalting chamber, and the desalting chamber is connected with the anode chamber in series, so that the chemical tail water is circularly treated in the desalting chamber and the anode chamber to remove salt and/or COD;
or firstly, nutrient solution is adopted to carry out internal circulation in the anode chamber, and after a certain retention time, the chemical tail water is introduced into a desalting chamber connected in series with the capacitance desalting reactor, so that the chemical tail water is circulated in the desalting chamber and the capacitance desalting reactor for desalting treatment.
Residual COD in the chemical tail water provides a carbon source for the anode electrogenesis microorganisms to complete the electrogenesis process, the electrogenesis microorganisms perform an extracellular electron transfer function to transfer electrons to the carbon material anode, the circulation of the anode chamber is simultaneously used for starting the whole system to operate, and the chemical tail water can begin to be desalted after entering the desalting chamber; after the anode is circularly stabilized, tail water enters a desalting chamber, and ions in the tail water are subjected to membrane migration under the condition that the anode generates current to form an electric field, so that the desalting process is completed; at the moment, the cathode is used as an electron acceptor of the anode to complete the reduction process and the electron transfer, so that an electric field is generated in the whole internal circulation system; on the other hand, the capacitor layer adsorbs membrane ions at the same time, and ions which can be reused are recovered. Compared with the traditional MDC, the invention combines the functions of the anode chamber and the desalting chamber in series for the first time to form an integrated treatment device, increases the recovery function of metal ions with high added value, and is suitable for treating chemical tail water containing certain residual organic matters. The operation mode of the MDC system in the prior art is that sequencing batch or continuous flow desalting treatment is carried out in the desalting chamber, the anode and the desalting chamber act independently without connection, the anode only generates energy by oxidizing and degrading a carbon source independently to promote the operation of the whole system, although the substrate type of the anode chamber is changed continuously, the treatment mode of the MDC is not changed substantially, the occupied area of the whole system is large due to independent operation of salt and organic matters, the operation difficulty is high, and the MDC system is difficult to apply on a large scale and directly apply to chemical tail water with complex components.
Preferably, the water inlet mode of the desalting chamber in the battery device comprises a circulation sequence batch or continuous flow, and when the circulation sequence batch water inlet mode is adopted, a separate recovery chamber is arranged, the circulation flow rate is 0.5-5mL/min, and the retention time is 2-120 h; the flow rate of water inflow by adopting continuous flow is 0.2-1 mL/min.
In the invention, the cell device can connect the desalting chamber and the anode chamber in series for removing organic matters and salt of tail water of the same species, and the mode can only carry out a circulating sequential batch mode with the circulating flow rate of 0.5-2 mL/min.
Preferably, the COD concentration of the chemical tail water entering the anode chamber of the cell device is 200-600 mg/L.
Preferably, the salt concentration of the chemical tail water entering the anode chamber of the cell device is 10-25 g/L.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) compared with the traditional MDC, the microbial desalination battery device provided by the invention fully absorbs the principle of capacitive desalination, takes the characteristics and treatment requirements of chemical tail water into consideration, is provided with a novel hollow carbon fiber-carbon film capacitive electrode with a long service life, and has the remarkable advantages that: the method can recover salt with high added value, realizes synchronous treatment of chemical tail water under the condition of no additional energy, and has wide application range;
(2) the novel hollow carbon fiber-carbon film capacitor electrode enters the titanium dioxide nanotube through a vacuum induced precursor, divalent nickel is reduced and simultaneously catalyzes graphitization of amorphous carbon in the anaerobic pyrolysis process, and forms firm titanium-nickel alloy with titanium atoms, so that hollow carbon fibers embedded in the titanium dioxide nanotube are obtained through in-situ growth, carbonized microspheres formed on the surface are fixed on the titanium dioxide nanotube array through bridging of the hollow carbon fibers to form a stable and uniform carbon film layer, and meanwhile, the anaerobic pyrolysis temperature is controlled to be 800-850 ℃ to promote TiO to2The titanium dioxide structure conversion improves the current collection efficiency of the capacitor electrode, enhances the electron conduction of the system, promotes the ion enrichment and release process of an MDC-capacitor system, solves the defects of weak acting force, weak water impact resistance and easy falling between a capacitor material and a conductive matrix of a conventional capacitor electrode, has the characteristics of double electric layer capacitance (such as a pure carbon material, an electric layer formed on the surface of the material due to electrostatic action has limited capacitance, but high charging and discharging speed and meets the adsorption requirement of free ions in water) and pseudocapacitance (a capacitor structure formed by metal oxide, and the capacitance of the capacitor layer is large due to the existence of the metal oxide), can ensure the electron transfer while adsorbing the ions, and is more suitable for the chemical tail water treatment with more complex components;
(3) according to the invention, the area of the hollow carbon fiber-carbon film capacitor electrode of the cathode is controlled to be 1/2-3/4 of the sectional area of the cathode chamber, so that transmitted electrons can be discharged into the cathode chamber in the waterproof layer, the electricity generation efficiency is improved while the electron transfer is not influenced, and higher desalting rate and adsorption rate are obtained;
(4) according to the invention, the internal resistance of the system is reduced by controlling the amount of the precursor dripped in the step S3 in the electrode preparation process and the thickness of the titanium matrix in the step S2, so that a higher desalting rate can be achieved;
(5) the invention relates to a capacitive microbial desalination method applied to chemical tail water treatment, which adopts the cell device, firstly, chemical tail water is internally circulated in an anode chamber, after specific retention time, the anode chamber of the cell device is connected with a desalination chamber in series, water treated by the anode chamber enters the desalination chamber and is circularly treated with desalination and/or COD in the desalination chamber and the anode chamber, and the functions of the anode chamber and the desalination chamber are firstly connected in series to combine, thereby forming an integrated treatment device and treatment method, increasing the recovery function of high-added-value metal ions, and being suitable for treating chemical tail water containing certain residual organic matters.
Drawings
FIG. 1 is a schematic view of the construction of a microbial desalination cell apparatus according to the present invention;
the respective symbols in the figure are as follows: 1. an anode chamber; 2. a desalting chamber; 3. a cathode chamber; 4. an anode material; 5. an anodically electrogenic microorganism; 6. anolyte; 7. an anion exchange membrane; 8. a cation exchange membrane; 9. a hollow carbon fiber-carbon film capacitor electrode (9.1, a capacitor layer, 9.2, a titanium-based layer, 9.3, a waterproof layer, 9.4, a catalyst layer); 10. an external circuit;
FIG. 2 is a schematic diagram of a process for fabricating a capacitor layer of a hollow carbon fiber-carbon film capacitor electrode and a structure thereof;
FIG. 3 is a cross-sectional SEM image (a) and a 45 DEG top cross-sectional SEM image (b) of a hollow carbon fiber-carbon film capacitor electrode;
FIG. 4 is a graph showing the effect of desalting and recovering salt concentrations in the operation of example 1;
FIG. 5 is a graph showing the effect of desalting and COD removal in example 3;
FIG. 6 is a graph showing the effect of different ratios of cathode area to cathode chamber cross-sectional area on the salt removal rate in example 7;
FIG. 7 is a graph showing the effects of different titanium substrate thicknesses and precursor dosages on the internal resistance of the cathode system and on the salt removal rate in example 8;
FIG. 8 is a comparison of the titanium suboxide formed in example 9 after high temperature anaerobic pyrolytic reduction at 850 ℃ versus 650 ℃;
FIG. 9 shows the internal resistance of the cathode system and the effect on the salt removal rate obtained by high-temperature oxygen-free pyrolysis reduction at different temperatures in example 9.
Detailed Description
It will be understood that when an element is referred to as being "mounted on" another element, it can be directly on the other element or the two elements can be directly connected together; when an element is referred to as being "connected" to another element, it can be directly connected to the other element or the two elements may be directly integrated. In addition, the terms "upper", "lower", "left", "right" and "middle" used in the present specification are for clarity of description, and are not intended to limit the scope of the present invention, and the relative relationship between the terms and the relative positions may be changed or adjusted without substantial technical changes.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs; as used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The materials, reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially. The experimental methods used are conventional methods unless otherwise specified.
As used herein, the term "about" is used to provide the flexibility and inaccuracy associated with a given term, measure or value. The degree of flexibility for a particular variable can be readily determined by one skilled in the art.
As used herein, "adjacent" refers to two structures or elements being in proximity. In particular, elements identified as "adjacent" may abut or be connected. Such elements may also be near or proximate to each other without necessarily contacting each other. In some cases, the precise degree of proximity may depend on the particular context.
Concentrations, amounts, and other numerical data may be presented herein in a range format. It is to be understood that such a range format is used merely for convenience and brevity and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a numerical range of about 1 to about 4.5 should be interpreted to include not only the explicitly recited limit values of 1 to about 4.5, but also include individual numbers (such as 2, 3, 4) and sub-ranges (such as 1 to 3, 2 to 4, etc.). The same principle applies to ranges reciting only one numerical value, such as "less than about 4.5," which should be construed to include all of the aforementioned values and ranges. Moreover, such an interpretation should apply regardless of the breadth of the range or feature being described.
Any steps recited in any method or process claims may be executed in any order and are not limited to the order presented in the claims. Method + function or step + function limitations are only employed if all of the following conditions exist within the limitations of a particular claim: a) a method for or a step for is. b) The corresponding functions are explicitly described. Structures, materials, or acts that support the method + functions are explicitly recited in the description herein. The scope of the invention should, therefore, be determined only by the appended claims and their legal equivalents, rather than by the descriptions and examples given herein.
Example 1
The microbial desalination cell device provided by the invention is used for treating salt in chemical tail water in pesticide production and recovering salt, and comprises the following steps:
step one, preparing a hollow carbon fiber-carbon film capacitor electrode
The first step is as follows: preparing 100mL of 120g/L glucose aqueous solution at room temperature, weighing 4g of nickel acetate solid, adding the nickel acetate solid into the glucose aqueous solution, and stirring and dissolving to obtain a precursor.
The second step is that: placing a titanium-based titanium dioxide nanotube array (5cm multiplied by 0.5mm, the thickness of a titanium substrate is 0.02mm) in a flask with a plug and two mouths, wherein one face of pure titanium faces downwards, one mouth of the flask is connected with a vacuum pump, the other mouth is connected with a dropping funnel with a plug and a constant pressure, and the funnel is filled with the precursor. Vacuumizing to 0.03MPa, opening a constant-pressure dropping funnel, dropping the precursor into the two-mouth bottle until the liquid level is higher than the horizontal plane of the current collector (the using amount of the precursor is 0.03 mu L), closing the funnel and a vacuum pump, and slowly releasing the air pressure in the bottle to the atmospheric pressure.
The third step: and taking out the current collector, placing the current collector on a horizontal table board, enabling the pure titanium surface to face downwards, dropwise adding 1mL of precursor on the upper surface, uniformly smearing the precursor to form a film, aging the film for 24 hours at room temperature in air, placing the film in a 65 ℃ vacuum resistance box for 12 hours, and taking out the film for later use. This step was repeated 5 times.
The fourth step: and (3) placing the electrode after vacuum drying in a muffle furnace, setting a temperature rise/reduction speed of 1 ℃/min, carrying out pyrolysis for 2h at 250 ℃ in the air, then placing the electrode in a nitrogen protective furnace, setting a temperature rise/reduction speed of 1 ℃/min, carrying out carbonization and anaerobic pyrolysis reduction for 1h at the high temperature of 850 ℃, then cooling to room temperature, and taking out to obtain the formed hydrophobic capacitance electrode.
The fifth step: and (3) putting the electrode into 5.5mol/L nitric acid solution, heating and acidifying at the constant temperature of 55 ℃ for 24 hours, and washing with deionized water until the electrode is neutral to obtain the hydrophilic capacitance electrode.
And a sixth step: using PTFE with the mass fraction of 60% and Nafion solution with the mass fraction of 5% to perform waterproof treatment on one side of the titanium base layer to form a waterproof layer, and uniformly coating 0.35mg/cm on the side of the waterproof layer2Pt-C catalyst, after which the capacitor electrode was trimmed to 3/4, the cross-sectional area of the cathode chamber.
Step two, assembling of microbial desalination cell
Soaking an anode carbon brush in the domesticated electrogenesis composite bacterial liquid for more than 12 hours, then placing the carbon brush in an anode chamber, and separating the anode chamber from a desalting chamber by using an anion exchange membrane with the thickness of 0.5 mm; the prepared hollow carbon fiber-carbon film capacitor electrode is arranged at the cathode, the capacitor layer is arranged towards the desalting chamber, the catalyst layer faces the air, the cathode chamber and the desalting chamber are separated by a cation exchange membrane of 0.5mm, and the cathode chamber and the desalting chamber are fastened by an iron hoop flange to prevent water leakage and air entering. And connecting the cathode and the anode through a lead and connecting the cathode and the anode in series into a resistor with the resistance of 1000 omega.
Step three, operation of the microbial desalination cell
Firstly, ordinary domestic sewage with COD of 550mg/L is used as anode nutrient solution to circulate in an anode chamber, the circulation flow rate is 1mL/min, then chemical tail water with the salt concentration of 25g/L to be treated is led into a desalting chamber, the circulation flow rate is 3.0mL/min, salt is collected through a cathode in the circulation process, and the retention time of the desalting chamber is 48h (one period). After 48h of treatment, as shown in FIG. 4 (120 cycles in total), the salt removal rate in the chemical tail water can reach 82% at most, the effluent desalination rate is 184.0mg/h, and the concentration of the concentrated solution salt (the concentration of the regenerated brine) recovered by the cathode is 697.23 mg/L.
Example 2
The microbial desalination cell provided by the invention is used for treating salt in chemical tail water produced by pharmaceutical intermediates and recovering the salt, and comprises the following steps:
step one, preparing a hollow carbon fiber-carbon film capacitor electrode, which is the same as the embodiment 1;
step two, assembling of microbial desalination cell
Soaking an anode carbon felt in the domesticated electrogenesis composite bacterial liquid for more than 12 hours, then placing the carbon felt in an anode chamber, and separating the anode chamber from a desalting chamber by using an anion exchange membrane with the thickness of 0.25 mm; the prepared hollow carbon fiber-carbon film capacitor electrode is arranged at the cathode, the capacitor layer is arranged towards the desalting chamber, the catalyst layer faces the air, the cathode chamber and the desalting chamber are separated by a cation exchange membrane of 0.25mm, and the cathode chamber and the desalting chamber are fastened by an iron hoop flange to prevent water leakage and air entering. And connecting the cathode and the anode through a lead and connecting the cathode and the anode in series into a resistor with the resistance of 800 omega.
Step three, operation of the microbial desalination cell
Firstly, food processing wastewater with COD of 480mg/L is used as anode nutrient solution to circulate in an anode chamber at a circulation flow rate of 0.8mL/min, then chemical tail water with the salt concentration of 15g/L to be treated is led into a desalting chamber at a circulation flow rate of 2.5mL/min, salt is collected through a cathode in the circulation process, and the retention time of the desalting chamber is 72h (one period). After 72 hours of treatment, the highest salt removal rate in the chemical tail water can reach 58 percent, the desalination rate of the effluent is 144.0mg/h, and the concentration of the concentrated solution salt recovered by the cathode is 537.16 mg/L.
Example 3
The microbial desalination cell provided by the invention is used for integrally treating residual organic pollutants and salt in pesticide chemical tail water, and comprises the following steps:
step one, preparing a hollow carbon fiber-carbon film capacitor electrode
The first step is as follows: 100mL of 100g/L glucose aqueous solution is prepared at room temperature, 2g of nickel acetate solid is weighed and added into the glucose aqueous solution, and stirring and dissolving are carried out to obtain a precursor.
The second step is that: placing a titanium-based titanium dioxide nanotube array (5cm multiplied by 0.5mm, the thickness of a titanium substrate is 0.02mm) in a flask with a plug and two mouths, wherein one face of pure titanium faces downwards, one mouth of the flask is connected with a vacuum pump, the other mouth is connected with a dropping funnel with a plug and a constant pressure, and the funnel is filled with the precursor. Vacuumizing to 0.01MPa, opening a constant-pressure dropping funnel, dropping the precursor into the two-mouth bottle until the liquid level is higher than the horizontal plane of the current collector (the using amount of the precursor is 0.03 mu L), closing the funnel and a vacuum pump, and slowly releasing the air pressure in the bottle to the atmospheric pressure.
The third step: and taking out the current collector, placing the current collector on a horizontal table board, enabling the pure titanium surface to face downwards, dropwise adding 0.5mL of precursor on the upper surface, uniformly smearing the precursor to form a film, aging the film for 24 hours in air at room temperature, placing the film in a vacuum resistance box at 60 ℃ for 12 hours, and taking out the film for later use. This step was repeated 4 times.
The fourth step: and (3) placing the vacuum-dried electrode in a muffle furnace, setting a temperature rise/reduction speed of 1 ℃/min, pyrolyzing the electrode in air at 200 ℃ for 2h, then placing the electrode in a nitrogen protective furnace, setting a temperature rise/reduction speed of 1 ℃/min, carbonizing at a high temperature of 800 ℃ for anaerobic pyrolysis reduction for 1h, reducing the temperature to room temperature, and taking out the electrode to obtain the formed hydrophobic capacitance electrode.
The fifth step: and (3) putting the electrode into 5mol/L nitric acid solution, heating and acidifying at the constant temperature of 55 ℃ for 24 hours, and washing with deionized water to be neutral to obtain the hydrophilic capacitance electrode.
And a sixth step: using PTFE with the mass fraction of 60% and nafion solution with the mass fraction of 5% to perform waterproof treatment on one side of the titanium base layer to form a waterproof layer, and uniformly coating 0.30mg/cm on the side of the waterproof layer2Pt-C catalyst, after which the capacitor electrode was trimmed to 3/4, the cross-sectional area of the cathode chamber.
Step two, assembling of microbial desalination cell
Soaking an anode carbon felt in the domesticated electrogenesis composite bacterial liquid for more than 12 hours, then placing a carbon brush in an anode chamber, and separating the anode chamber from a desalting chamber by using an anion exchange membrane with the thickness of 0.5 mm; the prepared hollow carbon fiber-carbon film capacitor electrode is arranged at the cathode, the capacitor layer is arranged towards the desalting chamber, the catalyst layer faces the air, the cathode chamber and the desalting chamber are separated by a cation exchange membrane of 0.5mm, and the cathode chamber and the desalting chamber are fastened by an iron hoop flange to prevent water leakage and air entering. And connecting the cathode and the anode through a lead and connecting the cathode and the anode in series into a resistor with the resistance of 800 omega.
Step three, operation of the microbial desalination cell
Firstly, circulating chemical tail water with the COD concentration of 350mg/L and the salt concentration of 20g/L in an anode chamber for more than 36h at the circulating flow rate of 1mL/min, then connecting a desalting chamber and an anode chamber in series, arranging a collecting container buffer flow in the middle, setting the overall circulating flow rate to be 1.5mL/min, and staying for 72h (one period). As shown in FIG. 5, the salt removal rate of the treated chemical tail water can reach up to 71%, and the COD removal rate is 59%.
Example 4
The method for integrally treating the resin processing chemical tail water by adopting the microbial desalination battery comprises the following steps:
step one, preparing a hollow carbon fiber-carbon film capacitor electrode, which is the same as the preparation process in the example 2;
step two, assembling of microbial desalination cell
Soaking an anode carbon felt in the domesticated electrogenesis composite bacterial liquid for more than 12 hours, then placing a carbon brush in an anode chamber, and separating the anode chamber from a desalting chamber by using an anion exchange membrane with the thickness of 1.0 mm; the prepared hollow carbon fiber-carbon film capacitor electrode is arranged at the cathode, the capacitor layer is arranged towards the desalting chamber, the catalyst layer faces the air, the cathode chamber and the desalting chamber are separated by a cation exchange membrane of 1.0mm, and the cathode chamber and the desalting chamber are fastened by an iron hoop flange to prevent water leakage and air entering. And connecting the cathode and the anode through a lead and connecting the cathode and the anode in series into a resistor with the resistance of 500 omega.
Step three, operation of the microbial desalination cell
Firstly, circulating resin processing chemical tail water with the COD concentration of 350mg/L and the salt concentration of 23g/L as anode nutrient solution in an anode chamber for more than 42h at the circulating flow rate of 1mL/min, then connecting a desalting chamber and the anode chamber in series, arranging a collecting container buffer solution flow in the middle, setting the overall circulating flow rate to be 2.0mL/min, and staying for 84h (one period). The salt removal rate of the treated chemical tail water can reach 73 percent at most, and the COD removal rate is 42 percent.
Example 5
The method for treating the pesticide chemical tail water by using the microbial desalination cell and the capacitance desalination technology comprises the following steps
Step one, preparing a hollow carbon fiber-carbon film capacitor electrode
The first step is as follows: 100mL of 100g/L glucose aqueous solution is prepared at room temperature, 3g of nickel acetate solid is weighed and added into the glucose aqueous solution, and stirring is carried out to dissolve the nickel acetate solid to obtain a precursor.
The second step is that: placing a titanium-based titanium dioxide nanotube array (5cm multiplied by 0.5mm, the thickness of a titanium substrate is 0.02mm) in a flask with a plug and two mouths, wherein one face of pure titanium faces downwards, one mouth of the flask is connected with a vacuum pump, the other mouth is connected with a dropping funnel with a plug and a constant pressure, and the funnel is filled with the precursor. Vacuumizing to 0.01MPa, opening a constant-pressure dropping funnel, dropping the precursor into the two-mouth bottle until the liquid level is higher than the horizontal plane of the current collector (the using amount of the precursor is 0.03 mu L), closing the funnel and a vacuum pump, and slowly releasing the air pressure in the bottle to the atmospheric pressure.
The third step: and taking out the current collector, placing the current collector on a horizontal table board, enabling the pure titanium surface to face downwards, dropwise adding 0.5mL of precursor on the upper surface, uniformly smearing the precursor to form a film, aging the film for 18h in air at room temperature, placing the film in a vacuum resistance box at 65 ℃ for 12h, and taking out the film for later use. This step was repeated 4 times.
The fourth step: and (3) placing the vacuum-dried electrode in a muffle furnace, setting a temperature rise/reduction speed of 1 ℃/min, pyrolyzing the electrode in air at 200 ℃ for 2h, then placing the electrode in a nitrogen protective furnace, setting a temperature rise/reduction speed of 1 ℃/min, carbonizing at a high temperature of 850 ℃ for anaerobic pyrolysis reduction for 1h, reducing the temperature to room temperature, and taking out the electrode to obtain the formed hydrophobic capacitance electrode.
The fifth step: and (3) putting the electrode into 5mol/L nitric acid solution, heating and acidifying at the constant temperature of 60 ℃ for 24 hours, and washing with deionized water to be neutral to obtain the hydrophilic capacitance electrode.
And a sixth step: using PTFE with the mass fraction of 60% and nafion solution with the mass fraction of 5% to perform waterproof treatment on one side of the titanium base layer to form a waterproof layer, and uniformly coating 0.30mg/cm on the side of the waterproof layer2Pt-C catalyst, after which the capacitor electrode was trimmed to 3/4, the cross-sectional area of the cathode chamber.
Step two, assembling the microbial desalination cell and connecting the microbial desalination cell with the capacitive desalination reactor
Soaking an anode carbon felt in the domesticated electrogenesis composite bacterial liquid for more than 12 hours, then placing a carbon brush in an anode chamber, and separating the anode chamber from a desalting chamber by using an anion exchange membrane with the thickness of 0.5 mm; the prepared hollow carbon fiber-carbon film capacitor electrode is arranged at the cathode, the capacitor layer is arranged towards the desalting chamber, the catalyst layer faces the air, the cathode chamber and the desalting chamber are separated by a cation exchange membrane of 0.5mm, and the cathode chamber and the desalting chamber are fastened by an iron hoop flange to prevent water leakage and air entering. And connecting the cathode and the anode to two sides of the capacitive desalting adsorption electrode through leads. The capacitance desalination electrode also adopts an electrode made of a hollow carbon fiber-carbon film capacitor, and the electrode distance is 2 mm.
Step three, operation of the microbial desalination cell and capacitance desalination combined system
Circulating domestic wastewater with COD of 480mg/L as an anode nutrient solution in an anode chamber at a circulating flow rate of 0.8mL/min, introducing chemical tail water to be treated with salt concentration of 25g/L into a desalting chamber, and connecting the desalting chamber with a capacitive desalting reactor (CDI), wherein the specific conditions of the capacitive desalting reactor are that the electrode area is 2cm multiplied by 1cm, the constant voltage is 20V, and the flow mode in the reactor is cross flow; the total circulation flow rate was 2.5mL/min, the salt was collected by the cathode during the circulation, and the total residence time was 60h (one cycle). After 60 hours of treatment, the removal rate of salt in the chemical tail water can reach 78%, and the salt concentration of the concentrated solution recovered by the cathode is 317.16 mg/L.
Example 6
The method for producing chemical tail water by treating the medical intermediate by using the microbial desalination cell and the capacitive desalination technology comprises the following steps
Step one, preparing a hollow carbon fiber-carbon film capacitor electrode, which is the same as the step one in the embodiment 5;
step two, the assembly of the microbial desalination cell and the connection with the capacitance desalination reactor are the same as the step two of the embodiment 5;
step three, operation of the microbial desalination cell and capacitance desalination combined system
Firstly, circulating domestic wastewater with COD of 500mg/L as anode nutrient solution in an anode chamber at a circulating flow rate of 0.8mL/min, then introducing chemical tail water to be treated with salt concentration of 20g/L into a desalting chamber, and connecting the desalting chamber with a capacitive desalting reactor, wherein the specific conditions of the capacitive desalting reactor are the same as those in example 5; the total circulation flow rate was 3.0mL/min, the salt was collected by the cathode during the circulation, and the total residence time was 48h (one cycle). After 48 hours of treatment, the removal rate of salt in the chemical tail water can reach 71%, and the salt concentration of the concentrated solution recovered by the cathode is 236.68 mg/L.
Example 7
The cathode of the traditional microbial desalination battery directly covers the cathode chamber, but the cathode of the capacitive microbial desalination battery is loaded with the titanium-based capacitor layer, so that the electron transfer of the cathode is hindered, and the electrons can be discharged into the cathode chamber in the waterproof layer by properly reducing the size of the cathode. However, the size of the cathode also limits the operation efficiency of the whole microbial desalination cell, and the excessively small area not only affects the desalination effect but also affects the adsorption effect of the capacitor layer, so other conditions in this embodiment are the same as those in embodiment 1, except that cathodes with different electrode area and cathode chamber cross-sectional area ratios are adopted, so as to investigate the optimal composite cathode area for completing the electron transfer process.
As shown in fig. 6, when the area of the cathode is 3/4 of the cross section of the cathode chamber, the transferred electrons can be discharged into the cathode chamber through the waterproof layer, the electricity generation efficiency is highest without affecting the electron transfer, and the highest desalination rate (77.03%) and adsorption rate are obtained.
Example 8
In the construction process of the invention, if the capacitor electrode and the microbial desalination battery are simply combined, the internal impedance of the microbial desalination battery is increased, so that the impedance of the whole system is overlarge, the desalination efficiency is low, and the operation effect of the whole reactor is greatly influenced. Based on the above, in order to reduce the internal impedance of the system, the thickness of the titanium substrate and the precursor amount of the capacitance layer are optimized. The other conditions in this example were the same as in example 1 except that titanium sheets having thicknesses of 0.01mm, 0.02mm, 0.03mm and 0.05mm were used for optimization, and the electrode preparation process was carried out before the dropping in the third stepThe amount of the flooding agent was 0.01. mu.L/cm2、0.02μL/cm2、0.03μL/cm2、0.05μL/cm2And (6) optimizing.
As shown in FIG. 7, the thickness of the titanium matrix used by the cathode is less than or equal to 0.02mm, the using amount of the precursor is less than or equal to 0.03 mu L, the internal resistance of the system is low, and the high desalting rate can be achieved.
Example 9
Conventional TiO used for capacitor electrode2The nanotube array, as a current collector in the process of capacitance adsorption, has conductivity inferior to that of pure Ti and TinO2n-1(titanium oxide) material. But due to the external voltage applied in the capacitive adsorption technology, the voltage is applied to TiO2The influence of the nanotube array layer is low. However, in the system of microbial desalination battery, due to the limited ability of microbes to generate electricity, the conductivity requirement of the current collector material during the adsorption process is higher, because TiO needs to be added2The nanotubes are converted to a more conductive titanium dioxide material as much as possible. On the basis, other conditions in this embodiment are the same as those in embodiment 1, except that the temperature of the fourth step of the high-temperature anaerobic thermal reduction in the electrode preparation process is optimized, and the oxygen-free reduction experiments are performed at 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃ and 850 ℃, respectively, wherein XRD of the material obtained by the high-temperature anaerobic thermal reduction (high-temperature anaerobic pyrolysis) at 650 ℃ and 850 ℃ is as shown in fig. 8, and it can be seen that titanium protoxide (Ti) in the material obtained by the high-temperature anaerobic thermal reduction at 850 ℃ is titanium protoxide (Ti) in the material obtained by the high-temperature anaerobic thermal reduction at 850 ℃5O9) The peak intensity is more obvious, and the capacitance electrode under 850 ℃ reduction has better desalting performance, which shows that the increase of titanium suboxide caused by temperature rise promotes electron transfer and optimizes the performance of a current collector, so that the preparation method adopts 800-850 ℃ high-temperature oxygen-free thermal reduction to promote TiO ion doping2The structure of the titanium suboxide is converted, the current collection efficiency of the capacitor electrode is improved, the electron conduction of the system is enhanced, and the ion enrichment and release process of the MDC-capacitor system is promoted.
In addition, as shown in the application experiment of FIG. 9, the material reduced at 800 ℃ or higher has better salt adsorption capacity.
The above description is of the preferred embodiment of the invention. It is to be understood that the invention is not limited to the particular embodiments described above, in that devices and structures not described in detail are understood to be implemented in a manner common in the art; those skilled in the art can make many possible variations and modifications to the disclosed embodiments, or modify equivalent embodiments to equivalent variations, without departing from the spirit of the invention, using the methods and techniques disclosed above. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the scope of the protection of the technical solution of the present invention, unless the contents of the technical solution of the present invention are departed.
Claims (8)
1. A capacitive microbial desalination cell device applied to chemical engineering tail water treatment is characterized by comprising an anode chamber, a desalination chamber and a cathode chamber, wherein the anode chamber and the desalination chamber are separated by an anion exchange membrane, and the cathode chamber and the desalination chamber are separated by a cation exchange membrane; the anode of the battery device adopts a carbon material to load microorganisms and transfer electrons, and the cathode of the battery device adopts a hollow carbon fiber-carbon film capacitor electrode which comprises a hollow carbon fiber-carbon film capacitor layer, a titanium-based layer, a waterproof layer and a catalyst layer which are sequentially arranged; the anode and the cathode are connected by an external circuit with a resistor; the hollow carbon fiber-carbon film capacitor layer structure is formed by covering a carbon film layer formed by carbonized microspheres on a titanium dioxide nanotube array embedded with hollow carbon fibers;
the preparation method of the hollow carbon fiber-carbon film capacitor electrode comprises the steps of taking a titanium-based titanium dioxide nanotube array as a conductive substrate, taking a mixed solution of glucose and nickel acetate as a precursor, and obtaining the integrated hollow carbon fiber-carbon film capacitor layer with an embedded structure through vacuum induction, anaerobic pyrolysis and hydrophilic modification, wherein the temperature in the anaerobic pyrolysis step is 800-850 ℃.
2. The capacitive microbial desalination cell device applied to chemical tail water treatment as claimed in claim 1, wherein the area of the hollow carbon fiber-carbon membrane capacitor electrode is 1/2-3/4 of the cross section of the cathode chamber.
3. The capacitive microbial desalination cell device applied to chemical tail water treatment as claimed in claim 1, wherein the anode carbon material of the cell device comprises carbon felt, carbon brush or activated carbon particles;
and/or the anion exchange membrane and the cation exchange membrane of the battery device are heterogeneous electrodialysis ion exchange membranes, the thickness is 0.5-1.0mm, the independent transmittance is not less than 90%, and the burst strength is more than 0.3 Mpa;
and/or a resistor is connected in series between the cathode and the anode in the battery device, and the resistance value is 10-1500 omega.
4. The capacitive microbial desalination cell device applied to chemical tail water treatment as claimed in claim 1, wherein the specific preparation steps of the hollow carbon fiber-carbon membrane capacitive electrode comprise:
preparation of S1 precursor: preparing a glucose aqueous solution with a certain concentration at room temperature, weighing a certain mass of nickel acetate solid, adding the nickel acetate solid into the glucose aqueous solution, and stirring and dissolving to obtain a precursor;
s2, placing the titanium-based titanium dioxide nanotube array in a container, and enabling the pure titanium surface to face downwards and the pipe orifice of the titanium dioxide nanotube array to face upwards; vacuumizing to a certain vacuum degree, then dripping the precursor into the container until the liquid level is higher than the horizontal plane of the titanium-based titanium dioxide nanotube array, stopping vacuumizing, and slowly releasing the air pressure in the container to atmospheric pressure;
s3, taking out the titanium-based titanium dioxide nanotube array processed in the step S2, placing the titanium-based titanium dioxide nanotube array on a horizontal table board, enabling one surface of pure titanium to face downwards, dropwise adding the precursor on the upper surface of the titanium-based titanium dioxide nanotube array, uniformly smearing the precursor to form a film, aging the film in air at room temperature, preheating and decomposing the film through a vacuum resistance box, and taking out the film for later use; this step is repeated several times to obtain the desired film thickness;
s4, placing the electrode dried in vacuum in the step S3 in a muffle furnace, pyrolyzing the electrode in air, placing the electrode in a nitrogen protective furnace for high-temperature carbonization and oxygen-free pyrolysis, and taking out the electrode to obtain the capacitor electrode with the formed hydrophobic capacitor layer;
s5, placing the capacitance electrode obtained in the step S4 in a nitric acid solution, heating and acidifying at a constant temperature, and washing with deionized water until the capacitance electrode is neutral to obtain a capacitance electrode of a hydrophilic capacitance layer;
s6, brushing a waterproof layer on the titanium base layer on the side of the capacitor layer obtained in the step S5 by adopting PTFE and nafion solution, and then uniformly coating Pt-C catalyst on the side of the waterproof layer to obtain the hollow carbon fiber-carbon film capacitor electrode.
5. The capacitive microbial desalination cell device applied to chemical tail water treatment as claimed in claim 4, wherein the glucose concentration in step S1 is 80-120g/L, and the nickel acetate concentration is 10-40 g/L;
and/or the vacuum degree in the step S2 is 0.01-0.03 MPa;
and/or the aging time in the step S3 is 12-24h, the vacuum heating temperature is 55-65 ℃, and the heating time is 12 h;
and/or the muffle furnace temperature rising/reducing speed of the air pyrolysis process in the step S4 is 1 ℃/min, and the heat preservation time at 200 ℃ and 250 ℃ is 2 h; in the oxygen-free pyrolysis process, the temperature rising/reducing speed of the nitrogen protection furnace is 1 ℃/min, and the temperature is kept for 1h at 850 ℃ with 800-;
and/or in the step S5, the concentration of nitric acid is 4.5-5.5mol/L, the constant-temperature heating temperature is 50-55 ℃, and the heating time is 18-24 h;
and/or the PTFE in the step S6 is a PTFE solution with a mass fraction of 60%, the Nafion solution is coated with 500 mu L of Nafion solution with a mass fraction of 5% per 5mg of Pt-C catalyst according to the coating amount of the Pt-C catalyst, and the coating amount of the Pt-C catalyst is 0.2-0.6mg/cm2；
And/or the adding amount of the dropwise added precursor in the step S2 is less than or equal to 0.03 mu L;
and/or the thickness of the titanium matrix in the titanium-based titanium dioxide nanotube array in the step S2 is less than or equal to 0.02 mm.
6. A capacitive microbial desalination method applied to chemical tail water treatment is characterized in that by adopting the cell device of any one of claims 1 to 5, chemical tail water is internally circulated in an anode chamber, after a certain retention time, the anode chamber and a desalination chamber of the cell device are connected in series, and water treated by the anode chamber enters the desalination chamber and is circularly treated in the desalination chamber and the anode chamber to remove salt and/or COD;
or firstly, nutrient solution is adopted to carry out internal circulation in the anode chamber, after specific retention time, chemical tail water is introduced into a desalting chamber to carry out circular treatment for desalting, and meanwhile, the salt in the tail water is recovered;
or firstly, nutrient solution is adopted to carry out internal circulation in the anode chamber, after specific retention time, chemical tail water is introduced into the desalting chamber, and the desalting chamber is connected with the anode chamber in series, so that the chemical tail water is circularly treated in the desalting chamber and the anode chamber to remove salt and/or COD;
or firstly, nutrient solution is adopted to carry out internal circulation in the anode chamber, and after a certain retention time, the chemical tail water is introduced into the desalting chamber connected with the capacitance desalting reactor in series, so that the chemical tail water is circulated in the desalting chamber and the capacitance desalting reactor for desalting treatment.
7. The capacitive microbial desalination method applied to chemical tail water treatment of claim 6, wherein the water inlet mode of the desalination chamber in the battery device comprises a circulation sequential batch mode or a continuous flow mode, when the circulation sequential batch water inlet mode is adopted, a separate recovery chamber is arranged, the circulation flow rate is 0.5-5mL/min, and the retention time is 2-120 h; the flow rate of water inflow by adopting continuous flow is 0.2-1 mL/min.
8. The capacitive microbial desalination method applied to chemical tail water treatment as claimed in claim 6, wherein the COD concentration of the chemical tail water entering the anode chamber of the cell device is 200-600 mg/L;
and/or the concentration of chemical tail water salt entering the anode chamber of the cell device is 10-25 g/L.
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