CN110085895B - Fluid battery and method for treating heavy metal ions and organic dye in wastewater by using fluid battery - Google Patents

Fluid battery and method for treating heavy metal ions and organic dye in wastewater by using fluid battery Download PDF

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CN110085895B
CN110085895B CN201910293713.4A CN201910293713A CN110085895B CN 110085895 B CN110085895 B CN 110085895B CN 201910293713 A CN201910293713 A CN 201910293713A CN 110085895 B CN110085895 B CN 110085895B
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wastewater
battery
fluid battery
fluid
heavy metal
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CN110085895A (en
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赵玉
侯贤华
罗婷
王韶峰
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South China Normal University
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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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • 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
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents
    • 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

Abstract

The invention discloses a fluid battery and a method for treating heavy metal ions and organic dye in wastewater by using the fluid battery. The method comprises the following steps of taking heavy metal ion wastewater as a battery anode, taking organic dye wastewater as a battery cathode, isolating the anode and the cathode through a diaphragm to form a fluid battery, and oxidizing the organic dye wastewater through the oxidization of the heavy metal ion wastewater so as to achieve double-effect treatment of the anode and cathode wastewater and generation of electric energy; the structure of the fluid battery also comprises a positive electrode current collector and a negative electrode current collector. The fluid battery has high discharge voltage, the degradation efficiency of the fluid battery on chromium ions in wastewater is close to 100%, and the degradation efficiency of the fluid battery on organic dye can reach 95.6%; the method has the advantages of simple and easy operation, environmental protection, economy and practicality, and has important significance for the method for treating the heavy metal ions and the organic dye in the sewage.

Description

Fluid battery and method for treating heavy metal ions and organic dye in wastewater by using fluid battery
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a fluid battery and a method for treating heavy metal ions and organic dyes in wastewater by using the fluid battery.
Background
In recent years, with the increasing industrialization pace in China, the environment is gradually deteriorated by the emission of pollutants, wherein industrial wastewater contains a large amount of toxic heavy metals and organic dyes, and the environmental pollution caused by the toxic heavy metals and the organic dyes is considered to be one of the most serious pollution. Heavy metal ions and dye waste liquid cannot be biodegraded after entering the environment, and serious harm can be caused to human and animals. Therefore, people pay more and more attention to how to treat industrial wastewater.
At present, the methods for treating chromium-containing wastewater mainly include a reduction neutralization method, an ion exchange method, an electrolysis method, a biological method, an adsorption method and the like. The most common method for treating chromium wastewater in industrial production is a reduction neutralization method, and compared with other methods, the method has high chromium removal rate, but the method also has many disadvantages, such as complex treatment process, easy secondary pollution and slag yard storage; other methods for treating chromium wastewater have many disadvantages, such as that the ion exchange resin method is greatly influenced by pH value, a large amount of precipitates generated after wastewater treatment by an electrolysis method and a chemical reduction method are difficult to treat, a biological method is sensitive to environmental conditions and poor in stability, the treatment capacity of an adsorption method is low, industrialization is difficult to realize, and the chemical hardness and stability of a common adsorbent are difficult to guarantee.
Meanwhile, the method for treating the organic dye wastewater mainly comprises methods such as an oxidation-reduction method, an electrolysis method, a coagulating sedimentation method, a membrane separation technology, an adsorption method and the like. Although the coagulating sedimentation method has a simple flow and a large amount of waste water, the method generates a large amount of sludge, and the subsequent treatment is troublesome. The oxidation method is widely applied due to the advantages of wide application range, high reaction speed, easily controlled conditions and the like, but the method is easy to introduce new pollutants in the reaction process, has strict requirements on the water quality of raw water and has higher cost. However, the selective semipermeable membrane used in the membrane separation method is easily contaminated to lose the treatment ability, and the method is expensive, and therefore, it is often used in the advanced treatment of wastewater.
In addition, because the chemical properties of the heavy metal ion wastewater (especially chromium wastewater) and the organic dye wastewater are different, the traditional treatment method generally needs to carry out treatment in a grading and grading manner, so that the method for economically and efficiently treating the heavy metal ion wastewater (especially chromium wastewater) and the organic dye wastewater by double effects is significant.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention mainly aims to provide a fluid battery.
The invention also aims to provide a method for double-effect treatment of heavy metal ions and organic dyes in wastewater by using the fluid battery. The method can produce electric energy while treating heavy metal ion wastewater and organic dye wastewater with double effects.
The purpose of the invention is realized by the following technical scheme:
a fluid battery, its positive pole is heavy metal ion waste water, the negative pole is organic dye waste water, the positive and negative pole is separated by the diaphragm, make up the fluid battery; the structure of the fluid battery also comprises a positive current collector, a negative current collector and a negative catalyst, wherein the negative catalyst is iron-based spinel oxide.
The heavy metal ion wastewater is preferably chromium ion wastewater, and the organic dye wastewater is preferably azo dye solution.
The chromium ion wastewater is preferably a potassium dichromate solution and/or a sodium dichromate solution, and the azo dye solution is preferably at least one of a methyl red solution, a methyl orange solution and a methylene blue solution.
The structure of the fluid battery also comprises an anode reaction bin, an anode liquid storage bin, a cathode reaction bin, a cathode liquid storage bin, carbon fiber cloth and foam carbon. The fluid cell can be obtained by reference to the fluid cell principle and the prior art assembly, for example, one of the ways is: limiting an anode in an anode reaction bin, placing foamy carbon in a cathode reaction bin, limiting a cathode in a cathode reaction bin, and coating a cathode catalyst on a cathode current collector; carbon fiber cloth of the anode, an anode current collector, an anode reaction bin, a diaphragm, a cathode reaction bin, a cathode current collector and carbon fiber cloth of the cathode are stacked and arranged; the positive electrode liquid storage bin is connected with the positive electrode reaction bin, and the negative electrode reaction bin is connected with the negative electrode liquid storage bin. The positive carbon fiber cloth and the negative carbon fiber cloth are connected with an external circuit so as to output voltage; the liquid in the positive electrode liquid storage bin and the negative electrode liquid storage bin respectively flows to the positive electrode reaction bin and the negative electrode reaction bin through the peristaltic pump.
The isolation area (positive and negative electrode contact area) of the diaphragm is preferably 3cm × 3 cm; the volumes of the anode reaction bin and the cathode reaction bin are preferably 3cm multiplied by 2 mm; the volumes of the positive electrode liquid storage bin and the negative electrode liquid storage bin are preferably 50 mL; the device mould of the fluid battery is preferably a plastic mould, and the performance of the device mould is stable; more preferably an acrylic material mould; the size of the device mould is preferably 10cm × 10cm × 1 cm; the size of the carbon fiber cloth is preferably 1cm × 2 cm.
The catalyst is more preferably at least one of nano nickel ferrite, nano zinc ferrite, nano cobalt ferrite and nano manganese ferrite, and the specific surface area of the catalyst is high; the catalyst has the main functions of catalyzing the decomposition and oxidation of dye molecules, on one hand, catalyzing the decomposition of the dye molecules, and on the other hand, catalyzing the oxidation of decomposed small molecules, so that a potential difference is formed between the catalyst and anode fluid, and current is generated.
The catalyst is coated on a negative current collector,the preferred dosage is 10-20 mg/cm2。
The catalyst is preferably mixed with conductive carbon and PVDF (polyvinylidene fluoride), dissolved in an organic solvent, stirred and ground, and then coated on a negative current collector.
The mass ratio of the catalyst, the conductive carbon and the PVDF is preferably (1-10): 1.5: 1.5, more preferably 7: 1.5: 1.5; the mass-to-liquid ratio of the catalyst to the organic solvent is preferably 0.01 to 0.1g/ml, more preferably 0.07g/ml and 0.1 g/ml.
The organic solvent is preferably NMP (N-methylpyrrolidone).
The separator is preferably a bipolar membrane; more preferably a bipolar membrane TRJBM; the primary function of the membrane is to conduct hydrogen or hydroxyl ions.
The positive current collector and the negative current collector are both graphite, wherein heavy metal ion wastewater serves as a battery positive active substance and a battery carrier, organic dye wastewater serves as a battery negative active substance and a battery carrier, positive and negative electrode fluids are respectively formed through a peristaltic pump, and the flow rates of the positive and negative electrode fluids are preferably 5-15 rpm.
The graphite is preferably graphite paper.
The fluid cell is more preferably: the potassium dichromate solution is used as a positive electrode, the methyl orange solution is used as a negative electrode, and the nano nickel ferrite is used as a catalyst; or the following steps: the potassium dichromate solution is used as an anode, the methyl red solution is used as a cathode, and the nano cobalt ferrite is used as a catalyst; or the following steps: the sodium dichromate solution is used as an anode, the methylene blue solution is used as a cathode, and the nano zinc ferrite or manganese ferrite is used as a catalyst.
The generation of the electric energy is realized by the potential difference of the positive and negative fluid.
The fluid battery can be applied to double-effect treatment of heavy metal ions and organic dyes in wastewater, and the specific application method comprises the following steps: the fluid battery is formed by taking heavy metal ion wastewater to be treated as a positive electrode and organic dye wastewater to be treated as a negative electrode; the organic dye wastewater is oxidized by the oxidability of the heavy metal ion wastewater, so that the double-effect treatment of the anode wastewater and the cathode wastewater and the generation of electric energy are achieved.
In the application method, the heavy metal ion wastewater is preferably chromium ion wastewater, and the organic dye wastewater is preferably azo dye solution.
The chromium ion wastewater is preferably a potassium dichromate solution and/or a sodium dichromate solution, and the azo dye solution is preferably at least one of a methyl red solution, a methyl orange solution and a methylene blue solution.
The concentration of dichromate ions in the chromium ion wastewater is preferably 30-90 mg/L; the concentration of the organic dye in the organic dye wastewater is preferably 30-90 mg/L.
The invention provides a fluid battery and a method for treating heavy metal ions and organic dyes in wastewater by using the fluid battery, which can continuously output electric energy to the outside while degrading wastewater. The method not only can meet the basic requirements of simultaneously treating heavy metal ions and organic dyes, but also can obtain electric energy in the process of wastewater treatment, and is an efficient and economic sewage treatment method.
The method takes organic dye wastewater (organic dye solution) as a negative active solution, a heavy metal ion (dichromate ion) solution as a positive active solution, and an iron-based spinel material as a negative catalyst material; after the fluid battery device is installed, the heavy metal ion (dichromate ion) solution and the organic dye solution respectively enter a positive electrode reaction bin and a negative electrode reaction bin of the fluid battery from positive and negative hoses through a peristaltic pump, and because potential difference exists between the heavy metal ion (dichromate ion) solution and the organic dye solution, oxidation-reduction reaction can be carried out spontaneously, and electric energy can be continuously obtained in the wastewater treatment process.
In the discharging process, the anode dichromate is subjected to a reduction reaction, so that hexavalent chromium ions are reduced to be trivalent, and the purpose of degrading chromium (VI) is achieved; the negative organic dye is subjected to oxidation reaction, so that azo double bonds of strong chromophore groups of the dye are oxidized and damaged, and the dye is gradually degraded to be colorless and transparent along with the reaction. Meanwhile, the iron-based spinel material is added to the negative electrode as a catalyst material, so that the degradation speed of the dye and the output voltage can be obviously improved.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention provides a fluid battery and an application thereof in treating heavy metal ions and organic dyes in wastewater, the fluid battery is utilized to treat the organic dye wastewater while degrading the heavy metal ions, the degradation rate of the heavy metal ions and chromium ions can reach 90 percent at least within 60min, and the concentration of hexavalent chromium in the wastewater during balancing is close to 0 mg/L; the removal rate of the organic dye can reach 82.7 percent at least within 60 min; meanwhile, the prepared iron-based spinel oxide has good catalytic performance and can improve the oxidative degradation rate of organic dyes.
(2) The invention utilizes the fluid battery to obtain electric energy while processing heavy metal ions and organic dye with double effects, and has economical practicability.
(3) The fluid battery has the advantages of low requirement on raw materials, less preparation process and simple and convenient operation.
Drawings
FIG. 1 is an XRD spectrum of nickel ferrite obtained in example 1.
FIG. 2 is a scanning electron micrograph of nickel ferrite obtained in example 1, at a magnification of 2 ten thousand.
Fig. 3 is a graph of electrochemical test discharge capacity of the fluid battery obtained in example 1.
FIG. 4 is a graph showing the degradation curve of the heavy metal chromium (VI) ion in example 2.
FIG. 5 is a graph showing the degradation curve of methylene blue, an organic dye in example 2.
Fig. 6 is a schematic diagram of a fluid cell device in an embodiment of the invention.
Fig. 7 is a schematic view of the fluid cell device and the small bulb driven by the fluid cell device in example 3 to generate electricity (the electricity generation shows the word "SCNU").
Fig. 8 is a schematic structural diagram of a fluid cell device according to an embodiment of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
In the embodiment of the application, the bipolar membranes are all bipolar membranes TRJBM (purchased from Beijing Tingrun membrane technology development Co., Ltd.), and the isolation areas (contact areas of positive and negative electrodes) of the diaphragms are all 3cm multiplied by 3 cm; the fluid battery device molds are all made of acrylic materials, and the sizes of the fluid battery device molds are 10cm multiplied by 1 cm; the volumes of the positive electrode reaction bin and the negative electrode reaction bin are both 3cm multiplied by 2 mm; the size of the carbon fiber cloth is 1cm multiplied by 2 cm.
Example 1
A fluid battery and a method for treating heavy metal ions and organic dyes in wastewater by using the fluid battery in a double-effect mode are characterized in that chromium (VI) wastewater is used as a positive electrode of the battery, organic dye wastewater is used as a negative electrode of the battery, iron-based spinel oxide is used as a negative electrode catalyst, the positive electrode and the negative electrode are separated by a diaphragm to form the fluid battery, and the organic dye wastewater is oxidized by oxidizing the chromium (VI) wastewater, so that double-effect treatment of the positive electrode wastewater and the negative electrode wastewater and generation of electric energy are achieved.
(1) The preparation method of the iron-based spinel oxide comprises the following specific steps:
preparing nano nickel ferrite: (1) 0.2986g of Ni (CH) were weighed3COO)2·4H2O (purchased from Aladdin reagent (Shanghai) Co., Ltd.) and 0.9696g of Fe (NO)3)3·9H2And O, mixing and dissolving in 15mL of DMF (N, N-dimethylformamide) solvent, wherein the molar ratio of nickel ions to iron ions is 1:2, magnetically stirring for 30min at room temperature, adding 1.8g of polyvinylpyrrolidone (PVP) as a binder after complete dissolution, and continuously magnetically stirring for 24h at room temperature to obtain the spinning solution.
(2) Winding aluminum foil paper around the roller for one circle for receiving the prepared NiFe2O4A fibrous membrane; injecting the spinning stock solution obtained in the step (1) into a 10mL injector, inversely emptying bubbles in the injector, installing a spinning needle with the inner diameter of 0.5mm, enabling the vertical distance between the front end of the needle and a roller to be 15cm, enabling the spinning injection speed to be 0.10mL/h, installing an electrostatic spinning device after adjustment is finished, connecting the spinning needle with a positive voltage, connecting the spinning roller with a negative voltage, adjusting the negative voltage to 1kv, slowly increasing the positive voltage until the front end of the spinning needle ejects a bud-shaped fiber yarn, and finishing alignmentAnd (5) debugging the voltage. Finally spinning to obtain NiFe2O4A fibrous membrane.
(3) NiFe obtained in the step (2)2O4Removing the fiber membrane from the aluminum foil paper by using tweezers, placing the fiber membrane into a muffle furnace, pre-calcining the fiber membrane for 5 hours at 280 ℃ in the air atmosphere, then calcining the fiber membrane for 4 hours at 600 ℃, and then grinding the fiber membrane into powder to obtain NiFe2O4(nickel ferrite catalyst).
(4) Graphite (graphite paper) is used as current collectors for the positive and negative electrodes, and 0.07g of NiFe is weighed respectively2O40.015g of conductive carbon and 0.015g of PVDF (polyvinylidene fluoride) were dissolved in 1mL of NMP (N-methylpyrrolidone), and the resulting solution was uniformly coated on 2cm × 2cm of graphite paper (coating area: 4 cm) after stirring and grinding for 0.5 hour2) And finally, placing the mixture in a vacuum drying oven, and drying the mixture for 20 hours at the temperature of 60 ℃ to obtain the cathode catalytic material for later use.
(II) preparing a positive electrode solution and a negative electrode solution, which comprises the following specific steps:
the anode solution is 30mg/L potassium dichromate solution, 15mg of potassium dichromate is weighed by an electronic balance and added into a 200mL beaker, and 100mL of deionized water is added and stirred for dissolution; and transferring the uniformly mixed solution into a volumetric flask, washing the beaker and the glass rod with deionized water, introducing the washing solution into the volumetric flask, adding the deionized water to a constant volume of 500mL, and putting 50mL into a 50mL beaker after preparation for later use.
The cathode solution is 30mg/L methyl orange solution, 15mg of methyl orange is weighed by an electronic balance and added into a 200mL beaker, and 100mL of deionized water is added and stirred for dissolution; and transferring the uniformly mixed solution into a volumetric flask, washing the beaker and the glass rod with deionized water, introducing the washing solution into the volumetric flask, adding the deionized water to a constant volume of 500mL, and putting 50mL into a 50mL beaker after preparation for later use.
(III) the fluid cell device is prepared by the following method:
assembling according to the self-assembly sequence of the fluid battery mold: from the negative electrode, a mold A, a carbon fiber cloth (negative electrode), graphite paper coated with nickel ferrite (negative current collector coated with a catalyst), carbon foam (negative electrode), a mold B (negative electrode), a bipolar membrane, another mold B (positive electrode), graphite paper (positive current collector), carbon fiber cloth (positive electrode) and another mold A (positive electrode) are sequentially placed. The positive molds A and B form a positive reaction bin, and the negative molds A and B form a negative reaction bin. Limiting an anode in an anode reaction bin, placing foamy carbon in a cathode reaction bin, limiting a cathode in a cathode reaction bin, and coating a cathode catalyst on a cathode current collector; the carbon fiber cloth of the anode, the anode current collector, the anode reaction bin, the bipolar membrane, the cathode reaction bin, the cathode current collector and the carbon fiber cloth of the cathode are stacked and arranged; the positive electrode liquid storage bin is connected with the positive electrode reaction bin through a hose, and the negative electrode reaction bin is connected with the negative electrode liquid storage bin through a hose. The positive carbon fiber cloth and the negative carbon fiber cloth are connected with an external circuit so as to output voltage; the liquid in the anode liquid storage bin and the liquid in the cathode liquid storage bin respectively flow to the anode reaction bin and the cathode reaction bin through the peristaltic pump and continuously flow in the anode reaction bin and the cathode reaction bin. After the fluid battery die is installed, the fluid battery die is fixed and tightly installed by screws and bolts, through hole plugs are screwed at the openings A of the two dies, a hose is externally connected, a potassium dichromate solution is introduced into the hose communicated with the positive electrode reaction bin, and a methyl orange solution is introduced into the hose communicated with the negative electrode reaction bin; the inlet hose and the outlet hose of the anode are simultaneously connected into a beaker (anode liquid storage bin) filled with potassium dichromate solution, and the inlet hose and the outlet hose of the cathode are simultaneously connected into a beaker (cathode liquid storage bin) filled with methyl orange solution. The battery clamp is clamped on the lug carbon cloth according to the positive and negative electrodes, and the positive and negative carbon cloths are separated by a non-conductive plastic sheet.
After the fluid battery device is assembled and debugged, the hose is clamped on the peristaltic pump by using a clamp, the peristaltic pump is opened to enable the solution in the positive and negative electrode reaction chambers to flow, the flow rate of positive and negative electrode fluids is set to be 10rpm, and an electrochemical test is carried out. The cyclic voltammetry test of the cell was performed under constant current conditions of 1 mA.
FIG. 1 is an XRD pattern of a nickel ferrite catalyst. The map is identical with the nickel ferrite standard card JCPDSno.10-0325, and NiO and Fe do not exist2O3And the diffraction peaks of the impurities indicate that the product is pure nickel ferrite. FIG. 2 is a scanning electron micrograph of a nickel ferrite catalyst, from which it can be seen that the electrospun fibers have passedThe calcined nickel ferrite is still fibrous, and the average diameter of the nano-fiber is about 200 nanometers, which shows that the nickel ferrite nano-fiber is successfully prepared by the method. Fig. 3 is a result of cyclic voltammetry, wherein a curve corresponding to a curve without a nickel ferrite catalyst shows that a fluid battery without a nickel ferrite catalyst is provided, other conditions are the same as those in example 1, and fig. 3 shows that a discharge platform of the fluid battery in this embodiment is 1.4V, which shows a better discharge performance.
Example 2
A fluid battery and a method for treating heavy metal ions and organic dyes in wastewater by using the fluid battery in a double-effect mode are characterized in that chromium (VI) wastewater is used as a positive electrode of the battery, organic dye wastewater is used as a negative electrode of the battery, iron-based spinel oxide is used as a negative electrode catalyst, the positive electrode and the negative electrode are separated by a diaphragm to form the fluid battery, and the organic dye wastewater is oxidized by oxidizing the chromium (VI) wastewater, so that double-effect treatment of the positive electrode wastewater and the negative electrode wastewater and generation of electric energy are achieved.
(1) The preparation method of the iron-based spinel oxide comprises the following specific steps:
preparing nano zinc ferrite: (1) 0.3293g of Zn (CH) were weighed out3COO)2·2H2O and 1.212g Fe (NO)3)3·9H2And O, mixing and dissolving in 15mL of DMF solvent, wherein the molar ratio of zinc ions to iron ions is 1:2, magnetically stirring for 30min at room temperature, adding 1.8g of polyvinylpyrrolidone (PVP) as a binder after complete dissolution, and continuously magnetically stirring for 24h at room temperature to obtain a spinning stock solution.
(2) Winding the roller by using aluminum foil paper for one circle for receiving the prepared zinc ferrite fiber membrane, injecting the spinning stock solution obtained in the step (1) into a 10mL injector, inversely emptying bubbles in the injector, installing a spinning needle head with the inner diameter of 0.6mm, wherein the vertical distance between the front end of the needle head and the roller is 18cm, and the spinning injection speed is 0.15 mL/h; after the adjustment is finished, an electrostatic spinning device is installed, the spinning needle is connected with a positive voltage, the spinning roller is connected with a negative voltage, after the negative voltage is adjusted to 1kv, the positive voltage is slowly increased until the spinning needle ejects the bud-shaped cellosilk, and then the positive voltage is stopped increasing. And finally spinning to obtain the zinc ferrite fiber membrane.
(3) Removing the zinc ferrite fiber membrane obtained in the step (2) from the tin foil paper by using a pair of tweezers, putting the tin foil paper into a muffle furnace, pre-calcining the zinc ferrite fiber membrane for 5 hours at 280 ℃ in the air atmosphere, then calcining the zinc ferrite fiber membrane for 4 hours at 600 ℃, and then grinding the zinc ferrite fiber membrane into powder to obtain ZnFe2O4。
(4) Graphite (graphite paper) is used as a current collector for both the positive electrode and the negative electrode, and 0.07g of ZnFe is weighed2O40.015g of conductive carbon and 0.015g of PVDF were dissolved in 1mL of NMP, stirred and ground for 0.5 hour to obtain a slurry, and the slurry was uniformly coated on 2cm × 2cm graphite paper (coating area of 4 cm)2) And finally, placing the mixture in a vacuum drying oven, and drying the mixture for 20 hours at the temperature of 60 ℃ to obtain the cathode catalytic material for later use.
(II) preparing a positive electrode solution and a negative electrode solution, which comprises the following specific steps:
the positive electrode solution was 60mg/L sodium dichromate solution, and 30mg of sodium dichromate (purchased from Aladdin reagent (Shanghai) Co., Ltd.) was weighed by an electronic balance into a 200mL beaker, and 100mL of deionized water was added and dissolved with stirring. And transferring the uniformly mixed solution into a volumetric flask, washing the beaker and the glass rod with deionized water, introducing the washing solution into the volumetric flask, adding the deionized water to a constant volume of 500mL, and putting 50mL into a 50mL beaker after preparation for later use.
The cathode solution is 60mg/L methylene blue solution, 30mg of methylene blue is weighed by an electronic balance and added into a 200mL beaker, and 100mL of deionized water is added and dissolved by stirring. And transferring the uniformly mixed solution into a volumetric flask, washing the beaker and the glass rod with deionized water, introducing the washing solution into the volumetric flask, adding the deionized water to a constant volume of 500mL, and putting 50mL into a 50mL beaker after preparation for later use.
(III) the fluid cell device is prepared by the following method:
assembling according to the self-assembly sequence of the fluid battery mould, wherein the specific assembly method is the same as that of the embodiment 1, after the fluid battery mould is installed, fixing and tightening the fluid battery mould by using screws and bolts, screwing through hole plugs at the openings A of the two moulds, externally connecting a hose, introducing a sodium dichromate solution into the hose communicated with the positive electrode reaction bin, and introducing a methylene blue solution into the hose communicated with the negative electrode reaction bin; the inlet hose port and the outlet hose of the anode are simultaneously connected into a beaker (anode liquid storage bin) filled with potassium dichromate, and the inlet hose and the outlet hose of the cathode are simultaneously connected into a beaker (cathode liquid storage bin) filled with methylene blue. The battery clamp is clamped on the lug carbon cloth according to the positive and negative electrodes, and the positive and negative carbon cloths are separated by a non-conductive plastic sheet.
After the fluid battery device is assembled and debugged, the hose is clamped on the peristaltic pump by the clamp, the peristaltic pump is started to enable the solution in the positive and negative reaction chambers to flow, the flow speed of positive and negative fluid is set to be 10rpm, and positive and negative lugs of the fluid battery device are externally connected with positive and negative clamps of the light-emitting plate to drive the light-emitting plate bulb to emit light.
After the fluid battery device is assembled, the flexible pipe is clamped on a peristaltic pump by a clamp, the peristaltic pump is opened to enable the solution in the positive and negative reaction chambers to flow, 2mL of solution is taken out of positive and negative beakers (positive and negative liquid storage chambers) by a dropper every 30min, and the concentrations of the potassium dichromate solution and the methylene blue solution are tested by an ultraviolet visible spectrophotometer, so that the degradation performance of the potassium dichromate solution and the methylene blue solution is obtained by the method in the embodiment.
FIG. 4 is a graph showing the degradation performance of the method of this embodiment on potassium dichromate, in which the degradation rate on chromium (VI) ions can reach 90% within 60min, and the concentration of hexavalent chromium in the solution at equilibrium is close to 0 mg/L; fig. 5 is a graph of the degradation performance of the method described in this example on methylene blue, the removal rate of methylene blue on the organic dye can reach 82.7% within 60min, the concentration of methylene blue in the solution at equilibrium is close to 1.32mg/L, and the degradation rate at equilibrium is (30-1.32)/30-95.6%.
Example 3
A fluid battery and a method for treating heavy metal ions and organic dyes in wastewater by using the fluid battery in a double-effect mode are characterized in that chromium (VI) wastewater is used as a positive electrode of the battery, organic dye wastewater is used as a negative electrode of the battery, iron-based spinel oxide is used as a negative electrode catalyst, the positive electrode and the negative electrode are separated by a diaphragm to form the fluid battery, and the organic dye wastewater is oxidized by oxidizing the chromium (VI) wastewater, so that double-effect treatment of the positive electrode wastewater and the negative electrode wastewater and generation of electric energy are achieved.
(1) The preparation method of the iron-based spinel oxide comprises the following specific steps:
preparing nano cobalt ferrite: (1) 0.2989g of Co (CH) were weighed out3COO)2·4H2O (purchased from Aladdin reagent (Shanghai) Co., Ltd.) and 0.9696g of Fe (NO)3)3·9H2And O, mixing and dissolving in 15mL of DMF solvent, wherein the molar ratio of cobalt ions to iron ions is 1:2, magnetically stirring for 30min at room temperature, adding 1.8g of polyvinylpyrrolidone (PVP) as a binder after complete dissolution, and continuously magnetically stirring for 24h at room temperature to obtain a spinning stock solution.
(2) Winding the roller by using aluminum foil paper for one circle for receiving the prepared cobalt ferrite fiber membrane, injecting the spinning stock solution obtained in the step (1) into a 10mL injector, inverting and emptying bubbles in the injector, and then installing a spinning needle head with the inner diameter of 0.5mm, wherein the vertical distance between the front end of the needle head and the roller is 18cm, and the spinning injection speed is 0.12 mL/h; after the adjustment is finished, an electrostatic spinning device is installed, the spinning needle is connected with a positive voltage, the spinning roller is connected with a negative voltage, after the negative voltage is adjusted to 1kv, the positive voltage is slowly increased to the front end of the spinning needle to spray the bud-shaped cellosilk, and then the adjustment of the positive voltage is finished. And finally spinning to obtain the cobalt ferrite fiber membrane.
(3) Removing the cobalt ferrite fiber membrane obtained in the step (2) from the tin foil paper by using a pair of tweezers, putting the tin foil paper into a muffle furnace, pre-calcining the tin foil paper for 5 hours at 280 ℃ in the air atmosphere, then calcining the tin foil paper for 4 hours at 600 ℃, and then grinding the tin foil paper into powder to obtain CoFe2O4。
(4) Graphite (graphite paper) is used as a current collector for both the positive electrode and the negative electrode, and 0.07g of CoFe is weighed2O40.015g of conductive carbon and 0.015g of PVDF were dissolved in 1mL of NMP, and the mixture was uniformly coated on 2cm × 2cm of graphite paper (coating area 4 cm) after stirring and grinding for 0.5 hour2) And finally, placing the mixture in a vacuum drying oven, and drying the mixture for 20 hours at the temperature of 60 ℃ to obtain the cathode catalytic material for later use.
(II) preparing a positive electrode solution and a negative electrode solution, which comprises the following specific steps:
the anode solution is 45mg/L potassium dichromate solution, 22.5mg of potassium dichromate is weighed by an electronic balance and added into a 200mL beaker, and 100mL of deionized water is added and dissolved by stirring. And transferring the uniformly mixed solution into a volumetric flask, washing the beaker and the glass rod with deionized water, introducing the washing solution into the volumetric flask, adding the deionized water to a constant volume of 500mL, and putting 50mL into a 50mL beaker after preparation for later use.
The cathode solution is a 45mg/L methyl red solution, 22.5mg of methyl red is weighed by an electronic balance and added into a 200mL beaker, and 100mL of deionized water is added and dissolved by stirring. And transferring the uniformly mixed solution into a volumetric flask, washing the beaker and the glass rod with deionized water, introducing the washing solution into the volumetric flask, adding the deionized water to a constant volume of 500mL, and putting 50mL into a 50mL beaker after preparation for later use.
(III) the fluid cell device is prepared by the following method:
assembling according to the self-assembly sequence of the fluid battery mould, wherein the specific assembly method is the same as that of the embodiment 1, after the fluid battery mould is installed, fixing and tightening the fluid battery mould by using screws and bolts, screwing through hole plugs at the openings A of the two moulds, externally connecting a hose, introducing a potassium dichromate solution into the hose communicated with the positive electrode reaction bin, and introducing a methyl red solution into the hose communicated with the negative electrode reaction bin; the inlet hose and the outlet hose of the anode are simultaneously connected into a beaker (an anode liquid storage bin) filled with potassium dichromate, and the inlet hose and the outlet hose of the cathode are simultaneously connected into a beaker (a cathode liquid storage bin) filled with methyl red. The battery clamp is clamped on the lug carbon cloth according to the positive and negative electrodes, and the positive and negative carbon cloths are separated by a non-conductive plastic sheet.
After the fluid battery device is assembled, the flexible pipe is clamped on the peristaltic pump by using a clamp, the peristaltic pump is started to enable the solution in the positive and negative reaction chambers to flow, the flow rates of positive and negative fluid are set to be 10rpm, positive and negative lugs of the fluid battery device are externally connected with positive and negative clamps of the light-emitting plate, the light-emitting plate bulb is driven to emit light, and the schematic diagram is as shown in fig. 7.
Fig. 6 is a schematic view of a fluid battery device according to all embodiments of the present invention, and fig. 7 is a schematic view of a fluid battery device according to embodiment 3 of the present invention and an external light-emitting lamp panel during discharging, which shows that the fluid battery according to this embodiment can generate electric energy while performing double-effect treatment on chromium (VI) ions and methyl red. Fig. 8 is a schematic structural view of a fluid cell device according to all embodiments of the present invention.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (8)

1. A fluid battery is characterized in that a positive electrode of the fluid battery is heavy metal ion wastewater, a negative electrode of the fluid battery is organic dye wastewater, and the positive electrode and the negative electrode are isolated by a diaphragm to form the fluid battery; the structure of the fluid battery also comprises a positive current collector, a negative current collector and a negative catalyst, wherein the negative catalyst is iron-based spinel oxide;
the heavy metal ion wastewater is chromium ion wastewater, and the organic dye wastewater is azo dye solution;
the iron-based spinel oxide is at least one of nano nickel ferrite, nano zinc ferrite, nano cobalt ferrite and nano manganese ferrite;
the diaphragm is a bipolar membrane.
2. The fluid cell of claim 1, wherein the separator is a bipolar membrane TRJBM.
3. The fluid battery according to claim 1 or 2, wherein the catalyst is coated on the negative electrode current collector in an amount of 10-20 mg/cm2。
4. The fluid battery according to claim 1 or 2, wherein the positive electrode current collector and the negative electrode current collector are both made of graphite, heavy metal ion wastewater is used as a battery positive electrode active substance and a battery carrier, organic dye wastewater is used as a battery negative electrode active substance and a battery carrier, positive and negative electrode fluids are respectively formed by a peristaltic pump, and the flow rates of the positive and negative electrode fluids are both 5-15 rpm.
5. The fluid battery according to claim 1 or 2, wherein the structure of the fluid battery further comprises a positive electrode reaction chamber, a positive electrode liquid storage chamber, a negative electrode reaction chamber, a negative electrode liquid storage chamber, a flow pipeline, carbon fiber cloth and carbon foam.
6. The fluid battery of any one of claims 1-5 can be applied to double-effect treatment of heavy metal ions and organic dyes in wastewater, and is characterized in that the specific application method comprises the following steps: the fluid battery of any one of claims 1-5 is formed by taking the heavy metal ion wastewater to be treated as a positive electrode and the organic dye wastewater to be treated as a negative electrode; the organic dye wastewater is oxidized by the oxidability of the heavy metal ion wastewater, so that the double-effect treatment of the anode wastewater and the cathode wastewater and the generation of electric energy are achieved.
7. The fluid battery of claim 6, wherein the chromium ion wastewater is a potassium dichromate and/or sodium dichromate solution, and the azo dye solution is at least one of a methyl red solution, a methyl orange solution and a methylene blue solution.
8. The fluid battery of claim 7, which is applicable to double-effect treatment of heavy metal ions and organic dyes in wastewater, wherein the concentration of dichromate ions in the chromium ion wastewater is 30-90 mg/L; the concentration of the organic dye in the organic dye wastewater is 30-90 mg/L.
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