CN116116224A - Electrodialysis system and application - Google Patents
Electrodialysis system and application Download PDFInfo
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- CN116116224A CN116116224A CN202211106906.2A CN202211106906A CN116116224A CN 116116224 A CN116116224 A CN 116116224A CN 202211106906 A CN202211106906 A CN 202211106906A CN 116116224 A CN116116224 A CN 116116224A
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- electrodialysis
- fuel cell
- electrodialysis system
- industrial wastewater
- gas collecting
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/46—Apparatus therefor
- B01D61/48—Apparatus therefor having one or more compartments filled with ion-exchange material, e.g. electrodeionisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/52—Accessories; Auxiliary operation
-
- 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
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
- C02F1/4695—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis electrodeionisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2313/00—Details relating to membrane modules or apparatus
- B01D2313/36—Energy sources
- B01D2313/365—Electrical sources
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- 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 application belongs to the technical field of electrochemistry, and particularly relates to an electrodialysis system and application. The running cost of the existing electrodialysis equipment is high. The application provides an electrodialysis system, including the electrodialysis ware, fuel cell, energy storage equipment and boost equipment connect gradually, boost equipment with the electrodialysis ware is connected. The fuel cell and the electrodialysis device work cooperatively, so that hydrogen and oxygen generated by the electrolysis of unit poles at two ends of the electrodialysis membrane stack are effectively recycled and used for supplementing electricity for the electrodialysis, and the purpose of reducing energy consumption is achieved.
Description
Technical Field
The application belongs to the technical field of electrochemistry, and particularly relates to an electrodialysis system and application.
Background
Water resources are the fundamental guarantee for human survival. Along with the rapid development of the economic level and industrialization process of China, the ecological problems of water resource pollution, water resource waste and the like of China are increasingly serious. According to statistics, 60% of industrial wastewater in China contains heavy metal pollutants. At present, common treatment methods for heavy metal ions in industrial sewage comprise a chemical precipitation method, an electrodialysis method, an adsorption method, an ion exchange method, a membrane separation method, a phytoremediation technology, a new technology and the like. The electrodialysis method has the advantages of mature process for treating heavy metal sewage, simple device, stable equipment operation, no pollution in the operation process and good development prospect.
Electrodialysis devices are typically stacks of multiple units with alternating anion and cation membranes. By applying an external electric field, anions and cations are directionally migrated by utilizing the selective permeability of the ion exchange membrane (namely cations can permeate the cation exchange membrane and anions can permeate the anion exchange membrane). Wherein the cationic membrane allows metal cations and other cations to pass through, but prevents anions from passing through; while the anionic membrane only allows anions to pass through, but cations cannot. In industrial sewage treatment, heavy metal cations and a part of anions are enriched from sewage, and the sewage from which the heavy metal ions are removed is recovered through crystallization and desalination and is discharged after subsequent treatment to reach the standard. Unlike the process of the intermediate electrodialysis unit, the electrolytes (polar water) at the two ends of the membrane stack undergo a water electrolysis reaction to generate hydrogen and oxygen, respectively.
Electrodialysis is used for sea water desalination initially, is widely used in chemical industry, light industry, metallurgy, paper making and medicine industry, and is especially important for preparing pure water and treating three wastes in environmental protection, such as acid-base recovery, electroplating waste liquid treatment and recovery of useful substances from industrial waste water. But the existing electrodialysis devices are relatively expensive to operate.
Disclosure of Invention
1. Technical problem to be solved
The electrodialysis method is initially used for sea water desalination, is widely used in chemical industry, light industry, metallurgy, papermaking and medicine industry, and is particularly used for preparing pure water and treating three wastes in environmental protection, such as acid-base recovery, electroplating waste liquid treatment, recovery of useful substances from industrial waste water and the like. However, the problem of higher cost of the conventional electrodialysis equipment is solved, and the application provides an electrodialysis system and application.
2. Technical proposal
To achieve the above object, the present application provides an electrodialysis system, including an electrodialyzer, a fuel cell, an energy storage device, and a voltage boosting device connected in sequence, the voltage boosting device being connected with the electrodialyzer.
Another embodiment provided herein is: the electrodialyzer comprises a first polar chamber and a second polar chamber, wherein the first polar chamber is connected with the fuel cell through a first gas collecting pipeline, and the second polar chamber is connected with the fuel cell through a second gas collecting pipeline.
Another embodiment provided herein is: the first pole chamber is provided with a first exhaust hole, the second pole chamber is provided with a second exhaust hole, the first exhaust hole is connected with the first gas collecting pipeline, and the second exhaust hole is connected with the second gas collecting pipeline.
Another embodiment provided herein is: the first gas collecting pipeline is a rubber pipe, and the second gas collecting pipeline is a rubber pipe; the energy storage device is a lithium ion battery or a lead-acid battery.
Another embodiment provided herein is: the fuel cell is connected with a monitoring device for monitoring the variation of the output voltage and current of the fuel cell.
The application also provides an application of the electrodialysis system, and the electrodialysis system is applied to industrial wastewater treatment.
Another embodiment provided herein is: the method comprises the steps of preprocessing industrial wastewater, introducing the preprocessed industrial wastewater into the electrodialysis device, introducing hydrogen and oxygen generated by electrolysis into the fuel cell to generate electricity, storing electric energy into the energy storage equipment, and raising the voltage through the boosting equipment and then conveying the electric energy to the electrodialysis device; meanwhile, fresh water is discharged, and concentrated solution is subjected to crystallization and desalination treatment.
Another embodiment provided herein is: and desalting one part of the industrial wastewater under the action of the electrodialysis device to obtain fresh water, and concentrating the other part of the industrial wastewater under the action of the electrodialysis device.
Another embodiment provided herein is: the current density is 10mA cm -2 ～30mA cm -2 The efficiency of the desalination increases rapidly, exceeding 30mA cm -2 The efficiency of the desalination increases slowly afterwards.
Another embodiment provided herein is: the industrial wastewater is injected into the electrodialysis device through a peristaltic pump, and the flow rate of the industrial wastewater is 60ml min -1 。
3. Advantageous effects
Compared with the prior art, the electrodialysis system and the beneficial effect of using lie in that this application provided:
the electrodialysis system provided by the application utilizes the electrodialysis technology and the oxyhydrogen fuel cell to combine, and a new system for treating industrial sewage with ultralow energy consumption is constructed.
The electrodialysis system provided by the application works together with the fuel cell and the electrodialysis device, effectively recovers and uses hydrogen and oxygen generated by the electrolysis of unit poles at two ends of the electrodialysis membrane stack, and is used for supplementing electricity for the electrodialysis, so that the purpose of reducing energy consumption is achieved.
The application of the electrodialysis system provided by the application adopts an electrodialysis method to treat heavy metal industrial sewage.
The application of the electrodialysis system provided by the application removes heavy metal ions in heavy metal wastewater through electrodialysis, simultaneously, hydrogen and oxygen formed by electrolysis of water at two ends of an electrodialyzer are introduced into a fuel cell, and generated direct current is supplied to an electrodialysis process in a supplementing manner, so that the energy consumption of sewage treatment is reduced.
The application of the electrodialysis system reduces the energy consumption of the electrodialysis treatment industrial sewage.
The application of the electrodialysis system can achieve the removal rate of heavy metal ions reaching more than 95% in the electrodialysis process, and the polar water is electrolyzed to form hydrogen and oxygen which are fed into the fuel cell to generate electricity, so that the electrodialysis system can be used for supplementing electricity for electrodialysis, and the purpose of reducing energy consumption is achieved.
Drawings
FIG. 1 is a schematic diagram of the electrodialysis system of the present application;
FIG. 2 is a schematic illustration of the effect of current density, treatment time and solution temperature of the present application on electrodialysis treatment of industrial wastewater;
fig. 3 is a graph of voltage, current, and power for a single fuel cell power generation module of the present application.
Detailed Description
Hereinafter, specific embodiments of the present application will be described in detail with reference to the accompanying drawings, and according to these detailed descriptions, those skilled in the art can clearly understand the present application and can practice the present application. Features from various embodiments may be combined to obtain new implementations or to replace certain features from certain embodiments to obtain other preferred implementations without departing from the principles of the present application.
Referring to fig. 1 to 3, the present application provides an electrodialysis system comprising an electrodialyzer 1, wherein the electrodialyzer 1, a fuel cell 2, an energy storage device and a pressure boosting device are sequentially connected, and the pressure boosting device is connected with the electrodialyzer 1. Specific energy storage equipment (such as a lithium ion battery, a lead-acid battery and the like) is adopted to store electric energy generated by the fuel cell, and after the voltage of the energy storage equipment is increased, the energy storage equipment is cut into an electrodialyzer and used for supplementing energy to treat industrial sewage, so that the aim of reducing energy consumption is fulfilled.
The anion membranes and the cation membranes in the electrodialyzer 1 are alternately arranged to form a fresh water chamber and a concentrated water chamber, and a water distribution hole, a water distribution groove, a water flow channel, a water collecting groove and a water collecting hole are formed in the partition plate, so that a water flow channel with water distribution and water collection functions can be formed. The two ends are a cathode chamber and an anode chamber, wherein the cathode is a titanium net, and the anode is a titanium net coated with a ruthenium coating.
The fuel cell 2 includes a seal assembly, a proton membrane, a core electrode assembly, a bus electrode, and the like.
Electrodialysis coupled fuel cell systems require tuning. When the electrodialysis current density is increased, the treatment rate of heavy metal ions in industrial wastewater is increased, the generation rate of cathode and anode gases is increased, and the output power of the power generation module of the fuel cell 2 is also increased. However, the increase of the current density leads to a significant increase of the energy consumption in the electrodialysis process, and also leads to energy loss such as electrolyte heating. Therefore, it is necessary to balance the efficiency of electrodialysis treatment of industrial wastewater and the power generation efficiency of the fuel cell 2 to obtain optimal experimental parameters.
The power supply is switched on, the electrodialysis device is started to be in a working state, the exhaust holes on the cathode chamber and the anode chamber are connected with the rubber tube, and the generated hydrogen and oxygen are introduced into the fuel cell 2 to generate electricity.
Further, the electrodialyzer 1 comprises a first polar chamber connected to the fuel cell 2 by a first gas collecting line and a second polar chamber connected to the fuel cell 2 by a second gas collecting line.
Further, a first exhaust hole is formed in the first pole chamber, a second exhaust hole is formed in the second pole chamber, the first exhaust hole is connected with the first gas collecting pipeline, and the second exhaust hole is connected with the second gas collecting pipeline.
Further, the first gas collecting pipeline is a rubber pipe, and the second gas collecting pipeline is a rubber pipe; the energy storage device is a lithium ion battery or a lead-acid battery.
Further, the fuel cell 2 is connected to a monitoring device for monitoring changes in the output voltage and current of the fuel cell 2. The monitoring device is a constant resistance, and a constant resistance (10-50Ω) is connected in series in the circuit to monitor the change of the output voltage and current of the fuel cell 2. The utilization rate of hydrogen and oxygen can be improved by connecting a plurality of power generation modules of the fuel cells 2 in series.
The constant resistance is used as a load for measuring the power generation amount of the fuel cell, and is therefore connected to only two electrodes of the fuel cell.
The application also provides an application of the electrodialysis system, and the electrodialysis system is applied to industrial wastewater treatment.
Further, the method comprises the steps of pretreating industrial wastewater, introducing the pretreated industrial wastewater into the electrodialysis device 1, introducing hydrogen and oxygen generated by electrolysis into the fuel cell 2 for power generation, storing electric energy into the energy storage equipment, and raising the voltage by the voltage raising equipment and then conveying the electric energy to the electrodialysis device 1; meanwhile, fresh water is discharged, and concentrated solution is subjected to crystallization and desalination treatment.
Industrial wastewater (raw water) should be pretreated before electrodialysis, including removal of suspended matters, organic matters, etc. in the wastewater. After pretreatment, the industrial wastewater is passed into an electrodialyzer 1. Under the action of an electric field, heavy metal cations in the wastewater enter a concentration chamber through a cation membrane; anions in the wastewater also pass through the anion membrane and partially enter the concentration chamber. As a result, a part of wastewater is deprived of heavy metal ions and a part of anions, so that the desalination treatment of industrial sewage is realized, and the wastewater can be discharged after reaching the comprehensive discharge standard (GB 8978-1996); while another part of the raw water becomes concentrated solution. The concentrated solution is subjected to crystallization and desalination treatment, and most heavy metal salts can be recovered.
The two end water chambers are pumped with sodium sulfate solution with certain concentration. In the electrodialysis process, hydrogen and oxygen generated by the polar hydrolysis are introduced into the fuel cell 2 for power generation. The overall process flow is shown in figure 1.
In the electrodialysis process, waste water and polar water are pushed into the electrodialyzer 1 by a pump, and sampling analysis is performed at intervals. The technological parameters are as follows: waste water volume 100-500 ml, circulation flow rate 40-120 mlmin -1 The electrolysis time is 0.5 to 3 hours, the temperature is 30 to 70 ℃ and the current density is 10 to 50mA cm -2 The method comprises the steps of carrying out a first treatment on the surface of the The electrolyte introduced into the anode and cathode chambers contains 3 percent sodium sulfate, the volume is 100-500 ml, and the circulating flow rate is 40-120 ml min -1 。
Further, the current density was 10mA cm -2 ～30mA cm -2 The desalination efficiency increases rapidly, exceeding 30mAcm -2 After that, the efficiency of the desalination increasesSlow in length.
Further, the industrial wastewater is injected into the electrodialyzer 1 by a peristaltic pump, and the flow rate of the industrial wastewater is 60ml min -1 。
Examples
A new system for reducing energy consumption of industrial wastewater treatment based on the combination of an electrodialyzer and a fuel cell comprises the following specific steps:
(1) Structure of electrodialyzer 1 and fuel cell power generation
The electrodialysis device 1 is characterized in that homogeneous cation exchange membranes (commercially available) and homogeneous anion exchange membranes (commercially available) are selected, the anion membranes and the cation membranes in the electrodialysis device 1 are alternately arranged to form a fresh water chamber and a concentrated water chamber, and water distribution holes, water distribution grooves, water flowing channels, water collecting grooves and water collecting holes are formed in a partition plate, so that water flowing channels with water distribution and water collecting functions can be formed. The two ends are a cathode chamber and an anode chamber, wherein the cathode is a titanium net, and the anode is a titanium net coated with a ruthenium coating. The external dimensions of the positive electrode and the negative electrode are 100mm multiplied by 15mm, and the external dimensions of the separator are 100mm multiplied by 1mm. The actual dimensions of the desalting chamber, the concentrating chamber and the electrolysis chamber are smaller and are 50mm multiplied by 1mm.
The fuel cell 2 used includes a seal assembly, a proton membrane, a core electrode assembly, a bus electrode, and the like. The fuel cell 2 has an effective size of 25×25mm, and has an output voltage of about 0.8V and a current of about 0.5A. The electric energy generated by the battery reaction is stored by an energy storage battery and fed back to the electrodialyzer 1 through a boosting device for supplementing the electric energy required by the industrial wastewater treatment.
(2) Electrodialysis treatment of heavy metal sewage
The experiment adopts simulated industrial wastewater, and the components are as follows:
taking 300ml of the prepared solution as raw water, synchronously injecting the raw water into the fresh water chamber and the concentrated water chamber of the electrodialyzer 1 in the step (1) by using a peristaltic pump, wherein the flow rate is 60ml min -1 . Meanwhile, preparing 300ml polar liquid containing 3% sodium sulfate, respectively pumping into anode and cathode chambers, and circulatingFlow rate 60ml min -1 。
It was found that with increasing current density, the current density was increased at 10mA cm -2 ～30mA cm -2 The desalination efficiency increases rapidly; higher than 30mA cm -2 Later, desalination efficiency increased slowly. To achieve a reduction in energy consumption, the power consumption is reduced by 30mA cm -2 As an optimal current density, fig. 2 shows. It has also been found that electrodialysis desalination efficiency increases significantly with time and temperature, since temperature increases facilitate solute ion transfer, and longer times allow sufficient time for metal ions to transport across the membrane, facilitating thermodynamic processes.
The optimum conditions are thus: the flow rate is 60ml min -1 The time is 2 hours, the temperature of the solution is 50 ℃, and the current density is 30mAcm -2 . The highest efficiency of electrodialysis treatment of metal ions in sewage and Zn 2+ 、Cu 2+ And Cd 2+ The removal rate of the plasma metal ions is over 95 percent, and the sewage discharge standard is reached.
(3) Electric power generation of electrodialysis coupling fuel cell system
A constant resistor (10Ω) is connected in series in the circuit to monitor the variation of the output voltage and current of the fuel cell 2. As a result, it was found that in the electrodialysis in the step (2), the flow rate was 60ml min -1 The time is 2 hours, the temperature of the solution is 50 ℃, and the current density is 30mA cm -2 In this case, the ion impurity removal efficiency is the highest. At this time, the efficiency of the fuel cell 2 for generating electricity to compensate the electrodialysis system is also high. The output voltage of the power generation module of the single fuel cell 2 reaches 0.62V, the current reaches 0.38A, and the power generation power reaches 0.23W (shown in FIG. 3). The generated electric energy is stored by a lithium ion battery and fed back to an electrodialysis system through a boosting device, so that the overall energy consumption of industrial wastewater treatment can be effectively reduced.
Although the present application has been described with reference to particular embodiments, those skilled in the art will appreciate that many modifications are possible in the principles and scope of the disclosure. The scope of the application is to be determined by the appended claims, and it is intended that the claims cover all modifications that are within the literal meaning or range of equivalents of the technical features of the claims.
Claims (10)
1. An electrodialysis system, characterized by: the fuel cell comprises an electrodialyzer, a fuel cell, an energy storage device and a boosting device, wherein the electrodialyzer, the fuel cell, the energy storage device and the boosting device are sequentially connected, and the boosting device is connected with the electrodialyzer.
2. Electrodialysis system according to claim 1, characterized in that: the electrodialyzer comprises a first polar chamber and a second polar chamber, wherein the first polar chamber is connected with the fuel cell through a first gas collecting pipeline, and the second polar chamber is connected with the fuel cell through a second gas collecting pipeline.
3. Electrodialysis system according to claim 2, characterized in that: the first pole chamber is provided with a first exhaust hole, the second pole chamber is provided with a second exhaust hole, the first exhaust hole is connected with the first gas collecting pipeline, and the second exhaust hole is connected with the second gas collecting pipeline.
4. Electrodialysis system according to claim 1, characterized in that: the first gas collecting pipeline is a rubber pipe, and the second gas collecting pipeline is a rubber pipe; the energy storage device is a lithium ion battery or a lead-acid battery.
5. Use of an electrodialysis system according to claim 1, characterized in that: the fuel cell is connected with a monitoring device for monitoring the variation of the output voltage and current of the fuel cell.
6. Use of an electrodialysis system according to any one of claims 1-5, characterized in that: the electrodialysis system is applied to industrial wastewater treatment.
7. Use of an electrodialysis system according to claim 5, characterized in that: the method comprises the steps of preprocessing industrial wastewater, introducing the preprocessed industrial wastewater into the electrodialysis device, introducing hydrogen and oxygen generated by electrolysis into the fuel cell to generate electricity, storing electric energy into the energy storage equipment, and raising the voltage through the boosting equipment and then conveying the electric energy to the electrodialysis device; meanwhile, fresh water is discharged, and concentrated solution is subjected to crystallization and desalination treatment.
8. Use of an electrodialysis system according to claim 6, characterized in that: and desalting one part of the industrial wastewater under the action of the electrodialysis device to obtain fresh water, and concentrating the other part of the industrial wastewater under the action of the electrodialysis device.
9. Use of an electrodialysis system according to claim 7, characterized in that: the current density is 10mA cm -2 ～30mA cm -2 The efficiency of the desalination increases rapidly, exceeding 30mA cm -2 The efficiency of the desalination increases slowly afterwards.
10. Use of an electrodialysis system according to claim 8, characterized in that: the industrial wastewater is injected into the electrodialysis device through a peristaltic pump, and the flow rate of the industrial wastewater is 60ml min -1 。
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211106906.2A CN116116224A (en) | 2022-09-09 | 2022-09-09 | Electrodialysis system and application |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211106906.2A CN116116224A (en) | 2022-09-09 | 2022-09-09 | Electrodialysis system and application |
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| CN116116224A true CN116116224A (en) | 2023-05-16 |
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