Electrolytic bath and super capacitor integrated device

Abstract

The invention discloses an electrolytic bath and super capacitor integrated device, and belongs to the technical field of membrane separation. Deep desalination, controllable concentration and tritium-deuterium selective separation are completed at low voltage, salt and isotope ions are efficiently adsorbed by an outer-side double-electric-layer carbon electrode, tritium-deuterium is selectively intercepted by an intermediate proton membrane and a diffusion layer, desorption and enrichment are performed by a reverse electric field, the volume can be reduced, the energy consumption is reduced, the 1.23 V bottleneck is broken through, and the method is suitable for industrial production. Specific adsorption groups can be modified and added on a cation membrane and a super capacitor electrode, limit electrolytic voltage is exceeded, electrolytic voltage is used, voltage for electrolysis and capacitance is met, two electrochemical modes are taken into consideration, and positive charging and voltage selection of the electrolytic voltage are beneficial to electrolysis of deuterium and tritium in an electrolytic bath, so that the deuterium and tritium are positively charged and adsorbed, such as 1.7 V, 2.0 V and 2.2 V; and when the voltage is lower than the electrolytic voltage, reverse charging is carried out, and deuterium and tritium and other ions adsorbed on the cation membrane and the carbon electrode are removed by utilizing a reverse electric field of the super capacitor and return to water, so that concentrated solutions such as 1.0 V, 1.1 V and 1.2 V are formed.

Description

Technical Field

[0001] This invention relates to the field of membrane separation technology, and in particular to an integrated device of an electrolyzer and a supercapacitor. Background Technology

[0002] Traditional desalination technologies, such as reverse osmosis and distillation, generally face challenges of excessive energy consumption and high costs associated with processing high-salt concentrates. Meanwhile, in the critical tritium-deuterium separation field of the nuclear industry, the currently relied-upon cryogenic distillation technology also consumes enormous amounts of energy, and its key materials often fail to meet the stringent requirements for long-term radiation resistance. These common energy and material bottlenecks highlight the urgent need for new, efficient, and low-consumption separation technologies.

[0003] Supercapacitors are energy storage devices based on the double-layer principle, storing charge by physically adsorbing electrolyte ions onto the surface of porous carbon electrodes. Their structure includes electrodes with high specific surface area, an electrolyte, a separator, and a current collector. This physical process endows them with outstanding characteristics such as rapid charging and discharging, high power, and ultra-long cycle life.

[0004] Supercapacitors have certain applications in desalination technology and tritium-deuterium separation, namely capacitive deionization technology. This capacitive deionization technology is essentially a targeted application and extension of the supercapacitor principle in the field of water treatment. Supercapacitors physically adsorb charges / ions by forming an electric double layer on the porous electrode surface. CDI technology utilizes this principle to desalinate salt ions by directionally adsorbing them into the electrode pores when a low voltage is applied, similar to charging. Under short-circuit or reverse voltage, the ions are rapidly released to obtain a concentrated solution, similar to discharging.

[0005] Therefore, the structure of a supercapacitor, such as the porosity and conductivity of its electrodes, directly determines the desalination capacity and rate of CDI.

[0006] However, existing CDI technology is limited by the electrode materials and structure of traditional supercapacitors. When the voltage exceeds 1.3V, side reactions such as water electrolysis occur, which disrupt the efficient cycle of "adsorption and desorption". As a result, it cannot achieve deep desalination and high-concentration controllable concentration in a single low-pressure system.

[0007] The current technological bottleneck points precisely to the need for the basic structure of supercapacitors, namely, to develop new electrode or membrane materials that can selectively adsorb and retain specific ions such as tritium and deuterium at lower voltage windows, thereby solving the problems of ion "directional enrichment" and "selective retention" and achieving a dual breakthrough in energy consumption and efficiency.

[0008] Therefore, an integrated electrolytic cell and supercapacitor device is proposed to solve or alleviate the above problems. Summary of the Invention

[0009] The purpose of this invention is to address the shortcomings of existing technologies by proposing an integrated electrolytic cell and supercapacitor device.

[0010] To achieve the above objectives, the present invention adopts the following technical solution: An integrated electrolytic cell and supercapacitor device includes a supercapacitor module and an electrolytic cell module integrated in the supercapacitor module. The electrolytic cell module includes a cation exchange membrane, and the cation exchange membrane is doped with materials or groups that adsorb or trap positively charged ions and charged groups.

[0011] Preferably, the supercapacitor module includes two carbon electrodes configured as positive and negative electrodes, and an anion exchange membrane disposed between the two carbon electrodes.

[0012] Preferably, the electrolytic cell module further includes a diffusion layer filled between a carbon electrode and an anion exchange membrane in the supercapacitor module to form an electrolytic cell, wherein the cation exchange membrane is disposed within the diffusion layer and located between the carbon electrode and the anion exchange membrane.

[0013] Preferably, the cation exchange membrane comprises a proton exchange membrane composed of pure sulfonic acid groups.

[0014] Preferably, the cation exchange membrane comprises a proton exchange membrane based on a proton exchange membrane and containing sulfonic acid groups.

[0015] Preferably, the carbon electrode comprises a supercapacitor activated carbon electrode.

[0016] Preferably, the carbon electrode has a specific surface area greater than or equal to 1000 m² / g, a pore size distribution of 0.5-2 nm to enhance ion adsorption capacity, and an operating voltage less than or equal to 1.2 V.

[0017] This invention provides an intelligent control system for concentrate, used for monitoring and controlling a device integrating an electrolyzer and a supercapacitor, including... The sensor network includes a conductivity sensor installed on the water production pipeline in the integrated electrolyzer and supercapacitor unit and a pH sensor installed in the treatment chamber of the integrated electrolyzer and supercapacitor unit, for real-time acquisition of the conductivity and pH data of the water. The actuator network includes a programmable DC power supply electrically connected to the electrodes of the electrolyzer and supercapacitor integrated unit, and electric valves and pumps installed on the concentrate pipeline and water inlet pipeline in the electrolyzer and supercapacitor integrated unit. A programmable logic controller (PLC) whose signal inputs are connected to a sensor network and whose control outputs are connected to an actuator network. The programmable logic controller receives data from the conductivity sensor. When the conductivity is below a preset threshold, it sends a command to the programmable DC power supply to switch the polarity of the output voltage and control the opening and closing of the electric valve, automatically executing the cycle from ion adsorption to reverse desorption to generate concentrated liquid.

[0018] This invention provides a multi-stage wastewater reduction process, which is implemented based on an integrated electrolyzer and supercapacitor device and a concentrated liquid intelligent control system, and includes the following steps: S1. The wastewater to be treated is fed into the first-stage electrolytic cell and supercapacitor integrated device, and electrochemical treatment is carried out under the condition of applying a first positive voltage, so that the ions in the wastewater are adsorbed on the electrodes of the device and the first product water is obtained. S2. Monitor the conductivity of the first product water in real time. When the conductivity drops to the first preset threshold, apply a first reverse voltage to the integrated electrolytic cell and supercapacitor device of the first stage to desorb the adsorbed ions and form the first concentrate. S3. The first concentrate is passed into the second-stage electrolytic cell and supercapacitor integrated device, and electrochemical treatment is carried out under the condition of applying a second positive voltage, so that the ions in the concentrate are adsorbed and the second product water is obtained. S4. Monitor the conductivity of the second product water in real time. When the conductivity drops to the second preset threshold, apply a second reverse voltage to the integrated electrolytic cell and supercapacitor device of the second stage to desorb the adsorbed ions and form a second concentrate.

[0019] The present invention has the following beneficial effects: This invention addresses the bottlenecks of traditional desalination and isotope separation technologies, such as high energy consumption and difficulty in concentration. Reverse osmosis and distillation are energy-intensive and produce difficult-to-treat concentrated wastewater. Tritium-deuterium separation relies on high-energy-consuming, low-temperature distillation, and existing materials are not radiation-resistant. Traditional capacitive deionization technology is limited by a 1.3-volt voltage, easily triggering side reactions and unable to simultaneously achieve deep desalination and high-concentration. It also lacks materials and devices for efficient directional migration and highly selective retention under low pressure. Furthermore, it constructs a complete system using a super-activated carbon electrode as the outer layer, with an internal cation exchange proton membrane and diffusion layer. The electrolyzer structure enhances ion driving force and transport rate, avoids side reactions during low-pressure operation, and simultaneously achieves ion adsorption and water electrolysis during forward charging. It relies on specific materials to screen and retain tritium and deuterium, and desorbs after reverse charging when adsorption is saturated. Ions are enriched and exported through membrane barrier. It can also be multi-stage series concentration and volume reduction, and overcomes voltage limitations. It couples ion concentration and isotope separation, reduces energy consumption, can specifically capture radionuclides, is automatically controlled and radiation resistant, and provides a highly efficient, low-consumption and highly selective solution for water treatment and isotope separation. Furthermore, since deuterium and tritium have no charge in water, supercapacitors cannot effectively perform adsorption and desorption. Electrolysis causes deuterium and tritium to acquire a positive charge in water, allowing them to pass through the cation exchange membrane towards the negative electrode. At this point, the high-efficiency electric field of the supercapacitor accelerates the movement of deuterium and tritium. Simultaneously, utilizing the charged and mobile characteristics of deuterium and tritium, and leveraging the specific retention and adsorption groups modified on the cation exchange membrane and carbon electrode, electrolysis imparts a positive charge to the previously uncharged deuterium and tritium, enabling them to be retained and adsorbed by the supercapacitor. The porous electrode of the supercapacitor significantly enhances the electric field. The increased intensity enhances the efficiency and volume of the electrolysis process. After the deuterium-tritium-containing wastewater is intercepted and adsorbed, the outflowing water is good water, achieving deuterium-tritium removal treatment, which can be reused. Furthermore, the deuterium-tritium adsorbed and intercepted to a certain extent can be reverse-charged and repelled by the low voltage of the supercapacitor, causing the positively charged deuterium-tritium ions to return from the ion exchange membrane and electrodes to the water, forming a deuterium-tritium concentrate. This concentrate is then flushed out with raw water and recycled into the concentrated wastewater zone. Meanwhile, the electrodes and cation exchange membranes remove deuterium-tritium, achieving regeneration and enabling reuse. Attached Figure Description

[0020] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0021] Figure 1 This is a schematic diagram of the structure of the present invention; Figure 2 This is a structural block diagram of the intelligent control system for concentrate in this invention; Figure 3 This is a flowchart of the multi-stage wastewater reduction process in this invention.

[0022] In the diagram: 1. Carbon electrode; 2. Anion exchange membrane; 3. Cation exchange membrane; 4. Diffusion layer; 5. Sensor network; 6. Programmable logic controller; 7. Actuator network. Detailed Implementation

[0023] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. The components of the embodiments of the present invention described and shown in the accompanying drawings can generally be arranged and designed in various different configurations.

[0024] Therefore, the following detailed description of the embodiments of the invention provided in the accompanying drawings is not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments of the invention. All other embodiments obtained by those skilled in the art based on the embodiments of the invention without inventive effort are within the scope of protection of the invention.

[0025] It should be noted that similar labels and letters in the following figures indicate similar items. Therefore, once an item is defined in one figure, it does not need to be further defined and explained in subsequent figures.

[0026] In the description of this invention, it should be understood that the terms "center," "upper," "lower," "left," "right," "vertical," "horizontal," "inner," and "outer," etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings, or the orientation or positional relationship commonly used when the product of this invention is in use, or the orientation or positional relationship commonly understood by those skilled in the art. They are only used to facilitate the description of this invention and to simplify the description, and are not intended to indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this invention.

[0027] Furthermore, the terms "first," "second," and "third" are used only to distinguish descriptions and should not be interpreted as indicating or implying relative importance.

[0028] In the description of this invention, it should also be noted that, unless otherwise explicitly specified and limited, the terms "set," "install," "connect," and "link" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal connection of two components. Those skilled in the art can understand the specific meaning of the above terms in this invention based on the specific circumstances.

[0029] An integrated device combining an electrolytic cell and a supercapacitor, such as Figure 1 As shown, it includes a supercapacitor module and an electrolytic cell module integrated within the supercapacitor module.

[0030] The supercapacitor module includes two carbon electrodes 1, which are set as positive and negative electrodes, and an anion exchange membrane 2 disposed between the two carbon electrodes 1. The carbon electrode 1 includes a supercapacitor activated carbon electrode. The specific surface area of ​​the carbon electrode 1 is greater than or equal to 1000 m² / g, and its pore size distribution is 0.5-2 nm to enhance the ion adsorption capacity. Its operating voltage is less than or equal to 1.2 V.

[0031] The electrolytic cell module includes a cation exchange membrane 3 and a diffusion layer 4 formed between a carbon electrode 1 and an anion exchange membrane 2 in the supercapacitor module. The cation exchange membrane 3 is doped with materials or groups that adsorb or trap positively charged ions and charged groups. The "positively charged ions and charged groups" mentioned in the materials or groups that adsorb or trap positively charged ions and charged groups in the cation exchange membrane 3 include positive metal ions such as salts, sodium, magnesium, calcium, potassium, and iron, as well as hydrogen isotopes such as deuterium and tritium. These positively charged ions and charged groups will also pass through the proton exchange membrane and be adsorbed on the electrode or directly on the proton exchange membrane. When the anion exchange membrane 2 is charged in the positive electrode direction, it adsorbs negatively charged ions or acid radicals at the same time as the electrode. The cation exchange membrane 3 is disposed in the diffusion layer 4 and located between the carbon electrode 1 and the anion exchange membrane 2. The cation exchange membrane 3 includes a proton exchange membrane composed of pure sulfonic acid groups, or the cation exchange membrane 3 includes a proton exchange membrane based on the proton exchange membrane and containing sulfonic acid groups.

[0032] More specifically, the anion exchange membrane 2 comprises 0.1-10% modified carbon nanotubes, 5-35% PVDF, 1-20% chloromethylstyrene, 1-20% divinylbenzene, 25-85% organic solvent, 5-45% glycidyl methacrylate, 0.01-1% polyvinylpyrrolidone, and 0.01-3% benzoyl peroxide.

[0033] The cation exchange membrane 3 comprises 0.1-10% modified carbon nanotubes, 45-70% organic solvent, 5-30% PVDF, 2-10% divinylbenzene, 10-35% glycidyl methacrylate, 0.1-3% polyvinylpyrrolidone, and 0.1-2% initiator.

[0034] Traditional desalination and isotope separation technologies have long faced bottlenecks such as high energy consumption and difficulty in concentration treatment. Processes such as reverse osmosis and distillation consume a lot of energy and produce concentrated waste liquid that is difficult to dispose of. Meanwhile, the critical tritium-deuterium separation in the nuclear industry relies heavily on the extremely energy-intensive low-temperature distillation process. At the same time, existing material systems are difficult to meet the stringent requirements of long-term radiation resistance.

[0035] While existing capacitive deionization technology offers a new approach to electronically controlled ion adsorption, its operating voltage inevitably triggers side reactions such as water electrolysis once it exceeds 1.3V. This not only disrupts the stable ion adsorption-desorption cycle but also makes it impossible to achieve the goals of deep desalination and controllable high-concentration in a single low-pressure system.

[0036] The problem lies in the lack of a new material and device system that can efficiently drive the directional migration and enrichment of ions and achieve high selectivity for specific isotope ions under low voltage window.

[0037] The integrated electrolytic cell and supercapacitor device proposed in this invention is designed to solve the above problems, achieving simultaneous and efficient desalination, concentration, and selective separation of tritium and deuterium at low voltage.

[0038] With a supercapacitor as the outer frame, the left and right sides are respectively positive and negative electrodes made of current collector-loaded high specific surface area super activated carbon material, which constitutes the basis of the double-layer ion adsorption of the device.

[0039] Inside the device, an ion exchange membrane is introduced between the two electrodes, preferably a cation exchange proton membrane with sulfonic acid groups, and a diffusion layer 4 is set between the membrane and the adjacent super activated carbon electrode, thereby constructing a complete electrolytic cell structure inside the supercapacitor.

[0040] The characteristics and functions of the two modules are preserved and enhanced synergistically. The high specific surface area carbon electrode 1 of the supercapacitor imparts its inherent strong electric field potential energy to the electrolysis process, which greatly improves the power density per unit area of ​​the electrode. It is estimated to be two orders of magnitude higher than that of traditional electrolysis electrodes. This means that the ion driving force and transport rate are significantly improved under the same voltage.

[0041] When water containing salt or tritium-deuterium isotopes flows through the device, the device simultaneously exerts the dual effects of physical adsorption by supercapacitors and electrochemical decomposition by electrolyzers.

[0042] On the one hand, cations in the solution, such as sodium ions, calcium ions, and positively charged tritium and deuterium isotope ions, pass through the cation exchange membrane 3 under the drive of the electric field and are efficiently adsorbed by the super activated carbon electrode on the negatively charged cathode side.

[0043] Meanwhile, anions such as chloride ions and sulfate ions migrate to the opposite anode side and are adsorbed.

[0044] This adsorption process is extremely rapid and efficient due to the huge specific surface area of ​​the carbon electrode 1 and the enhanced electric field, and the adsorption rate of tritium is high in the flowing state.

[0045] On the other hand, under a set voltage, water molecules simultaneously undergo electrolysis on the electrode surface to generate hydrogen and oxygen, with the hydrogen mainly coming from the proton exchange membrane side.

[0046] More importantly, by doping or combining materials with specific recognition functions, such as graphene and boron nitride hybrid structures, in the proton exchange membrane and its adjacent electrode region, it is possible to precisely sieve and retain deuterium and tritium ions with slightly larger kinetic diameters during ion migration, while allowing protons with smaller diameters to pass through freely. This achieves selective enrichment of tritium and deuterium isotopes without significantly hindering hydrogen production from water electrolysis.

[0047] Once adsorption reaches saturation, the workflow automatically transitions to the desorption and concentration stage. At this point, a reverse charging voltage is applied, and using the principle of repulsion between like charges, all ions previously adsorbed on the electrodes and ion exchange membranes are strongly repelled.

[0048] Due to the physical barrier effect of the ion exchange membrane in the device, these rejected anions and cations cannot return to the original electrode chamber. Instead, they are driven away and enriched in the intermediate channels or specific chambers formed by the membrane separation.

[0049] By directionally extracting a solution rich in high concentrations of salt and tritium-deuterium isotopes, a concentrated solution with a significantly reduced volume can be formed. Subsequently, the electrode is regenerated, and the next adsorption-desorption cycle can be started immediately, enabling continuous or batch processing.

[0050] This device successfully breaks through the 1.3V voltage limit of traditional capacitive deionization technology and operates stably at voltages of 1.2 to 2.5V. This avoids the damage to the electrodes and solution caused by side reactions such as oxygen and hydrogen evolution due to high voltage, and makes full use of the promoting effect of this voltage range on electrolysis, thus achieving the parallel and efficient desalination adsorption and electrolysis enhancement.

[0051] By coupling ion electro-controlled enrichment and concentration with isotope selective separation in the same low-pressure process, and using reverse electric field repulsion to replace traditional thermal evaporation or distillation to achieve concentration, energy consumption is significantly reduced.

[0052] Furthermore, the composite membrane solves the problem of directional enrichment and high selective retention of tritium and deuterium ions under low voltage, and can specifically capture tritium and deuterium radionuclides while efficiently removing common salt ions.

[0053] This invention also provides an intelligent control system for concentrate in an integrated electrolyzer and supercapacitor device, such as... Figure 2 As shown, including Sensor network 5 includes a conductivity sensor installed on the water production pipeline in the integrated electrolyzer and supercapacitor unit and a pH sensor installed in the treatment chamber of the integrated electrolyzer and supercapacitor unit, for real-time acquisition of conductivity and pH data of the water body. The actuator network 7 includes a programmable DC power supply electrically connected to the electrodes of the integrated electrolytic cell and supercapacitor unit, and electric valves and pumps installed on the concentrate pipeline and water inlet pipeline in the integrated electrolytic cell and supercapacitor unit. The programmable logic controller 6 has its signal input terminal connected to the sensor network 5 and its control output terminal connected to the actuator network 7. The programmable logic controller 6 receives data from the conductivity sensor. When the conductivity is below a preset threshold, it sends a command to the programmable DC power supply to switch the polarity of the output voltage and control the opening and closing of the electric valve, automatically executing the cycle from ion adsorption to reverse desorption to generate concentrate.

[0054] The structure of this intelligent control system for the concentrate can be divided into a perception layer, a decision-making layer, and an execution layer. The perception layer includes a sensor network 5. Conductivity sensors are installed on the freshwater output pipelines of each electrolyzer and the integrated supercapacitor unit to monitor desalination efficiency in real time and serve as the main criterion for triggering the concentration cycle. At the same time, pH sensors are installed at the outlets of the anode and cathode chambers of the electrolyzer and the integrated supercapacitor unit to monitor acid-base fluctuations that may be caused by the electrolysis process and ensure the stability of the electrodes and membranes. Flow meters and pressure transmitters are deployed on the inlet pipes and concentrate pipes of the electrolyzer and the integrated supercapacitor unit to establish process safety interlocks. For applications involving tritium-deuterium separation, a radioactivity monitor will also be added to the concentrate output pipeline.

[0055] At the decision-making level, the programmable logic controller 6 receives continuous analog or digital signals from all sensors through its input module and processes and judges them through internal preset program logic. For example, when the conductivity value of the freshwater side of the first-stage device is lower than the preset threshold, the programmable logic controller 6 determines that the adsorption of that stage is saturated.

[0056] At the execution layer, the output module of the programmable logic controller 6 sends control commands to each actuator. Its primary control object is the programmable DC power supply. The programmable logic controller 6 issues commands to the power supply through the communication protocol, causing its output voltage to switch from 1.5-2.5V for forward adsorption to 1.2-2.5V for reverse desorption within milliseconds, and maintains it precisely for the set duration. At the same time, the programmable logic controller 6 controls multiple electric valves installed in the concentrate pipeline and inlet / outlet water pipeline of the integrated electrolytic cell and supercapacitor device to open and close in strict sequence. For example, during the reverse charging phase, the concentrate outlet valve is closed first to enrich ions in the chamber. After completion, the valve is opened and the flow rate of the inlet water pump is adjusted to discharge the high-concentration concentrate. In addition, the start, stop and speed of all pumps are also controlled by the programmable logic controller 6 through the frequency converter.

[0057] Other features enable unmanned, automated operation of the concentration process. Through precise conductivity feedback control, concentrate is generated only when needed, greatly improving overall operating efficiency and concentration ratio, and reducing wastewater volume by more than 99%.

[0058] Furthermore, the system integrates real-time monitoring and interlocking protection of multiple parameters such as pH, flow rate, and pressure, which can effectively prevent faults such as electrode damage, scaling, or overpressure, ensuring the long-term stable operation of the device under complex water quality conditions. In particular, it precisely controls the operating voltage within a window that avoids water electrolysis side reactions, ensuring the sustainability of desalination, concentration, and circulation.

[0059] Ultimately, through the flexible configuration of the programmable logic controller 6 program, the system can easily adapt to different influent water qualities and multi-stage series processes, and can be linked with special sensors such as radioactivity monitoring, providing a precise control platform for the selective enrichment and monitoring of specific components such as tritium and deuterium.

[0060] It solves the bottleneck of extremely high energy consumption in traditional thermal concentration (such as distillation and rectification) in traditional concentration technology and early capacitor deionization technology. It replaces the high-energy-consuming phase change process with low-voltage electrically controlled ion migration, and the overall energy consumption can be reduced by more than 90%.

[0061] It also breaks through the technical barrier of existing capacitor deionization technology, which causes harmful electrolytic side reactions due to working voltage exceeding 1.3V, thereby interrupting the adsorption and desorption cycle. Through intelligent control, the device can operate stably and cyclically under safe voltage.

[0062] Finally, it solves the problems of uncontrollable concentration process and inability to work synchronously with deep desalination and selective separation, and realizes the unification of deep purification and controllable concentration in the same low-pressure system.

[0063] However, the sensor network 5 in the intelligent control system for the concentrate is indeed highly susceptible to data acquisition drift, inaccuracy, or even damage. The β and γ rays released by radioactive nuclides such as tritium, cesium, and strontium in the nuclear wastewater directly affect the electronic components inside the sensors, causing ionization and displacement damage. This leads to signal baseline drift, increased noise, and altered response characteristics. For example, the electrodes of the conductivity sensor may experience surface property changes under continuous radiation, rendering their calibration parameters ineffective. Secondly, the corrosive effects of extreme chemical and physical environments are a direct cause. During the desorption phase of the concentration cycle, the ion concentration, pH, and temperature in localized areas within the integrated device's chamber may rise sharply and instantaneously, accompanied by strong oxidizing substances such as hydroxyl radicals generated during electrolysis. This can cause irreversible chemical poisoning and fouling of the glass membrane and reference electrode of the pH sensor. Simultaneously, high-concentration salts may crystallize on the sensor surface, physically isolating it from the measured liquid, resulting in response lag and reading errors. Finally, the distortion of measurement representativeness caused by non-uniform enrichment is a systematic source of error. Due to the combined effects of electric field and fluid dynamics, the enrichment of ions in the chamber is not completely uniform. If the sensor probe happens to be installed in a hot enrichment area or flow dead zone, the local data it collects will not be able to represent the overall average value of the chamber or pipeline, thus misleading the control system to make incorrect timing judgments.

[0064] To address the aforementioned issues, the surface of each sensor in the sensor network 5 of the concentrate intelligent control system is coated with an inert coating material such as diamond film or special ceramics.

[0065] Furthermore, the programmable logic controller 6 in the concentrate intelligent control system needs to perform the following steps: Signal preprocessing and sensor health diagnosis steps: Adaptive signal decomposition is performed on the raw output signals of multiple sensors to separate noise components, drift components, and effective signal components. Based on the decomposition results, the noise level index and drift rate index of each sensor are calculated, and combined with the consistency index of readings from similar sensor arrays, a dynamic health score of the sensor is comprehensively calculated. The specific method for comprehensively calculating the dynamic health score is as follows: weights are assigned to the noise level index, drift rate index, and consistency index, and then a weighted sum is performed. The negative exponential function value of the sum is used as the dynamic health score. This score is used to quantify the instantaneous reliability of the sensor and can help determine the fault mode based on the dominance of each index. For example, noise dominance may indicate radiation interference, while persistent drift dominance may indicate chemical corrosion. The weights of each index are obtained by training the sensor on accelerated aging test data under simulated radiation and corrosion environments. The noise level index is obtained by calculating the ratio of noise energy to total signal power, the drift rate index is obtained by differentiating and filtering the drift trend, and the consistency index is obtained by calculating and averaging the standardized difference between the sensor reading and the median reading of a similar sensor array. The confidence-based multimodal spatiotemporal data fusion steps are as follows: Based on the spatial representative static weight of each sensor determined in advance through fluid dynamics simulation, and combined with the dynamic health score obtained in step S1, the fusion weight of each sensor at the current moment is calculated; using the fusion weight, data from sensors of different locations and types are weighted and fused to obtain a fusion estimate of the system state and its uncertainty measure. The specific calculation method of the fusion weight is as follows: multiply the spatial representative static weight by the Kth power of the dynamic health score to obtain the initial weight of the sensor, and then normalize the initial weights of all sensors to obtain the final fusion weight; where K is an amplification factor greater than 1; for heterogeneous sensors monitoring different physical quantities, their readings are first mapped to a unified system state quantity through their respective known functional relationships, and then weighted fusion is performed using the fusion weight. At the same time, based on the uncertainty of each sensor and the fusion weight, the uncertainty range of the fusion value is estimated. More specifically, the fusion weights include a static spatial prior weight, which is obtained through computational fluid dynamics and electric field coupling simulation of the processing chamber in the early stage, and represents the representativeness of the data measured by each sensor installation position to the global average state of the chamber; the other part is a dynamic health weight, which is generated by power-law amplification and normalization of the dynamic health scores of each sensor obtained in the first step, and is used to enhance the influence of high health sensors. The synchronous verification and residual analysis steps based on the mechanism model are as follows: A soft sensor model is established based on the mass conservation and electrochemical principles of the electro-adsorption process. High-reliability process variables are used as inputs to estimate the system state in real time, serving as the verification benchmark value. The normalized residual between the fused estimate and the verification benchmark value is calculated, and statistical process control analysis is performed on the normalized residual sequence to determine the overall reliability of the physical sensor network. The soft sensor model is implemented using a state observer algorithm, and the high-reliability process variables include the total operating current of the processing device and the fluid flow rate. The statistical process control analysis employs sequential probability ratio testing or cumulative sum control chart methods. Adaptive fault-tolerant decision-making and maintenance triggering steps: Based on the judgment results of the synchronous verification and residual analysis steps based on the mechanism model, if the statistical test accepts the null hypothesis, the system is in normal monitoring mode, and the fused estimated value or the verification benchmark value is selected as the final system state value for control decision-making; if the statistical test rejects the null hypothesis and accepts the alternative hypothesis, the system immediately enters fault-tolerant mode. At this time, the fused value of the physical sensor network is discarded, the physical sensor network is determined to be unreliable, potential faulty sensors are located, and the corresponding automatic cleaning and calibration maintenance program is triggered. Specifically, the method for locating potential faulty sensors is as follows: after determining that the physical sensor network is unreliable, the deviation between the readings of each sensor and the verification benchmark value is calculated, and a comprehensive judgment is made in combination with its dynamic health score; before the final system state value is used for control decision-making, it needs to be processed by exponential smoothing filtering to suppress fluctuations, and the triggering of control actions needs to meet the hysteresis comparison and continuous timing confirmation logic based on the filtered state value. Predictive maintenance steps: In normal mode, if the health score of a certain sensor shows a trend of deterioration, a predictive maintenance plan is generated; in fault-tolerant mode, a pre-set high-intensity automatic maintenance program is immediately triggered for the subset of faulty sensors, including calibration. Finally, to prevent control command jitter, the selected final system state value is smoothed and filtered, and logic with hysteresis characteristics and time delay confirmation is used to trigger the actual control action to ensure the robustness of system operation.

[0066] This invention provides a multi-stage wastewater reduction process based on an integrated electrolyzer and supercapacitor device, such as... Figure 3 As shown, it includes the following steps: S1. The wastewater to be treated is fed into the first-stage electrolytic cell and supercapacitor integrated device, and electrochemical treatment is carried out under the condition of applying a first positive voltage, so that the ions in the wastewater are adsorbed on the electrodes of the device and the first product water is obtained. More specifically, the raw water to be treated is first pumped from the raw water storage tank to the pretreatment unit by a feed pump to remove suspended solids and other particulate impurities that may damage subsequent equipment. The pretreated water then enters the first-stage electrolytic cell and supercapacitor integrated unit, which consists of multiple electrolytic cells and supercapacitor integrated units connected in parallel to ensure the processing throughput. The water is pumped into the anode and cathode chambers of each module. At this time, a programmable DC power supply applies a positive voltage of 1.5V to 2.5V to the module, and the device simultaneously starts the capacitive adsorption and electrolysis process. Under the action of a strong electric field, the anions and cations migrate to the two electrodes and are adsorbed by the super activated carbon electrodes with a high specific surface area. At the same time, the water undergoes electrolysis, and tritium and deuterium ions are selectively retained at the specific composite membrane. The treated fresh water flows out, and its conductivity is continuously monitored by an online conductivity sensor installed on the outlet manifold. When the conductivity value drops to a preset threshold, the programmable logic controller 6 determines that adsorption is saturated. Then perform the following actions: 1) Close the electric valve on the output pipeline of this stage of concentrate; 2) Keep the inlet and freshwater outlet valves open; 3) Switch the DC power supply to reverse charging mode. Under the action of the reverse electric field repulsion force, the adsorbed ions are desorbed and enriched in the middle chamber of the module.

[0067] After reverse charging is complete, the control unit opens the concentrate valve and briefly increases the inlet water flow for flushing, discharging the high-concentration concentrate into the primary concentrate storage tank, while the deeply desalinated freshwater enters the freshwater storage tank. At this point, the raw water volume has been concentrated approximately 10 times. S2. Monitor the conductivity of the first product water in real time. When the conductivity drops to the first preset threshold, apply a first reverse voltage to the integrated electrolytic cell and supercapacitor device of the first stage to desorb the adsorbed ions and form the first concentrate. More specifically, the high-salt wastewater in the primary concentrate storage tank is pumped into the second-stage electrolyzer and supercapacitor integrated unit by a secondary feed pump. The unit has a similar structure to the primary unit, but it has been optimized for the extremely high ion concentration of the influent. For example, it uses a smaller electrode spacing to generate a stronger electric field and operates at a positive voltage of 1.5-2.5V to perform ion adsorption and electrolysis.

[0068] This stage of treatment has extremely high influent concentration and faster adsorption saturation. Its outlet is equipped with a more precise secondary online conductivity sensor with a lower threshold setting. When the threshold is reached, the programmable logic controller 6 triggers a reverse charging procedure similar to the first stage but with potentially optimized parameters, controlling the opening and closing of the electric valve at the concentrate outlet. The ultra-high concentration solution formed after reverse charging is discharged into the secondary concentrate storage tank through an electric valve. Its volume can be further reduced to about 1% relative to the original water. If the purity of the effluent after secondary treatment is qualified, it can be returned to the primary raw water tank or collected separately. S3. The first concentrate is passed into the second-stage electrolytic cell and supercapacitor integrated device, and electrochemical treatment is carried out under the condition of applying a second positive voltage, so that the ions in the concentrate are adsorbed and the second product water is obtained. More specifically, the concentrate is processed via different pathways based on its properties. The ultra-high salinity wastewater in the secondary concentrate storage tank of high-salinity wastewater in Path A is pumped into the evaporator crystallizer. Since the amount of water to be evaporated is only 1% of the original water, this step has extremely low energy consumption. The final products are solid salt residue and condensate, and the condensate can be reused at the front end of the system.

[0069] After the first two stages of treatment, the tritium and deuterium-containing radioactive wastewater in Path B is highly enriched in the concentrate. This radioactive concentrate is then safely transferred to the radioactive waste solidification system. Because the volume has been reduced by 99%, the solidification volume and final disposal cost are greatly reduced. S4. Monitor the conductivity of the second product water in real time. When the conductivity drops to the second preset threshold, apply a second reverse voltage to the integrated electrolytic cell and supercapacitor device of the second stage to desorb the adsorbed ions and form a second concentrate. More specifically, online pH sensors are installed in the effluent or key chambers of each treatment unit to prevent drastic pH fluctuations caused by localized electrolysis. When the pH value exceeds the safe range, the programmable logic controller 6 can adjust the influent flow rate or trigger a cleaning program.

[0070] Flow meters and pressure transmitters are installed on the main pipelines, and their signals are interlocked with pumps and valves to prevent dry operation, overpressure, or insufficient flow. After long-term operation, a preset chemical cleaning program is executed to restore electrode performance by injecting cleaning agent and applying specific electrical signals.

[0071] Through the above steps, the wastewater to be treated first enters the first-stage device, where electrochemical adsorption and preliminary separation are carried out under low pressure. The produced freshwater is monitored in real time. When the conductivity drops to a set threshold, the system automatically triggers a reverse electric field to desorb the adsorbed ions and form a first-stage concentrate. This concentrate is then pumped into the second-stage device, where the adsorption and desorption cycle is repeated under an optimized and stronger electric field, producing a second-stage concentrate with extremely high concentration and compliant freshwater.

[0072] The entire process is automatically coordinated by the concentrate intelligent control system based on sensor data, including the operation mode of each stage of the device, valve switching, and power polarity reversal.

[0073] By replacing the phase change process with electronically controlled ion migration, the electrolytic side reactions caused by high pressure are avoided. It has a high degree of automation and can achieve deep desalination and ultra-high concentration simultaneously. It solves the problems of excessive energy consumption of traditional reverse osmosis and distillation methods, the inability of capacitor deionization technology to achieve both deep desalination and high concentration due to voltage limitations, and the reliance on high-energy-consuming distillation for tritium-deuterium separation.

[0074] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. An integrated device for electrolytic cell and supercapacitor, characterized in that, It includes a supercapacitor module and an electrolytic cell module integrated in the supercapacitor module. The electrolytic cell module includes a cation exchange membrane (3), and the cation exchange membrane (3) is doped with materials or groups that adsorb or intercept positively charged ions and charged groups.

2. The integrated electrolytic cell and supercapacitor device according to claim 1, characterized in that, The supercapacitor module includes two carbon electrodes (1) configured as positive and negative electrodes, and an anion exchange membrane (2) disposed between the two carbon electrodes (1).

3. The integrated electrolytic cell and supercapacitor device according to claim 1, characterized in that, The electrolytic cell module also includes a diffusion layer (4) filled between a carbon electrode (1) and an anion exchange membrane (2) in the supercapacitor module to form an electrolytic cell. The cation exchange membrane (3) is disposed in the diffusion layer (4) and located between the carbon electrode (1) and the anion exchange membrane (2).

4. The integrated electrolytic cell and supercapacitor device according to claim 1, characterized in that, The cation exchange membrane (3) includes a proton membrane composed of pure sulfonic acid groups.

5. The integrated electrolytic cell and supercapacitor device according to claim 1, characterized in that, The cation exchange membrane (3) includes a proton exchange membrane based on a proton exchange membrane and containing sulfonic acid groups.

6. The integrated electrolytic cell and supercapacitor device according to claim 2, characterized in that, The carbon electrode (1) includes a supercapacitor activated carbon electrode.

7. An integrated electrolytic cell and supercapacitor device according to claim 2 or 6, characterized in that, The carbon electrode (1) has a specific surface area greater than or equal to 1000 m² / g, a pore size distribution of 0.5-2 nm to enhance ion adsorption capacity, and an operating voltage less than or equal to 1.2 V.

8. A concentrated liquid intelligent control system for monitoring and controlling based on the integrated electrolyzer and supercapacitor device as described in any one of claims 1-7, comprising: The sensor network (5) includes a conductivity sensor installed on the water production pipeline in the integrated electrolyzer and supercapacitor device and a pH sensor installed in the treatment chamber in the integrated electrolyzer and supercapacitor device, for real-time acquisition of the conductivity value and acidity / alkalinity data of the water body. The actuator network (7) includes a programmable DC power supply electrically connected to the electrodes of the electrolytic cell and supercapacitor integrated unit, and electric valves and pumps installed on the concentrate pipeline and water inlet pipeline in the electrolytic cell and supercapacitor integrated unit. A programmable logic controller (6) has its signal input terminal connected to a sensor network (5) and its control output terminal connected to an actuator network (7); The programmable logic controller (6) receives data from the conductivity sensor. When the conductivity is below a preset threshold, it sends a command to the programmable DC power supply to switch the polarity of the output voltage and control the opening and closing of the electric valve, automatically executing the cycle from ion adsorption to reverse desorption to generate concentrated liquid.

9. A multi-stage wastewater reduction process, executed based on the integrated electrolytic cell and supercapacitor device as described in any one of claims 1-7 and the intelligent control system for concentrate as described in claim 8, comprising the following steps: S1. The wastewater to be treated is fed into the first-stage electrolytic cell and supercapacitor integrated device, and electrochemical treatment is carried out under the condition of applying a first positive voltage, so that the ions in the wastewater are adsorbed on the electrodes of the device and the first product water is obtained. S2. Monitor the conductivity of the first product water in real time. When the conductivity drops to the first preset threshold, apply a first reverse voltage to the integrated electrolytic cell and supercapacitor device of the first stage to desorb the adsorbed ions and form the first concentrate. S3. The first concentrate is passed into the second-stage electrolytic cell and supercapacitor integrated device, and electrochemical treatment is carried out under the condition of applying a second positive voltage, so that the ions in the concentrate are adsorbed and the second product water is obtained. S4. Monitor the conductivity of the second product water in real time. When the conductivity drops to the second preset threshold, apply a second reverse voltage to the integrated electrolytic cell and supercapacitor device of the second stage to desorb the adsorbed ions and form a second concentrate.

Images