System and method for on-line monitoring of ceramic desalination effect based on ion selective electrode

Abstract

The application relates to the technical field of cultural relic protection, in particular to a system and a method for online monitoring of ceramic desalination effect based on ion selective electrodes, which comprises a monitoring pool, an ion selective electrode array, a conductivity detection module, a pH value detection module, a data acquisition and control module and a central processing unit; the data acquisition and control module is used for receiving and processing detection signals output by the ion selective electrode array, the conductivity detection module and the pH value detection module, and generating real-time monitoring data; the central processing unit is in communication connection with the data acquisition and control module, and is used for comprehensively judging a desalination process and an end point according to the real-time monitoring data. The application realizes real-time online monitoring of a ceramic desalination process, realizes multi-parameter collaborative precise control, has high system anti-interference capability, high automation degree, and the triggering and execution of water replacement verification and continuous desalination can be automatically completed by the system, manual intervention is reduced, and the consistency and efficiency of desalination treatment are improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of cultural relic protection, and in particular to a system and method for online monitoring of ceramic desalination effect based on ion selective electrodes. BACKGROUND

[0002] Before being preserved and repaired for a long time, marine ceramic cultural relics must be subjected to systematic desalination treatment to reduce the irreversible and serious damage to the cultural relics caused by crystallization and redissolution of salt. How to accurately and quickly evaluate the desalination effect of ceramic membranes is crucial for judging the desalination process and desalination effect.

[0003] The existing desalination effect evaluation mainly relies on offline sampling detection method and single conductivity monitoring method:

[0004] One is the offline sampling detection method. The operator regularly collects water samples from the desalination tank and sends them to the laboratory for analysis by ion chromatograph or conductivity meter. This method has obvious defects: long sampling period, detection lag, and cannot reflect the real-time dynamic changes of the desalination process.

[0005] The other is the single conductivity monitoring method. Although some desalination devices are equipped with conductivity detectors, conductivity alone cannot distinguish different ion concentrations and it is difficult to determine the desalination endpoint. In an open operating environment, single conductivity data is difficult to distinguish between environmental disturbances (such as temperature fluctuations, water or container impurities, etc.) and real salt dissolution of cultural relics, and the anti-interference ability is weak. In addition, conductivity is significantly affected by temperature, pH value and other factors, and single parameter monitoring has insufficient reliability, which may cause misjudgment of the desalination endpoint, resulting in unnecessary extension of the treatment time and risk of long-term immersion of the cultural relics.

[0006] Therefore, there is an urgent need in the art for a method and system capable of real-time, online, multi-parameter collaborative monitoring of ceramic desalination effect to achieve precise control of the desalination process and scientific determination of the endpoint. SUMMARY

[0007] To solve the above technical problems, the embodiments of the present application propose a system and method for online monitoring of ceramic desalination effect based on ion selective electrodes to solve the technical problems of the prior art that the desalination process cannot be precisely controlled and the endpoint determination accuracy is poor.

[0008] To solve the above technical problems, in one aspect, some embodiments of the present application disclose a system for online monitoring of ceramic desalination effect based on ion selective electrodes, comprising:

[0009] A monitoring tank in communication with the soaking tank for ceramic desalination and being closed;

[0010] An ion selective electrode array arranged in the monitoring tank for real-time detection of the concentration change of ions in the monitoring tank;

[0011] a conductivity detection module comprising a conductivity electrode arranged in the monitoring cell for monitoring conductivity value of the desalination medium in the monitoring cell in real time;

[0012] a pH value detection module comprising a pH composite electrode arranged in the monitoring cell for monitoring pH value of the desalination medium in the monitoring cell in real time;

[0013] a data acquisition and control module, which is in communication connection with the ion selective electrode array, the conductivity detection module and the pH value detection module, for receiving and processing detection signals output by the ion selective electrode array, the conductivity detection module and the pH value detection module to generate real-time monitoring data;

[0014] a central processing unit, which is in communication connection with the data acquisition and control module, for comprehensively determining desalination process and endpoint according to the real-time monitoring data.

[0015] Preferably, a temperature sensor is further included, which is arranged in the monitoring cell for monitoring temperature of the desalination medium in the monitoring cell in real time; the data acquisition and control module compensates measurement value of the conductivity detection module based on monitoring result of the temperature sensor.

[0016] Preferably, a display and alarm module is further included, which is connected to the central processing unit for displaying the real-time monitoring data and change curve in real time and issuing a prompt when preset desalination endpoint condition is reached.

[0017] Preferably, a defoaming module is further included, which comprises a sample inlet pipeline, a sample return pipeline and a peristaltic pump connected to the monitoring cell, wherein the monitoring cell is connected to a return pipe of a circulating pipeline of the desalination system through the sample inlet pipeline, and a liquid outlet of the monitoring cell is connected to the soaking tank through the sample return pipeline and the peristaltic pump.

[0018] Preferably, the sample inlet pipeline has a length and an inner diameter for eliminating nanobubbles in fluid flowing therethrough.

[0019] Preferably, the outer wall of the sample inlet pipeline is further wrapped with a cooling device for cooling fluid in the sample inlet pipeline to 20-25℃.

[0020] Preferably, the length of the sample inlet pipeline is 2.3-2.7m, the inner diameter is 3.5-4.5mm, the flow rate of fluid in the sample inlet pipeline is 1.0-1.5m / s, and the residence time of fluid in the pipeline is 1.7-2.5min.

[0021] Preferably, the cooling rate of the cooling device is 0.5-2℃ / min.

[0022] Preferably, the ion-selective electrode array comprises Na + K + Ca 2+ Cl - NO3 - An array of ion-selective electrodes.

[0023] On the other hand, embodiments of the present invention also disclose a method for online monitoring of ceramic desalination effect based on an ion-selective electrode, which includes:

[0024] (1) Start the desalination cycle system and calibrate each ion-selective electrode in the ion-selective electrode array;

[0025] (2) The ion-selective electrode array detects the ion concentration in the desalination medium in real time and outputs the corresponding potential signal, the conductivity detection module detects the conductivity of the desalination medium in real time, and the pH detection module detects the pH value of the desalination medium in real time.

[0026] (3) The data acquisition and control module acquires conductivity, pH value and potential signal output by the ion selection array at a set sampling frequency, thereby obtaining the dissolution rate and concentration change trend of each target ion;

[0027] (4) The central processing unit comprehensively evaluates the desalination process based on the dissolution rate and concentration change trend of each target ion, conductivity and pH value;

[0028] Preferably, the formula for calculating the dissolution rate of the target ion is:

[0029] Among them, R i C represents the dissolution rate of target ion i. i (t) represents the ion concentration at time t, C i (t-Δt) represents the ion concentration before time Δt.

[0030] Preferably, step (2) further includes: performing temperature compensation correction on the conductivity detection result based on the temperature of the desalination medium detected by the temperature sensor.

[0031] Preferably, in step (4), the central processing unit comprehensively evaluates the desalination process based on the dissolution rate and concentration change trend of each target ion, conductivity, and pH value, including:

[0032] The central processing unit calculates the dissolution rate of each target ion based on the concentration change trend of each target ion. When the dissolution rate of all target ions is lower than the preset threshold within a continuously set time period, it is determined that the ion dissolution tends to be gradual.

[0033] The central processing unit analyzes the trend of the conductivity of the desalination medium based on the collected conductivity values. When the standard deviation of the conductivity is lower than the preset threshold within a continuously set time period, the conductivity of the system is determined to be stable.

[0034] The central processing unit determines that the system has reached equilibrium when the pH value is stable within the range of 6.5 to 7.5 and the fluctuation range is lower than a preset threshold within a continuous predetermined time, based on the collected pH value data.

[0035] Preferably, the formula for calculating the standard deviation of the conductivity is:

[0036] Where, σ K K represents the standard deviation of conductivity, N is the number of data points within a continuously set time period, and K is the standard deviation of conductivity. 25，j To set the temperature-compensated conductivity value for the j-th data point within a continuously defined time period, The arithmetic mean of conductivity over a continuously defined time period;

[0037] Preferably, according to the calculation formula:

[0038] Calculate the pH drift rate, where D pH The pH drift rate is given by pH(t), where pH(t) is the pH value measured at the current time t, and pH(t-12h) is the pH value measured 12 hours ago. The pH drift rate is used to represent the pH fluctuation range.

[0039] Preferably, in step (4), the central processing unit further includes comprehensively evaluating the desalination process based on the dissolution rate and concentration change trend of each target ion, conductivity, and pH value:

[0040] The central processing unit determines that desalination has reached its scientific endpoint only when all three conditions are met simultaneously: ion dissolution tends to be gradual, conductivity is stable, and pH reaches equilibrium.

[0041] Preferably, the method further includes: when all three conditions are met simultaneously—the ion dissolution rate tends to be gradual, the conductivity is stable, and the pH reaches equilibrium—the method re-equilibrates for a predetermined time after replacing the desalination medium, and compares the dissolution rate, standard deviation of conductivity, and pH value of all target ions detected after re-equilibration with the data before replacing the desalination medium, and confirms whether desalination is completed based on the comparison results.

[0042] Preferably, if the dissolution rate, standard deviation of conductivity, and pH value of all target ions detected after rebalancing are basically the same as the data before changing the desalination medium, then desalination is confirmed to be complete. If any one of the dissolution rate, standard deviation of conductivity, and pH value of all target ions detected after rebalancing is higher than the data before changing the desalination medium by a predetermined value, then desalination is initiated to continue.

[0043] By adopting the above technical solution, the present invention has at least the following beneficial effects:

[0044] This invention provides a system and method for online monitoring of ceramic desalination effect based on ion-selective electrodes. It realizes real-time online monitoring of the ceramic desalination process, achieves precise control of multiple parameters, has strong anti-interference ability, high degree of automation, and can automatically complete water exchange verification and triggering and execution of continued desalination, reducing manual intervention and improving the consistency and efficiency of desalination treatment. Attached Figure Description

[0045] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0046] Figure 1 This is a schematic diagram of the structure of a system for online monitoring of ceramic desalination effect based on an ion-selective electrode, as disclosed in some embodiments of the present invention.

[0047] Figure 2 This is a schematic diagram of a system for online monitoring of ceramic desalination effect based on an ion-selective electrode, as disclosed in some embodiments of the present invention. Detailed Implementation

[0048] The embodiments of this disclosure will be further described in detail below with reference to the accompanying drawings and examples. The detailed description of the embodiments and the accompanying drawings are used to illustrate the principles of this disclosure by way of example, but should not be used to limit the scope of this disclosure. This disclosure can be implemented in many different forms and is not limited to the specific embodiments disclosed herein, but includes all technical solutions falling within the scope of the claims.

[0049] These embodiments are provided to make the disclosure thorough and complete, and to fully express the scope of the disclosure to those skilled in the art. It should be noted that, unless otherwise specifically stated, the relative arrangement of components and steps, material composition, numerical expressions, and values ​​set forth in these embodiments should be interpreted as exemplary only and not as limiting.

[0050] Furthermore, words such as "include" or "contain" mean that the element preceding the word covers the element listed after the word, and do not exclude the possibility that it may also cover other elements.

[0051] It should also be noted that, in the description of this disclosure, unless otherwise expressly specified and limited, the specific meaning of each term in this disclosure can be understood by those skilled in the art as appropriate. All terms used in this disclosure have the same meaning as understood by those skilled in the art to which this disclosure pertains, unless otherwise specifically defined. It should also be understood that terms defined in general dictionaries should be interpreted as having a meaning consistent with their meaning in the context of the relevant art, and should not be interpreted with an idealized or highly formalized meaning, unless expressly defined herein.

[0052] Techniques, methods, and equipment known to those skilled in the art may not be discussed in detail, but where appropriate, they should be considered part of the specification.

[0053] like Figure 1 , Figure 2 As shown, some embodiments of the present invention disclose a system for online monitoring of ceramic desalination effects based on ion-selective electrodes. Addressing the problems of offline detection lag, insufficient information from single conductivity monitoring, and lack of scientific basis for desalination endpoint determination in existing technologies, the system aims to achieve real-time synchronous monitoring of key ion concentrations, conductivity, pH value, and temperature during the desalination process, providing multi-dimensional data support for desalination process optimization and endpoint determination. The system may include a monitoring cell 1, an ion-selective electrode array 2, a conductivity detection module, a pH detection module 3, a data acquisition and control module 6, and a central processing unit 7.

[0054] Monitoring pool 1 is connected to the soaking tank used for ceramic desalination and is closed. Monitoring pool 1 can generally be set downstream of the soaking tank, for example, at the end of the circulation pipeline of the desalination pool. It is a closed flow system. The contact area between the desalination medium and the air in the circulation pipeline is extremely small, which greatly reduces the dissolution of CO2. Each sensor electrode is installed in the monitoring sampling pool. When conditions are limited, each sensor electrode can also be directly installed in the cultural relic desalination pool.

[0055] An ion-selective electrode array 2 is disposed within the monitoring cell 1 to detect changes in the concentration of ions in the monitoring cell 1 in real time, including but not limited to Na+. + K + Ca 2+ Cl ━ NO3 ━ Electron-selective electrodes. For example, ion-selective electrode array 2 includes electrodes made of Na... + K + Ca 2+ Cl- NO3 ━ An array of ion-selective electrodes is included. The conductivity detection module includes conductivity electrodes disposed within the monitoring cell 1 for real-time monitoring of the conductivity value of the desalination medium in the monitoring cell 1. The pH detection module 3 includes a pH composite electrode disposed within the monitoring cell 1 for real-time monitoring of the pH value of the desalination medium in the monitoring cell 1.

[0056] The data acquisition and control module 6 is communicatively connected to the ion-selective electrode array 2, the conductivity detection module, and the pH detection module 3, and is used to receive and process the detection signals output by the ion-selective electrode array 2, the conductivity detection module, and the pH detection module 3 to generate real-time monitoring data.

[0057] The central processing unit 7 is communicatively connected to the data acquisition and control module 6, and is used to comprehensively determine the desalination process and endpoint based on the real-time monitoring data. It can use a built-in desalination effect evaluation algorithm to comprehensively determine the desalination process and endpoint based on the ion concentration change rate (ion dissolution rate), conductivity stability, and pH drift.

[0058] To avoid the influence of temperature on conductivity detection, the system in the above embodiment may further include a temperature sensor 4, which is installed in the monitoring pool 1 to monitor the temperature of the desalination medium in the monitoring pool 1 in real time. The data acquisition and control module 6 compensates for the measured value of the conductivity detection module based on the monitoring result of the temperature sensor 4. In addition, in some embodiments, the above system also includes a display and alarm module 5, which is connected to the central processing unit 7 to view the real-time monitoring data and change curves in real time and to issue a prompt when the preset desalination endpoint condition is reached.

[0059] The system for online monitoring of ceramic desalination effect based on ion-selective electrodes disclosed in some embodiments of the present invention may include a defoaming module to achieve real-time synchronous monitoring and ensure the accuracy of the detection results. This module defoams the desalination solution to be tested before detection, which can be achieved through an inlet pipe, a return pipe, and a peristaltic pump connected to the monitoring cell. The monitoring cell is connected to the return pipe of the circulation pipe via the inlet pipe, and the outlet of the monitoring cell is connected to the soaking tank via the return pipe and the peristaltic pump. The inlet pipe should have a length and inner diameter sufficient to dissolve nanobubbles in the fluid passing through it. The monitoring cell is connected to the soaking tank (desalination tank) via the inlet pipe, and a cooling device may also be provided on the inlet pipe. Downstream of the monitoring cell is a monitoring probe such as an ion-selective electrode. The rear end of the ion-selective electrode is connected to the soaking tank via the return pipe and the peristaltic pump. The peristaltic pump is placed at the beginning of the return pipe and is used to extract the desalination solution sample from the soaking tank and transport it to the soaking tank.

[0060] In some preferred embodiments, to ensure maximum efficiency in dissipating air bubbles in the sample fluid, the length of the injection tubing can be selected to be approximately 2.5 m, and the inner diameter approximately 4 mm. The flow rate of the desalted sample in the injection tubing is 1.0–1.5 m / s, the residence time of the sample in the tubing is 1.7–2.5 min, and the cooling rate of the cooling device is 0.5–2 °C / min to lower the temperature of the desalted sample to room temperature (20–25 °C). The flow rate of the peristaltic pump is 100 mL / min.

[0061] In operation, the desalted solution to be tested flows into the monitoring cell through a slender inlet tube via a circulation pump. During the flow, the nanobubbles gradually break down due to the shear force of the inner wall of the tube. Simultaneously, a cooling device installed on the inlet tube cools the desalted solution sample (a cooling medium can be wrapped around the outer wall of the inlet tube for heat exchange; for example, a double-layered tube can be used, with the inner layer transporting the desalted solution to be tested and the outer layer carrying the cooling medium). The decrease in temperature reduces the interfacial stability of the nanobubbles and increases the gas solubility, further promoting bubble collapse, until the nanobubbles are almost completely dissolved. The dissolved desalted solution sample flows through an ion-selective electrode and other monitoring probes for ion concentration, pH value, and conductivity detection. After the detection is completed, the sample is returned to the soaking tank via a peristaltic pump through the reflux tube. That is, the monitoring cell is connected to the soaking tank through the return tube, which is equipped with a peristaltic pump. The peristaltic pump can be set at the beginning of the return tube to extract the desalted solution sample from the soaking tank and transport it to the soaking tank.

[0062] In some implementations, the sample inlet tubing is 5–20 m long and has an inner diameter of 2–6 mm. The desalting solution sample flows slowly within the slender tubing, and the nanobubbles collapse naturally under the flow shear force, requiring no additional energy input. The peristaltic pump has a flow rate of 100 mL / min.

[0063] In the above embodiments, the cooling device lowers the temperature of the desalination sample to room temperature (20-25°C), ensuring that the sample is under suitable and stable temperature conditions when passing through the ion-selective electrode for detection, thereby guaranteeing the accuracy of ion concentration, conductivity, and pH detection results. Simultaneously, the temperature reduction also helps decrease the interfacial stability of the nanobubbles, playing an auxiliary role in defoaming. This, combined with the length and inner diameter of the sample inlet tube, completes bubble elimination. If elimination is incomplete, residual nanobubbles may adhere to the surface of the sensitive membrane of the ion-selective electrode, hindering effective contact between the sensitive membrane and the test solution, leading to slow electrode response, reading drift, and low detection values, severely affecting the accuracy and repeatability of the detection results. Furthermore, bubble adhesion accelerates electrode aging and shortens its lifespan. This invention, through the above elimination process, ensures that there are no residual bubbles in the desalination sample entering the detection cell, fundamentally avoiding bubble contamination and interference with the electrode's sensitive membrane. Some embodiments of this invention disclose a system for online monitoring of ceramic desalination effects based on ion-selective electrodes, such as... Figure 2 As shown, the desalination medium is first pumped into the auxiliary flow and cleaning tank via an auxiliary flow peristaltic pump. In the cleaning tank, nanobubbles and other air bubbles that interfere with electrode measurements are eliminated through settling and degassing. The pre-treated desalination medium then enters the distribution valve at a constant flow rate. After being switched and selected by the distribution valve, it enters the monitoring module, which is equipped with an ion-selective electrode array, conductivity electrode, pH electrode, and temperature sensor. The detected medium is returned to the desalination tank, forming a closed-loop circulation. The distribution valve is controlled by the central processing unit, enabling automatic switching between detection and cleaning / calibration modes. This flow path structure isolates the sensor from the artifact desalination tank, ensuring the real-time performance and reliability of the monitoring data while preventing sensor disturbance to the artifact. Furthermore, the closed design effectively reduces environmental interference with pH and conductivity measurements.

[0064] Some embodiments of the present invention also disclose a method for online monitoring of ceramic desalination effect based on an ion-selective electrode, which can be implemented by the above-described system for online monitoring of ceramic desalination effect based on an ion-selective electrode. The method includes:

[0065] (1) Start the desalination cycle system and calibrate each ion-selective electrode in the ion-selective electrode array 2;

[0066] (2) The ion selective electrode array 2 detects the ion concentration in the desalination medium in real time and outputs the corresponding potential signal. The conductivity detection module detects the conductivity of the desalination medium in real time, and the pH detection module 3 detects the pH value of the desalination medium in real time. In this step, the conductivity detection result can be corrected by temperature compensation based on the temperature of the desalination medium detected by the temperature sensor 4.

[0067] (3) The data acquisition and control module 6 acquires conductivity, pH value and potential signal output by the ion selection array at a set sampling frequency, thereby obtaining the dissolution rate and concentration change trend of each target ion;

[0068] (4) The central processing unit 7 comprehensively evaluates the desalination process based on the dissolution rate and concentration change trend of each target ion, conductivity and pH value. Preferably, the formula for calculating the dissolution rate of the target ion is:

[0069] Among them, R i C represents the dissolution rate of target ion i. i (t) represents the ion concentration at time t, C i (t-Δt) represents the ion concentration before time Δt.

[0070] In some specific real-time steps (4), the central processing unit 7 comprehensively evaluates the desalination process based on the dissolution rate and concentration trend of each target ion, conductivity, and pH value, including:

[0071] The central processing unit 7 calculates the dissolution rate of each target ion based on the concentration change trend of each target ion. When the dissolution rate of all target ions is lower than the preset threshold within a continuously set time period, it is determined that the ion dissolution tends to be gradual.

[0072] The central processing unit 7 analyzes the trend of the conductivity of the desalination medium based on the collected conductivity values. When the standard deviation of the conductivity is lower than the preset threshold within a continuously set time period, the conductivity of the system is determined to be stable.

[0073] The central processing unit 7 determines that the system has reached equilibrium when the pH value is stable within the range of 6.5 to 7.5 and the fluctuation range is lower than the preset threshold within a continuous predetermined time, based on the collected pH value data.

[0074] Preferably, the formula for calculating the standard deviation of the conductivity is:

[0075] Where, σ K K represents the standard deviation of conductivity, N is the number of data points within a continuously set time period, and K is the standard deviation of conductivity. 25，j To set the temperature-compensated conductivity value for the j-th data point within a continuously defined time period, The arithmetic mean of conductivity over a continuously defined time period;

[0076] Preferably, it can be calculated according to the following formula:

[0077] Calculate the pH drift rate, where D pH The pH drift rate is given by pH(t), where pH(t) is the pH value measured at the current time t, and pH(t-12h) is the pH value measured 12 hours ago. The pH drift rate is used to represent the pH fluctuation range.

[0078] Central processing unit 7 determines that desalination has reached its scientific endpoint only when all three conditions are met simultaneously: ion dissolution tends to be gradual, conductivity is stable, and pH reaches equilibrium.

[0079] Furthermore, to further ensure the accuracy of the judgment results, after determining that desalination has reached the scientific endpoint, a water (desalination medium) replacement verification operation can be performed. This means that only when three conditions are simultaneously met—ion dissolution becoming gradual, conductivity stabilizing, and pH reaching equilibrium—the desalination medium is replaced, and reequilibration is initiated after a predetermined time. The dissolution rate, standard deviation of conductivity, and pH value of all detected target ions after reequilibration are compared with the data before the desalination medium replacement. The comparison results confirm whether desalination is complete. If the dissolution rate, standard deviation of conductivity, and pH value of all detected target ions after reequilibration are essentially the same as the data before the desalination medium replacement, then desalination is confirmed to be complete. If any one of these values ​​is higher than a predetermined value than the data before the desalination medium replacement, then desalination continues.

[0080] The system and method for online monitoring of ceramic desalination based on ion-selective electrodes disclosed in the above embodiments of the present invention achieve real-time online monitoring of the ceramic desalination process, avoiding the lag and disturbance to the desalination system caused by frequent manual offline sampling, and providing real-time basis for dynamic adjustment of the desalination process. It achieves precise control of multiple parameters through coordinated operation. By introducing an ion-selective electrode (ISE) array, combined with conductivity and pH detection, it can not only reflect changes in total salinity but also accurately identify the most destructive key ions (such as Cl-). - Na + The system utilizes the kinetic dissolution law of ions, solving the problem that single conductivity cannot distinguish ion types. The endpoint determination is scientifically reliable, based on a multi-dimensional determination model established by "ion dissolution rate," "conductivity stability," and "pH drift," changing the traditional endpoint assessment method that relies on experience and a single judgment standard. This effectively avoids secondary damage to cultural relics caused by excessive desalination or safety hazards caused by incomplete desalination. The system has strong anti-interference capabilities, employing multiple mechanisms such as closed monitoring tank design to reduce CO2 interference, temperature compensation correction, data consistency verification, and blank background threshold calibration to ensure the accuracy and reliability of monitoring data in an open operating environment. The system is highly automated; water exchange verification and the triggering and execution of continued desalination can be completed automatically, reducing manual intervention and improving the consistency and efficiency of desalination treatment.

[0081] This invention discloses a method for online monitoring of ceramic desalination effect based on an ion-selective electrode, comprising:

[0082] Desalination preparation: Place the ceramic artifact to be desalinated into the porous suspended partition of monitoring pool 1, and inject deionized water as the desalination medium, ensuring the ceramic artifact is completely submerged. Start the circulating water pump and constant temperature heater to stabilize the temperature of the desalination medium at 20~25℃. Perform low-concentration gradient precision calibration on each ion-selective electrode to adapt to the trace salt detection scenario in the later stage of artifact desalination.

[0083] Multi-parameter real-time monitoring: An ion-selective electrode (ISE) array is introduced, combined with conductivity and pH detection, to construct a multi-parameter collaborative monitoring system. The ion-selective electrode array 2 detects the selective response of ions in the desalination medium in real time, outputting potential signals related to ion activity. These signals are converted into real-time concentration values ​​by the data acquisition module, thereby obtaining the dissolution rate and concentration change trend of each target ion. Conductivity is detected in real time using a conductivity electrode, providing a total reference and verification for the ion-selective electrode data. pH is detected in real time using a pH composite electrode. Temperature is detected in real time using a temperature sensor 4, and the conductivity is temperature-compensated to the 25℃ standard value. The data from these three sources are aggregated in the central processing unit 7. Using the "type identification" and "concentration change rate" of the ion-selective electrodes as core indicators, conductivity as "total evidence," and pH as "environmental stability criterion," a multi-dimensional cross-verification from ion type, total salt concentration, to medium acidity and alkalinity is achieved.

[0084] Data acquisition and processing: The data acquisition and control module 6 acquires signals from each sensor at a set sampling frequency (e.g., once every 5 to 30 minutes), and transmits them to the central processing unit 7 after amplification, filtering, and analog-to-digital conversion; the central processing unit 7 performs smoothing filtering on the raw data to eliminate measurement noise.

[0085] By detecting ion concentration at predetermined intervals (i.e., the set sampling interval), a continuous data sequence of the concentration of each target ion over time can be obtained, thereby obtaining the dynamic laws such as the dissolution rate, concentration change trend, and steady-state fluctuation range of each ion.

[0086] Desalination Process Assessment: Central Processing Unit 7 comprehensively assesses the desalination process based on the following criteria:

[0087] Quantitative analysis of the rate of salt leaching from cultural relics and the degree of desalination stability distinguishes between the rapid leaching stage, the slow desalination stage, and the steady-state equilibrium stage. The entire process involves only data statistics and state analysis without changing the desalination process parameters.

[0088] Key ion dissolution rate calculation: Based on corrected continuous ion concentration data, the main destructive ions (such as Cl) are calculated in real time. - Na +The rate of change of concentration of ( ). The calculation formula is:

[0089] Among them, R i C represents the dissolution rate of target ion i. i (t) represents the ion concentration at time t, C i (t-Δt) represents the ion concentration Δt before time Δt (e.g., 24 hours ago). It represents the rate of change R of the concentration of all target ions within a continuously set time period (e.g., 24 hours). i When all values ​​are below the preset threshold εR, it is determined that the ion dissolution tends to be gradual.

[0090] Conductivity decay and stability assessment: The trend of change in the temperature-compensated standard conductivity EC25 was analyzed. The system's conductivity is considered stable when...

[0091] Where, σ K K represents the standard deviation of conductivity, N is the number of data points within the window, and K is the standard deviation of conductivity. 25，j The temperature-compensated conductivity value for the j-th data point within the window. This is the arithmetic mean of the conductivity within the window. When K... 25 (t) drops to the background extreme value (e.g., ≤2 μS / cm), and σ K The system's conductivity is considered stable when it remains below the threshold εK for a continuously set time period. Here, the background extreme value refers to the background value of the desalination solution; for example, if pure water is used for immersion, it would be the initial conductivity value of the pure water at the time of immersion.

[0092] pH balance and stability determination: Monitor the pH value of the desalination medium. When the pH value is stable within the range of 6.5~7.5 and the fluctuation range is less than the threshold εpH, the system is considered to have reached equilibrium.

[0093] Among them, D pH This refers to the pH drift rate, where pH(t) is the pH value measured at the current time t, and pH(t-12h) is the pH value measured 12 hours ago. This indicator reflects the range of pH changes over a short period; the smaller the value, the more stable the acid-base balance. When the pH value is stable within the range of 6.5 to 7.5, and D... pH The system is considered to have reached equilibrium when the pH value remains below the threshold εpH (e.g., 0.1) for 12 consecutive hours.

[0094] Comprehensive Desalination Process and Endpoint Determination: Based on the collected multi-dimensional data, the central processing unit 7 performs real-time evaluation of the desalination process and determines the endpoint using a built-in algorithm.

[0095] The central processing unit 7 determines that desalination has reached its scientific endpoint and sends a desalination completion signal to the display and alarm module 5 only when all three conditions are met simultaneously: ion dissolution tends to be gradual, conductivity is stable, and pH reaches equilibrium.

[0096] Before determining the desalination endpoint, a water change verification operation can be performed: after replacing the desalination medium, rebalance for 24 hours. If there is no significant rebound in any parameter, the desalination is finally confirmed to be complete; if the parameters rebound significantly, desalination will be automatically triggered to continue.

[0097] The present invention will be further described below with reference to specific embodiments.

[0098] Example 1

[0099] like Figure 1 As shown, this embodiment discloses a system for online monitoring of ceramic desalination effect based on ion-selective electrodes. The system includes a sensor electrode assembly: securely installed inside the monitoring cell 1, comprising Na... + K + Ca 2+ Cl - NO3 - The system includes an ion-selective electrode array 2, a conductivity electrode, a pH composite electrode, and a temperature sensor 4; signal processing and central control hardware: all sensor electrodes are connected to a data acquisition and control module 6 (with a built-in high input impedance preamplifier and analog-to-digital converter). The data acquisition and control module 6 transmits the data to the central processing unit 7, and the display and alarm module 5 provides interactive presentation.

[0100] Example 2

[0101] This embodiment discloses a method for online monitoring of ceramic desalination effect based on ion-selective electrodes. This method is mainly used for online monitoring and endpoint determination of ceramic desalination, including:

[0102] Preparation before desalination: Start the desalination circulation system, place the ceramic vessels from the "Nanhai No. 1" effluent on the porous partition of the soaking tank, and inject deionized water (mass ratio 1:10) until completely submerged. The data acquisition and control module synchronously collects the potential values ​​of each electrode and related physical quantity signals every 15 minutes, and applies a temperature compensation formula to normalize the conductivity data to the standard conductivity value at 25℃.

[0103] Electrode low-concentration calibration: using prepared low-concentration gradient standard solutions (such as Cl) - The ISE electrode was calibrated at multiple points using concentrations of 0.1 mg / L, 1.0 mg / L, and 10.0 mg / L, and the Nernst response curves at extremely low concentrations were fitted to ensure the accuracy of trace salt measurements at the end of desalination. The sampling interval was set to 1 day, and the total monitoring period was 31 days.

[0104] Data Acquisition and Preprocessing: The desalination cycle is initiated, and the data acquisition module and control module synchronously collect the electrode potential values ​​and physical quantities every 15 minutes. An automatic temperature compensation formula is applied to normalize the conductivity to the conductivity at 25℃.

[0105] Online monitoring of the desalination process:

[0106] Initial phase (days 2-8), Cl - The concentration rapidly increased from an initial 0 to 1.39 mg / L, with a dissolution rate R i The concentration was maintained at 0.18–0.22 mg / (L·d), and the conductivity increased from 6.42 μS / cm to 19.2 μS / cm; during the intermediate phase (days 9–19), Cl... - The increase in concentration slowed down, R cl The concentration gradually decreased to 0.03–0.05 mg / (L·d), with conductivity fluctuating between 12 and 27 μS / cm; in the later stage (days 20–30), Cl... - The concentration slowly increased from 1.86 mg / L to 2.46 mg / L, R cl When the concentration drops below 0.004 mg / (L·d), the conductivity stabilizes in the range of 15–19 μS / cm.

[0107] Endpoint determination and water change verification:

[0108] σ K The calculated value was 0.56 μS / cm, and the pH value remained stable between 6.5 and 7.5 (D). pH <0.1), of the three conditions, the ion dissolution rate and pH have been satisfied, and the conductivity stability σ K The pH value (0.56 μS / cm) was not lower than the threshold εK (e.g., 0.15 μS / cm), therefore the system determined that the three conditions were not simultaneously met, and the desalination endpoint signal was not triggered; monitoring continued. By day 31, the pH value abnormally dropped to 6.02. The central processing unit determined that the three conditions were not simultaneously met, and the desalination endpoint signal was not triggered; monitoring continued or the soaking solution (deionized water) was replaced.

[0109] The embodiments of this disclosure have now been described in detail. To avoid obscuring the concept of this disclosure, some details known in the art have not been described. Those skilled in the art can fully understand how to implement the technical solutions disclosed herein based on the above description.

[0110] While specific embodiments of this disclosure have been described in detail by way of examples, those skilled in the art should understand that the examples are for illustrative purposes only and not intended to limit the scope of this disclosure. Those skilled in the art should understand that modifications can be made to the above embodiments or equivalent substitutions can be made to some technical features without departing from the scope and spirit of this disclosure. In particular, as long as there is no structural conflict, the technical features mentioned in the various embodiments can be combined in any manner.

Claims

1. A system for online monitoring of ceramic desalination effect based on ion-selective electrodes, characterized in that, include: The monitoring tank is connected to the soaking tank used for ceramic desalination and is a closed system; An ion-selective electrode array is disposed in the monitoring cell to detect changes in ion concentration in the monitoring cell in real time. The conductivity detection module includes a conductivity electrode disposed in the monitoring pool for real-time monitoring of the conductivity value of the desalination medium in the monitoring pool; The pH detection module includes a pH composite electrode installed in the monitoring tank for real-time monitoring of the pH value of the desalination medium in the monitoring tank. The data acquisition and control module is communicatively connected to the ion-selective electrode array, conductivity detection module, and pH detection module. It is used to receive and process the detection signals output by the ion-selective electrode array, conductivity detection module, and pH detection module to generate real-time monitoring data. A central processing unit, which is communicatively connected to the data acquisition and control module, is used to comprehensively determine the desalination process and endpoint based on the real-time monitoring data.

2. The system according to claim 1, characterized in that, It also includes a temperature sensor, which is installed in the monitoring pool to monitor the temperature of the desalination medium in the monitoring pool in real time; the data acquisition and control module compensates the measured value of the conductivity detection module based on the monitoring result of the temperature sensor.

3. The system according to claim 1, characterized in that, It also includes a display and alarm module, which is connected to the central processing unit and is used to monitor the real-time data and change curves in real time, and to issue a prompt when the preset desalination endpoint conditions are reached; Preferably, it further includes a defoaming module, which includes an inlet pipe, a return pipe, and a peristaltic pump connected to the monitoring tank. The monitoring tank is connected to the return pipe of the circulation pipe of the desalination system through the inlet pipe, and the outlet of the monitoring tank is connected to the soaking tank through the return pipe and the peristaltic pump. Preferably, the sample inlet line has a length and inner diameter that allow nanobubbles in the fluid passing through it to dissipate; Preferably, the outer wall of the injection line is also wrapped with a cooling device to cool the fluid in the injection line to 20-25°C; Preferably, the length of the sample inlet tube is 2.3-2.7m, the inner diameter is 3.5-4.5mm, the flow rate of the fluid in the sample inlet tube is 1.0-1.5m / s, and the residence time of the fluid in the tube is 1.7-2.5min. Preferably, the cooling rate of the cooling device is 0.5 to 2 °C / min.

4. The system according to claim 1, characterized in that, The ion-selective electrode array includes components made of Na + K + Ca 2+ Cl - NO3 - An array of ion-selective electrodes.

5. A method for online monitoring of ceramic desalination effect based on ion-selective electrodes, characterized in that, include: (1) Start the desalination cycle system and calibrate each ion-selective electrode in the ion-selective electrode array; (2) The ion-selective electrode array detects the ion concentration in the desalination medium in real time and outputs the corresponding potential signal, the conductivity detection module detects the conductivity of the desalination medium in real time, and the pH detection module detects the pH value of the desalination medium in real time. (3) The data acquisition and control module acquires conductivity, pH value and potential signal output by the ion selection array at a set sampling frequency, thereby obtaining the dissolution rate and concentration change trend of each target ion; (4) The central processing unit comprehensively evaluates the desalination process based on the dissolution rate and concentration change trend of each target ion, conductivity and pH value; Preferably, the formula for calculating the dissolution rate of the target ion is: Among them, R i C represents the dissolution rate of target ion i. i (t) represents the ion concentration at time t, C i (t-Δt) represents the ion concentration before time Δt.

6. The method according to claim 5, characterized in that, Step (2) further includes: performing temperature compensation correction on the conductivity detection results based on the temperature of the desalination medium detected by the temperature sensor.

7. The method according to claim 5, characterized in that, In step (4), the central processing unit comprehensively evaluates the desalination process based on the dissolution rate and concentration trend of each target ion, conductivity, and pH value, including: The central processing unit calculates the dissolution rate of each target ion based on the concentration change trend of each target ion. When the dissolution rate of all target ions is lower than the preset threshold within a continuously set time period, it is determined that the ion dissolution tends to be gradual. The central processing unit analyzes the trend of the conductivity of the desalination medium based on the collected conductivity values. When the standard deviation of the conductivity is lower than the preset threshold within a continuously set time period, the conductivity of the system is determined to be stable. The central processing unit determines that the system has reached equilibrium when the pH value is stable within the range of 6.5 to 7.5 and the fluctuation range is lower than a preset threshold within a continuous predetermined time, based on the collected pH value data. Preferably, the formula for calculating the standard deviation of the conductivity is: Where, σ K K represents the standard deviation of conductivity, N is the number of data points within a continuously set time period, and K is the standard deviation of conductivity. 25，j To set the temperature-compensated conductivity value for the j-th data point within a continuously defined time period, The arithmetic mean of conductivity over a continuously defined time period; Preferably, according to the calculation formula: Calculate the pH drift rate, where D pH The pH drift rate is given by pH(t), where pH(t) is the pH value measured at the current time t, and pH(t-12h) is the pH value measured 12 hours ago. The pH drift rate is used to represent the pH fluctuation range.

8. The method according to claim 7, characterized in that, In step (4), the central processing unit comprehensively evaluates the desalination process based on the dissolution rate and concentration change trend of each target ion, conductivity, and pH value, and also includes: The central processing unit determines that desalination has reached its scientific endpoint only when all three conditions are met simultaneously: ion dissolution tends to be gradual, conductivity is stable, and pH reaches equilibrium.

9. The method according to claim 8, characterized in that, Also includes: If and only if all three conditions are met simultaneously—the ion dissolution rate tends to be gradual, the conductivity is stable, and the pH reaches equilibrium—the desalination medium is replaced and re-equilibrated for a predetermined time. Based on the data obtained after re-equilibration, the dissolution rate, standard deviation of conductivity, and pH value of all target ions detected are compared with the data before the desalination medium was replaced, and the desalination is confirmed to be complete based on the comparison results.

10. The method according to claim 8, characterized in that, If the dissolution rate, standard deviation of conductivity, and pH value of all target ions detected after rebalancing are basically the same as the data before changing the desalination medium, then desalination is confirmed to be complete. If any one of the values ​​of dissolution rate, standard deviation of conductivity, and pH value of all target ions detected after rebalancing is higher than the predetermined value before changing the desalination medium, then desalination will continue.

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