Search

CN-121994765-A - Fluorescence sensing-based on-line monitoring method and extraction method for fluoride ion extraction of photoelectric panel wastewater

CN121994765ACN 121994765 ACN121994765 ACN 121994765ACN-121994765-A

Abstract

The invention discloses a fluorescence sensing-based on-line monitoring method and an extraction method for fluoride ion extraction of photoelectric panel wastewater, belonging to the field of wastewater detection. The invention monitors the fluorine ion concentration monitoring sensor in advance, judges whether to trigger a sensor calibration mechanism based on the pre-monitoring result, monitors the fluorine ion concentration in real time through the sensor, judges whether to perform dynamic compensation to correct the fluorine ion concentration based on parameters in the monitoring process, simultaneously acquires extraction quality indexes and judges whether to perform extraction process optimization to improve the extraction effect of the fluorine ion, and finally performs stripping reaction to acquire stripping quality indexes and judges whether to perform stripping process optimization, thereby preventing accumulation of the fluorine ion in an oil phase, improving the on-line monitoring accuracy of the fluorine ion extraction, and solving the problem of low on-line monitoring accuracy of the fluorine ion extraction in the prior art.

Inventors

  • HUANG JIAHUI
  • LI SHIYU
  • Hu Wanda

Assignees

  • 广东臻鼎环境科技有限公司

Dates

Publication Date
20260508
Application Date
20260312

Claims (10)

  1. 1. The on-line monitoring method for the fluoride ion extraction of the wastewater of the photoelectric panel based on fluorescence sensing is characterized by comprising the following steps of: a1, pre-monitoring a fluorine ion concentration monitoring sensor, judging whether to trigger a sensor calibration mechanism based on a pre-monitoring result, if so, monitoring the fluorine ion concentration in real time through the calibrated sensor after the sensor is calibrated, otherwise, continuously monitoring the fluorine ion concentration in real time through the sensor; a2, monitoring the concentration of the fluoride ions in the extraction reaction, judging whether to perform dynamic compensation to correct the concentration of the fluoride ions based on parameters in the monitoring process, simultaneously acquiring extraction quality indexes and judging whether to perform extraction process optimization to improve the extraction effect of the fluoride ions, if so, performing back extraction reaction on the oil phase subjected to alkali washing after optimization of the extraction process and ammonia water with preset back extraction concentration, otherwise, directly performing back extraction reaction; A3, monitoring the concentration of the fluoride ions in the back extraction reaction, obtaining a back extraction quality index and judging whether the back extraction process is optimized or not, thereby preventing the accumulation of the fluoride ions in the oil phase.
  2. 2. The fluorescence sensing-based on-line monitoring method for fluoride ion extraction of photoelectric panel wastewater is characterized in that the pre-monitoring comprises dual-sensor parallel monitoring and sensor drift judgment; The dual-sensor parallel monitoring means that the fluorescence sensor and the electrochemical sensor are installed at key monitoring points in parallel, and calibration judgment is carried out based on monitoring data of the fluorescence sensor and the electrochemical sensor according to a set sensor calibration period; The fluorescence sensor adopts a ratio type fluorescence probe comprising a response peak which changes along with the concentration of the fluorine ions and a reference peak which does not change along with the concentration of the fluorine ions; The electrochemical sensor is used as a calibration standard of the fluorescence sensor and is used for updating the slope and intercept of the calibration curve; the sensor drift judgment specifically comprises the following steps: Acquiring a probe measurement state value in the fluorescent sensor under a preset concentration, wherein the probe measurement state value is a ratio of the response peak intensity and the reference peak intensity of the probe in the fluorescent sensor under the preset concentration; If the probe measurement state fluctuation value reflecting the probe measurement state value fluctuation condition is not smaller than the probe measurement state fluctuation limit value, judging that the sensor drifts and triggering a sensor self-checking mechanism, otherwise, not triggering the sensor self-checking mechanism; the probe measurement state fluctuation limit value is the maximum fluctuation condition of the allowed probe measurement state value.
  3. 3. The fluorescence sensing-based on-line monitoring method for fluoride ion extraction of photoelectric panel wastewater, as set forth in claim 2, is characterized in that the monitoring data based on the fluorescence sensor and the electrochemical sensor are calibrated and judged, and the specific flow is as follows: Obtaining the concentration of the fluoride ions monitored by the fluorescent sensor and the concentration standard of the fluoride ions monitored by the electrochemical sensor; If the absolute value of the relative deviation reflecting the deviation degree between the fluoride ion concentration and the fluoride ion concentration reference is larger than the fluorescence correction threshold value, correcting the calibration curve of the fluorescence sensor, wherein the correction curve specifically comprises the steps of updating the slope and intercept of the calibration curve of the fluorescence sensor according to the obtained fluoride ion concentration and the fluoride ion concentration reference by a recursive least square method; otherwise, the calibration curve of the fluorescence sensor is not corrected; The fluorescence correction threshold is a maximum value of the allowable degree of deviation between the fluoride ion concentration and the fluoride ion concentration reference.
  4. 4. The fluorescence sensing-based on-line monitoring method for fluoride ion extraction of photoelectric panel wastewater, as set forth in claim 2, characterized in that the sensor self-checking mechanism comprises one or more of static stability check, electronic component check and optical path integrity check; monitoring the measurement state of a probe in a fluorescent sensor in a standard fluoride ion solution, if the fluctuation value of the measurement state of the probe is not smaller than the fluctuation limit value of the measurement state of the probe, checking an electronic component to check the working state of a core electronic component in the sensor, otherwise, directly judging that the sensor is normal; Reading sensor parameters including light source driving current, photoelectric detector dark current and temperature sensor reading, comparing the sensor parameters with sensor baseline parameters, prompting preset personnel that the electronic components are abnormal if sensor deviation reflecting deviation degree between the sensor parameters and the corresponding sensor baseline parameters exists, otherwise, performing light path integrity check, wherein the light source driving current represents current supplied to a luminous element in the sensor, and the photoelectric detector dark current represents current generated by the detector when no light irradiates the detector; The optical path integrity check specifically comprises the steps of prompting preset personnel that the optical path integrity is abnormal if the intensity change rate of a reference peak is larger than the upper limit of the intensity change rate of the reference peak in a preset time period, otherwise prompting the preset personnel that a sensor is abnormal, wherein the intensity change rate of the reference peak reflects the change condition of the intensity of the reference peak along with time, and the upper limit of the intensity change rate of the reference peak is the maximum allowable intensity change rate of the reference peak.
  5. 5. The on-line monitoring method for fluoride ion extraction of photoelectric panel wastewater based on fluorescence sensing as claimed in claim 1, wherein the method is characterized in that the method comprises the following specific procedures: Acquiring monitoring response time of the fluorescence sensor during the extraction reaction; If the monitoring response time of the fluorescence sensor is larger than the monitoring response upper limit, the monitoring response upper limit is the maximum value of the acceptable monitoring response, and the monitoring response upper limit is used for representing that the sensor is abnormal in monitoring and dynamically compensating, otherwise, the monitoring response upper limit is not dynamically compensated; the dynamic compensation is specifically as follows: collecting measurement signals of a blank oil phase without fluorine to obtain background fluorescence intensity; Performing point-by-point deviation treatment on the calibrated fluoride ion concentration and the background fluorescence intensity of each key monitoring point to obtain the fluoride ion concentration after background compensation so as to reduce common mode interference caused by light source fluctuation, temperature change or detector sensitivity drift; Carrying out multi-parameter fusion compensation on the concentration of the fluoride ions after the background compensation to obtain the fluoride ions after the compensation; The fluoride ion concentration after calibration is the fluoride ion concentration obtained after pre-monitoring.
  6. 6. The fluorescence sensing-based on-line monitoring method for fluoride ion extraction of photoelectric panel wastewater, as set forth in claim 1, is characterized in that the judgment of the extraction process optimization is carried out or not, and the specific flow is as follows: If the turbidity obtained by the turbidity meter is greater than the turbidity upper limit, gradually reducing the stirring intensity according to a preset stirring adjustment proportion until the turbidity is not greater than the turbidity upper limit, so that emulsification is avoided, otherwise, the stirring intensity is not reduced; the upper turbidity limit is the maximum value of acceptable turbidity; the stirring intensity is increased step by step when the turbidity after the extraction process is optimized is not more than the turbidity upper limit, and monitoring and judging are carried out, specifically, if the turbidity is more than the turbidity upper limit in the process of increasing the stirring intensity step by step, the current stirring intensity is recorded as temporary stirring intensity, meanwhile, a preset person is prompted to have abnormal stirring intensity after the extraction is finished, and demulsifier is added in the subsequent extraction agent preparation process, otherwise, the stirring intensity is continuously reduced; Meanwhile, if the fluoride ion concentration of the raffinate phase is larger than the target fluoride ion concentration of the raffinate phase, the rotating speed of the extract phase pump is increased to increase the flow rate of the extract phase, if the fluoride ion concentration of the raffinate phase is smaller than the target fluoride ion concentration of the raffinate phase, the rotating speed of the extract phase pump is reduced to decrease the flow rate of the extract phase, and if the fluoride ion concentration of the raffinate phase is equal to the target fluoride ion concentration of the raffinate phase, the flow rate of the extract phase is not adjusted, so that the fluoride ion concentration of the raffinate phase is controlled; When the fluoride ion concentration of the raffinate phase is not equal to the target fluoride ion concentration of the raffinate phase, if the fluoride ion concentration deviation of the raffinate phase is larger than the upper limit of the fluoride ion concentration deviation, the PID controller is used for adjusting after the feedforward control is used for adjusting so as to balance the stability and timeliness of the flow control, otherwise, the PID controller is directly used for adjusting; the optimization of the extraction process comprises the steps of reducing the stirring intensity and adjusting the flow rate of the extraction phase.
  7. 7. The fluorescence sensing-based on-line monitoring method for fluoride ion extraction of photoelectric panel wastewater, as set forth in claim 1, is characterized in that the judging whether the stripping process is optimized comprises the following specific procedures: If the fluoride ion concentration of the strip liquor is larger than the target fluoride ion concentration of the strip liquor, the rotating speed of the ammonia water pump is reduced to reduce the ammonia water flow, if the fluoride ion concentration of the strip liquor is smaller than the target fluoride ion concentration of the strip liquor, the rotating speed of the ammonia water pump is increased to increase the ammonia water flow, and if the fluoride ion concentration of the strip liquor is equal to the target fluoride ion concentration of the strip liquor, the ammonia water flow is not adjusted, so that the fluoride ion concentration in the strip liquor is controlled; When the fluoride ion concentration of the back extraction liquid is not equal to the target fluoride ion concentration of the back extraction liquid, if the fluoride ion concentration deviation amount of the back extraction liquid is larger than the fluoride ion concentration deviation amount upper limit, the feedforward control is used for adjusting the fluoride ion concentration deviation amount, and then the PID controller is used for adjusting the fluoride ion concentration deviation amount, otherwise, the PID controller is directly used for adjusting the fluoride ion concentration deviation amount.
  8. 8. The method for online monitoring of fluoride ion extraction of wastewater from an optoelectronic panel based on fluorescence sensing as set forth in claim 6, wherein the adjusting by using a PID controller further comprises: if the adjusting response time of the PID controller is larger than the adjusting response time upper limit, optimizing the PID controller, otherwise, not optimizing the PID controller, wherein the adjusting response time upper limit is the maximum value of the acceptable adjusting response time; the PID controller is optimized, namely the PID control is optimized by combining a Smith predictor, so that the PID controller adapts to the working condition change and the timeliness of the PID control is improved; the PID controller is optimized, specifically: Recording a change curve of the fluoride ion concentration of the raffinate phase, identifying gain, time constant and lag time in the extraction process, and accordingly establishing a transfer function model describing the change of the rotating speed of the pump and the change of the fluoride ion concentration; After each control period is finished, the transfer function model parameters are obtained again through a recursive least square method by utilizing the calibrated fluoride ion concentration and the control signals in the historical control period, and the transfer function model in the Smith predictor is updated; And in each control period, obtaining model output and hysteresis-free model output according to the transfer function model and the hysteresis time, and obtaining a synthesized feedback signal according to the calibrated fluoride ion concentration, the model output and the hysteresis-free model output, so that the synthesized feedback signal is input into the PID controller to obtain a new control signal.
  9. 9. The fluorescence sensing-based on-line monitoring method for fluoride ion extraction of photoelectric panel wastewater, as set forth in claim 5, is characterized in that the method for performing multiparameter fusion compensation on the fluoride ion concentration after background compensation comprises the following specific procedures: Combining the sensitivity coefficient and the background fluorescence intensity to construct a linear equation between the probe measurement state value and the fluoride ion concentration, so as to obtain a fluoride ion correction equation; synchronously measuring the pH value, the interfering anion concentration and the oil phase ratio of the corresponding solvent; Performing pH interference correction treatment on the dissociation constant and the pH value of the fluorescent sensor probe to obtain a pH correction factor, wherein the dissociation constant is used for describing the capability of the fluorescent probe molecule to release or combine hydrogen ions at a specific pH; Obtaining a solvent correction factor according to the solvent influence coefficient and the oil phase ratio, and compensating a fluoride ion correction equation based on the existence of competitive anions in the interference anions, thereby obtaining compensated fluoride ions; Introducing a pH correction factor, a solvent correction factor and an anion correction factor, correcting the initial sensitivity to obtain effective sensitivity to replace a sensitivity coefficient and obtain a new fluoride ion correction equation so as to eliminate measurement errors caused by pH change or coexisting ion interference, wherein the anion correction factor represents a result obtained by carrying out anion interference correction processing on the concentration of interfering anions of each interfering anion and a corresponding site occupation coefficient, and the site occupation coefficient is used for describing the capacity of the competitive anions to occupy probe sites; Adding a fluorescence quenching compensation term in the fluoride ion correction equation, introducing a pH correction factor and a solvent correction factor, correcting the initial sensitivity to obtain effective sensitivity to replace a sensitivity coefficient, and obtaining a new fluoride ion correction equation so as to reduce chemical interference, wherein the fluorescence quenching compensation term represents the result of anion quenching compensation processing of the concentration of the interfering anions and the corresponding quenching coefficient, and the quenching coefficient is used for describing the capability of the interfering anions to quench fluorescence signals.
  10. 10. The fluorescence sensing-based photoelectric panel wastewater fluoride ion extraction method for realizing the fluorescence sensing-based photoelectric panel wastewater fluoride ion extraction on-line monitoring method according to claims 1-9 is characterized by comprising the following steps: S1, taking etching wastewater of a photoelectric panel as a water phase, and carrying out an extraction reaction with an extraction phase according to a preset extraction volume ratio and preset extraction mixing conditions to obtain a raffinate water phase and an oil phase loaded with fluorine; S2, carrying out alkaline washing reaction on the obtained oil phase loaded with fluorine and ammonia water with preset alkaline washing concentration according to a preset alkaline washing volume ratio and preset alkaline washing mixing conditions to obtain an oil phase after alkaline washing; S3, carrying out back extraction reaction on the obtained alkaline washed oil phase and ammonia water with preset back extraction concentration according to a preset back extraction volume ratio and preset back extraction mixing conditions to obtain fluorine-containing back extraction liquid and regenerated oil phase, and conveying the regenerated oil phase to an extraction phase storage tank for recycling, wherein the regenerated oil phase is an extraction phase for recycling extraction after returning to an initial form.

Description

Fluorescence sensing-based on-line monitoring method and extraction method for fluoride ion extraction of photoelectric panel wastewater Technical Field The invention relates to the technical field of sewage detection, in particular to an online monitoring method and an extraction method for fluoride ion extraction of photoelectric panel wastewater based on fluorescence sensing. Background With the rapid development of new generation information industries such as semiconductors and photoelectric panels, hydrofluoric acid and fluoride thereof are used as key materials, and play an irreplaceable role in core process links such as chip etching. In order to realize green and efficient recovery of fluorine resources, fluoride ion extraction is required, wherein the extractant is generally prepared by mixing components such as P204, cyanex923, TBP and the like according to a specific proportion, and is dissolved in a diluting agent such as kerosene or ethyl acetate to form an organic phase. The organic phase and fluorine-containing wastewater (water phase) are mixed and reacted in a stirrer according to a certain volume ratio, temperature and stirring speed, so that the transfer of fluorine ions is realized. And then, the organic phase loaded with fluorine is subjected to alkaline washing, back extraction and other steps to finally obtain an ammonium fluoride solution, and the ammonium fluoride product is obtained through unit operations such as impurity removal and filtration, reduced pressure evaporation, cooling crystallization, drying and the like. The equipment involved in each step comprises a stirring kettle, a precise filter, a multi-effect evaporator, a crystallization tank, a centrifugal machine, drying equipment and the like. The extraction process is a dynamic equilibrium, and its efficiency and stability are directly affected by the reaction conditions. In order to ensure the optimal operation of the process, it is important to perform real-time and comprehensive on-line monitoring on the extraction process. The monitoring of the extraction process integrates the real-time monitoring of the physicochemical parameters such as reaction temperature, stirring rate, pH value, etc. These basic parameters are collected by various types of sensors (e.g., thermometer, pH meter, level gauge) and are collectively incorporated into a central process control system, such as a programmable logic controller (Programmable Logic Controller, PLC). The PLC automatically adjusts heating power, stirring motor rotation speed and the like according to a preset process curve, and ensures extraction under the optimal condition. Among the numerous monitoring parameters, the concentration distribution of fluoride ions in the aqueous phase and the organic phase is the most critical index for directly measuring the extraction efficiency, judging the reaction endpoint and evaluating the loading capacity of the organic phase. The fluorine ion extraction on-line monitoring technology not only can measure the fluorine concentration in the initial wastewater and the final strip liquor, but also needs to go deep into the extraction reaction, and the changes of the residual concentration of the aqueous phase and the load saturation of the organic phase are tracked in real time, for example, the changes of the fluorine concentration in a water body can be continuously tracked through an ion selection electrode in an ion selection electrode method, and a fluorescence sensor in an optical analysis method can realize the accurate measurement of trace fluorine in a complex sample. An on-line monitoring device and method for high concentration chloride ions in wastewater, for example, disclosed in Chinese patent application publication No. CN119827593A, comprises a water supply pump, a filter, a water inlet regulating valve, an overflow tank, a mixing tank, a detection tank, a wastewater peristaltic pump, a medicament bottle, a chloride ion concentration detector and a composite electrode, wherein a water outlet pipe of the water supply pump is connected with a water inlet of the overflow tank through the filter and the water inlet regulating valve in sequence, a water inlet end of the wastewater peristaltic pump is connected with the overflow tank, a water outlet end of the wastewater peristaltic pump is connected with the mixing tank, a water inlet end of the medicament peristaltic pump is connected with the medicament bottle, a water outlet end of the medicament peristaltic pump is connected with the mixing tank, the detection tank is communicated with the mixing tank, the composite electrode is arranged in the detection tank, and a signal output end of the composite electrode is connected with the chloride ion concentration detector. An on-line monitoring system and a monitoring method thereof for general fluoride ions are disclosed in Chinese patent application with publication number of CN118294609A, and comprise a PLC controller for