A hydrochloric acid pH control device and control method in the germanium oxide production process

Abstract

The embodiment of the present invention provides a hydrochloric acid pH control device and control method for the germanium oxide production process, which belongs to the field of chemical process automatic control. The device includes: an acid storage tank for storing raw hydrochloric acid, connected to a mixed acid tank via a raw acid addition control valve; a mixed acid tank for mixing acid with a diluent, connected to a pH adjustment reaction tank via a mixed acid addition control valve; an alkali storage tank, connected to a pH adjustment reaction tank via an alkali addition control valve; a pH adjustment reaction tank for receiving mixed acid and alkali and adjusting the pH value of the reaction system, and is equipped with a pH sensor for real-time detection of the pH value; a control unit for dynamically adjusting the opening of each valve to control the pH value within the target range based on the detection results of the pH sensor using an improved fuzzy adaptive PID control algorithm. The solution of the present invention reduces the overshoot and hysteresis problems caused by traditional fixed parameter PID adjustment, thereby ensuring the stability of the solution pH value and the consistency of the process during the germanium oxide production process.

Description

Technical Field

[0001] The present invention relates to the field of automatic control of chemical processes, and in particular to a hydrochloric acid pH control device in a germanium oxide production process and a control method for the hydrochloric acid pH control device in a germanium oxide production process. Background Art

[0002] Germanium oxide, an important rare metal material, is widely used in optical fibers, electronic devices, solar cells, and other fields. In the industrial production of germanium oxide, hydrochloric acid is often used to dissolve the intermediate product in order to adjust the pH of the reaction system and promote an efficient reaction. However, in actual production, the pH value of the hydrochloric acid in the reaction tank often fluctuates due to factors such as fluctuating reactant properties, delayed response to acid and alkali additions, and frequent changes in operating conditions. This in turn affects the conversion rate of subsequent reactions and the stability of product quality.

[0003] In the prior art, hydrochloric acid pH control generally relies on traditional PID controllers, which adjust the amount of acid or alkali solution added based on real-time pH test results. However, due to the strong nonlinear variation characteristics of the hydrochloric acid system and the unpredictable changes in the concentration of the recycled acid, traditional PID control suffers from response lag, large overshoot, and insufficient adjustment accuracy, making it difficult to achieve accurate and stable pH control under dynamic conditions. At the same time, some existing processes fail to effectively utilize the recycled acid from the germanium oxide production process, and the recycled acid is directly discharged or roughly reused, resulting in a waste of acid resources and further exacerbating the instability of pH control.

[0004] Therefore, how to introduce a more intelligent, responsive and adaptive control method for hydrochloric acid pH control in the germanium oxide production process, and at the same time combine it with the intelligent allocation of recycled acid to achieve high-precision and stable pH adjustment, has become an urgent problem to be solved in the current technical field. Summary of the Invention

[0005] The purpose of the embodiments of the present invention is to provide a hydrochloric acid pH control device and a control method for the germanium oxide production process, so as to at least solve the problems in the prior art of delayed response of hydrochloric acid pH control, insufficient adjustment accuracy, low utilization rate of recovered acid solution, and impact on system stability.

[0006] To achieve the above objectives, the present invention provides, in a first aspect, a hydrochloric acid pH control device for a germanium oxide production process, the device comprising: an acid storage tank for storing raw hydrochloric acid, the device being connected to a mixed acid tank via a raw acid dosing control valve; a mixed acid tank for mixing the acid with a diluent, the device being connected to a pH adjustment reaction tank via a mixed acid dosing control valve; an alkali storage tank for storing alkali, the device being connected to a pH adjustment reaction tank via an alkali dosing control valve; a pH adjustment reaction tank for receiving the mixed acid and alkali and adjusting the pH value of the reaction system, the device being equipped with a pH sensor for real-time pH detection; and a control unit for dynamically adjusting the opening of each valve based on the detection result of the pH sensor using an improved fuzzy adaptive PID control algorithm to control the pH value within a target range.

[0007] Optionally, the control unit is configured with a prediction module and a control logic module; the prediction module includes a data acquisition module, a sliding window processing module and a trend extrapolation module; the data acquisition module is used to record the detection value and detection time of the pH sensor in real time to form a corresponding data set; the sliding window processing module is used to extract continuous pH value change data within a set time window from the data set; the trend extrapolation module uses a first-order linear extrapolation method based on the pH change rate within the sliding window to predict the expected future pH change trend, and inputs the predicted pH change trend into the control logic module, and the control logic module adjusts the opening of the original acid addition control valve and the alkali solution addition control valve at a preset time in advance according to the prediction result.

[0008] Optionally, a temperature sensor is further provided in the pH adjustment reaction tank; the temperature sensor is used to collect temperature data of the solution in the pH adjustment reaction tank in real time; the control unit is provided with a temperature compensation module; the temperature compensation module calls a preset pH temperature compensation curve according to the temperature data of the solution; the original pH detection value is adjusted and corrected based on the pH temperature compensation curve, and the corrected pH value is transmitted to the control unit.

[0009] Optionally, the device also includes a hydrochloric acid recovery device arranged between the germanium oxide production unit and the mixed acid tank, and the hydrochloric acid recovery device includes: a solid-liquid separation device connected to the recovery port of the germanium oxide production unit, used to separate solid impurities in the recovered liquid from the liquid phase; an acid liquid recovery tank connected between the solid-liquid separation device and the mixed acid tank, the other end of the acid liquid recovery tank is connected to the mixed acid tank through a recovered acid output control valve, and the acid liquid recovery tank is used to collect and temporarily store the acidic liquid after solid-liquid separation.

[0010] Optionally, the acid liquid recovery tank is equipped with a liquid detection module; the liquid detection module includes an acidity detection module and a liquid level detection module; the acidity detection module is used to detect the pH value of the recovered liquid in the acid liquid recovery tank in real time and send a detection signal to the control unit; the liquid level detection module is used to monitor the liquid level height in the acid liquid recovery tank in real time and send a liquid level signal to the control unit; the control unit is also used to: when it is detected that the pH value of the recovered liquid is within the set reuse range and the liquid level height exceeds the set value, control the recovered acid output control valve to open and transport the recovered acid liquid to the mixed acid tank for reuse; when it is detected that the pH value of the recovered liquid is not within the set reuse range or the liquid level height does not exceed the set value, close the recovered acid output control valve to prevent the acid liquid from flowing back.

[0011] Optionally, the control unit includes: an input membership function module, a fuzzy reasoning module and an output correction module; the input membership function module is used to fuzzify the pH deviation value and the pH deviation change rate obtained from the pH sensor detection result; wherein, the pH deviation value represents the difference between the pH set value and the pH sensor detection value; the pH deviation change rate is the rate of change of the pH deviation value over time; the fuzzy reasoning module generates correction amounts of proportional gain, integral gain and differential gain based on a preset fuzzy rule table; the output correction module is used to superimpose the correction amounts of proportional gain, integral gain and differential gain on the current PID parameters and apply them to the controller output in real time.

[0012] A second aspect of the present invention provides a control method for a hydrochloric acid pH control device in a germanium oxide production process. The method includes the following steps: transporting raw hydrochloric acid from an acid storage tank to a mixed acid tank through a raw acid addition control valve, and mixing the raw hydrochloric acid with a diluent in the mixed acid tank to form a mixed acid solution; controlling the mixed acid solution to flow into a pH adjustment reaction tank through the mixed acid addition control valve, and simultaneously adding alkali solution to the pH adjustment reaction tank through the alkali solution addition control valve; detecting the pH value of the solution in the pH adjustment reaction tank in real time through a pH sensor, and sending the detection value to a control unit; and dynamically adjusting the openings of the raw acid addition control valve, the mixed acid addition control valve, and the alkali solution addition control valve based on the pH detection value to adjust the pH value of the hydrochloric acid within a target range using an improved fuzzy adaptive PID control algorithm.

[0013] Optionally, the method further includes: introducing the recovered liquid from the recovery port of the germanium oxide production unit into a solid-liquid separation device to separate the liquid phase and solid impurities; transporting the separated acidic liquid to an acid liquid recovery tank for temporary storage; detecting the pH value of the acidic liquid in the acid liquid recovery tank by an acidity detection module, and detecting the liquid level of the recovered liquid by a liquid level detection module; sending the detected acidity signal and liquid level signal to a control unit; when the control unit detects that the pH value of the recovered liquid is within a set reuse range and the liquid level exceeds a set threshold, the control unit opens the recovered acid output control valve to lead the recovered acid back to the mixed acid tank to participate in the preparation of the mixed acid liquid; when it is detected that the pH value or liquid level does not meet the set conditions, the recovered acid output control valve is closed to prevent the recovered acid from flowing back.

[0014] Optionally, the control unit adopts an improved fuzzy adaptive PID control algorithm according to the pH detection value to dynamically adjust the opening of the raw acid addition control valve, the mixed acid addition control valve and the alkali solution addition control valve to adjust the pH value of the hydrochloric acid within the target range, including: collecting the pH detection value and the set value at the current moment to calculate the pH deviation value; calculating the change rate of the pH deviation value within the set time interval as the deviation change rate; inputting the pH deviation value and the deviation change rate into the input membership function module for fuzzy processing; through the fuzzy reasoning module, according to the preset fuzzy rule table, inferring the correction amount of the proportional gain, integral gain and differential gain; superimposing the correction amount on the proportional parameter, integral parameter and differential parameter of the current PID controller through the output correction module to obtain the corrected PID parameters; and applying the corrected PID parameters to real-time adjustment of the opening of the raw acid addition control valve, the mixed acid addition control valve and the alkali solution addition control valve to achieve closed-loop dynamic control of the pH value.

[0015] On the other hand, the present invention provides a computer-readable storage medium having instructions stored thereon, which, when executed on a computer, enables the computer to execute the above-mentioned method for controlling the hydrochloric acid pH control device in the germanium oxide production process.

[0016] Through the above technical solution, the present invention establishes an independent supply and precise dosing system for raw acid, mixed acid, and alkali by setting up an acid storage tank, a mixed acid tank, an alkali storage tank, and a pH adjustment reaction tank, which can flexibly adjust the solution composition according to different reaction stages. The pH sensor detects pH changes in the reaction tank in real time, allowing the system to obtain solution status data in a timely manner. Combined with the improved fuzzy adaptive PID control algorithm adopted by the control unit, dynamic adjustment of the opening of each dosing valve is achieved, effectively improving the response speed and control accuracy during the pH adjustment process, reducing the overshoot and lag problems caused by traditional fixed parameter PID adjustment, thereby ensuring the stability of the solution pH value and process consistency during the germanium oxide production process.

[0017] Other features and advantages of the embodiments of the present invention will be described in detail in the subsequent detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] The accompanying drawings are used to provide a further understanding of the embodiments of the present invention and constitute a part of the specification. Together with the following detailed description, they are used to explain the embodiments of the present invention, but do not constitute a limitation of the embodiments of the present invention. In the accompanying drawings:

[0019] Figure 1 This is a structural diagram of a hydrochloric acid pH control device in a germanium oxide production process provided by one embodiment of the present invention;

[0020] Figure 2 This is a structural diagram of a hydrochloric acid pH control device in a germanium oxide production process provided with a hydrochloric acid recovery device, provided in one embodiment of the present invention;

[0021] Figure 3 A control method for a hydrochloric acid pH control device in a germanium oxide production process is provided in one embodiment of the present invention.

[0022] Description of Reference Numerals

[0023] 10-acid storage tank; 20-mixed acid tank; 30-alkali storage tank; 40-pH adjustment reaction tank; 50-control unit; 60-pH sensor; 70-germanium oxide production unit; 80-solid-liquid separation device; 90-acid recovery tank;

[0024] 101-Original acid addition control valve; 201-Mixed acid addition control valve; 301-Alkali solution addition control valve; 401-Recovered acid output control valve. DETAILED DESCRIPTION

[0025] The following describes the specific embodiments of the present invention in detail with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention and are not intended to limit the present invention.

[0026] Figure 1 This is a structural diagram of a hydrochloric acid pH control device in a germanium oxide production process provided by one embodiment of the present invention. Figure 1As shown, an embodiment of the present invention provides a hydrochloric acid pH control device for a germanium oxide production process, the device comprising: an acid storage tank 10 for storing raw hydrochloric acid, connected to a mixed acid tank 20 via a raw acid dosing control valve 101; the mixed acid tank 20 for mixing the acid with a diluent, connected to a pH adjustment reaction tank 40 via a mixed acid dosing control valve 201; an alkali storage tank 30 for storing alkali, connected to the pH adjustment reaction tank 40 via an alkali dosing control valve 301; the pH adjustment reaction tank 40 for receiving the mixed acid and alkali and adjusting the pH value of the reaction system, and being equipped with a pH sensor 60 for real-time detection of the pH value; and a control unit 50 for dynamically adjusting the opening of each valve based on the detection result of the pH sensor 60 to control the pH value within a target range using an improved fuzzy adaptive PID control algorithm.

[0027] In this embodiment of the present invention, the apparatus includes an acid storage tank 10, an acid mixing tank 20, an alkali storage tank 30, a pH adjustment reactor 40, a pH sensor 60, and a control unit 50. The acid storage tank 10 is used to store raw hydrochloric acid, typically industrial hydrochloric acid with a concentration between 28% and 32%. A raw acid dosing control valve 101 is installed at the outlet of the acid storage tank 10. One end of the raw acid dosing control valve 101 is connected to the acid storage tank 10 and the other end is connected to the acid inlet of the acid mixing tank 20. The opening of the control valve can adjust the amount of acid added. The acid mixing tank 20 is used to mix and dilute hydrochloric acid with a diluent (such as deionized water or process water). A stirring paddle or circulation pump may be installed to promote thorough mixing of the acid and diluent and avoid localized high concentrations. A mixed acid dosing control valve 201 is installed at the outlet of the acid mixing tank 20. The mixed acid dosing control valve 201 is connected to the pH adjustment reactor 40 to supply the mixed acid to the reactor on demand.

[0028] The alkali solution storage tank 30 is used to store alkaline solutions, such as sodium hydroxide solutions, with a concentration generally controlled at 20% to 30%. The discharge port of the alkali solution storage tank 30 is provided with an alkali solution addition control valve 301, through which the alkali solution enters the pH adjustment reaction tank 40 to neutralize the excess acidic components in the reaction solution. The pH adjustment reaction tank 40 is provided with multiple feed ports, which are respectively connected to the outlet of the mixed acid tank 20 and the outlet of the alkali solution storage tank 30. At the same time, a stirring mechanism is arranged inside the reaction tank to ensure that the mixed acid solution and the alkali solution can react quickly and evenly. A pH sensor 60 is installed in the reaction tank to collect the pH value data of the solution in the tank in real time and transmit the collected signal to the control unit 50.

[0029] The control unit 50 incorporates an improved fuzzy adaptive PID control algorithm. Specifically, the algorithm compares the real-time pH value detected by the pH sensor 60 with the set target pH value to obtain a deviation value, and further calculates the rate of change of the deviation. This deviation value and its rate of change are then fuzzified using membership functions and fed into a fuzzy inference module, which infers corrections for the proportional, integral, and differential coefficients using a fuzzy rule table. Based on these inference results, the control unit 50 updates the PID parameters in real time and calculates new control instructions based on the updated PID values. This dynamically adjusts the openings of the raw acid dosing control valve 101, the mixed acid dosing control valve 201, and the alkali solution dosing control valve 301, thereby precisely controlling the pH value in the reaction tank to maintain it within the target range.

[0030] Preferably, the control unit 50 is configured with a prediction module and a control logic module; the prediction module includes a data acquisition module, a sliding window processing module and a trend extrapolation module; the data acquisition module is used to record the detection value and detection time of the pH sensor 60 in real time to form a corresponding data set; the sliding window processing module is used to extract the continuous pH value change data within a set time window from the data set; the trend extrapolation module uses a first-order linear extrapolation method based on the pH change rate within the sliding window to predict the expected future pH change trend, and inputs the predicted pH change trend into the control logic module, and the control logic module adjusts the opening of the raw acid addition control valve 101 and the alkali solution addition control valve 301 at a preset time in advance according to the prediction result.

[0031] In this embodiment of the present invention, the control unit 50 is equipped with a prediction module and a control logic module, which are used to proactively adjust the dosage of acid and alkali solutions based on pH trend changes. The prediction module specifically includes a data acquisition module, a sliding window processing module, and a trend extrapolation module. The data acquisition module receives pH values ​​detected by the pH sensor 60 in real time and simultaneously records the corresponding detection timestamps to form a time series dataset. To ensure real-time data, the sampling period is generally set between 1 and 10 seconds, adjustable depending on production conditions. The collected dataset is stored in pairs of (time, pH value) to facilitate subsequent processing.

[0032] The sliding window processing module is used to extract continuous data within a set time window from the dataset. Specifically, the time window is typically set to 30 seconds to 5 minutes, preferably 60 seconds. This means that at any given moment, pH data collected continuously within the last 60 seconds is extracted. The data within the window is arranged in chronological order, and no sampling points are discarded. Each time the sliding window collects new data, it slides forward one time step, ensuring that the data used for prediction is always the most up-to-date, reflecting the state of the reaction system.

[0033] The trend extrapolation module analyzes the data within a sliding window. It first calculates the rate of change of the pH value within the current window, that is, the ratio of the change in pH value to the change in time within the window period. The rate of change can be calculated using a simple two-point method (the latest pH value minus the earliest pH value divided by the time difference), or using the least squares method to perform a straight line fit and extract the slope as the pH rate of change indicator. The trend extrapolation module then uses a first-order linear extrapolation method based on the current pH rate of change to predict the pH value change trend within a preset time interval (for example, 30 seconds or 1 minute). The prediction formula can be set as:

[0034] ;

[0035] in, is the expected pH value at a certain time in the future, The pH value of the latest test is the pH change rate estimated within the sliding window. The amount of time to shift the forecast forward.

[0036] The predicted future pH trend data is input into the control logic module. Based on the predicted results, the control logic module compares the deviation of the future pH value with the set target pH range and determines whether preemptive valve opening adjustment is necessary. If the predicted pH trend indicates that the pH value will reach a low or high boundary value in the future, the control logic module will issue an adjustment command within a preset lead time (for example, 20 seconds or 30 seconds) to adjust the opening of the raw acid injection control valve 101 and the alkali solution injection control valve 301 accordingly, thereby intervening in advance and suppressing abnormal pH fluctuations.

[0037] Preferably, a temperature sensor is also provided in the pH adjustment reaction tank 40; the temperature sensor is used to collect temperature data of the solution in the pH adjustment reaction tank 40 in real time; the control unit 50 is provided with a temperature compensation module; the temperature compensation module calls a preset pH temperature compensation curve according to the temperature data of the solution; the original pH detection value is adjusted and corrected based on the pH temperature compensation curve, and the corrected pH value is transmitted to the control unit 50.

[0038] In an embodiment of the present invention, a temperature sensor is provided within the pH adjustment reaction tank 40 for real-time acquisition of temperature data of the solution within the tank. The temperature sensor can be a conventional corrosion-resistant thermocouple, thermistor, or integrated temperature probe. It is generally installed near the pH electrode and should be in full contact with the solution to ensure representativeness and real-time accuracy of the detected temperature. To avoid the effects of temperature drift, the sensor should preferably have a regular calibration function, and the detection frequency is typically set to once per second to meet the real-time tracking requirements in rapidly changing environments.

[0039] The collected temperature data is transmitted to the temperature compensation module for processing. The temperature compensation module pre-stores a temperature compensation curve for the pH electrode. This curve can be obtained based on data provided by the electrode manufacturer or through preliminary calibration. Typically, a mapping relationship is established between temperature as the independent variable and pH correction value as the dependent variable. The temperature compensation curve can be implemented using piecewise linear interpolation, quadratic curve fitting, or table lookup. In specific applications, an interpolation algorithm is preferred to improve compensation accuracy while maintaining a moderate calculation speed.

[0040] When the temperature compensation module receives new temperature data, it first calls the preset pH temperature compensation curve based on the currently detected solution temperature to determine the corresponding compensation correction value. If the temperature is between two calibration points, linear interpolation is used to obtain the correction value. Subsequently, the correction value is applied to the original pH detection value to calculate the corrected pH value. The corrected pH value will be transmitted to the control unit 50 for subsequent pH adjustment control calculations. The control unit 50 will execute the valve opening adjustment decision based on the corrected pH value rather than the original pH value, thereby making the pH adjustment process more accurate and reliable. Especially in production scenarios with large temperature fluctuations (such as reaction exotherm or cooling abnormalities), the above-mentioned temperature compensation mechanism can effectively avoid pH measurement errors caused by changes in electrode response with temperature, and prevent the occurrence of erroneous acid or alkali addition instructions.

[0041] Preferably, Figure 2 The device also includes a hydrochloric acid recovery device arranged between the germanium oxide production unit 70 and the mixed acid tank 20, and the hydrochloric acid recovery device includes: a solid-liquid separation device 80 connected to the recovery port of the germanium oxide production unit 70, used to separate solid impurities in the recovered liquid from the liquid phase; an acid liquid recovery tank 90 connected between the solid-liquid separation device 80 and the mixed acid tank 20, the other end of the acid liquid recovery tank 90 is connected to the mixed acid tank 20 through the recovered acid output control valve 401, and the acid liquid recovery tank 90 is used to collect and temporarily store the acidic liquid after solid-liquid separation.

[0042] Furthermore, the acid liquid recovery tank 90 is provided with a liquid detection module; the liquid detection module includes an acidity detection module and a liquid level detection module; the acidity detection module is used to detect the pH value of the recovered liquid in the acid liquid recovery tank 90 in real time and send a detection signal to the control unit 50; the liquid level detection module is used to monitor the liquid level height in the acid liquid recovery tank 90 in real time and send a liquid level signal to the control unit 50; the control unit 50 is also used to: when it is detected that the pH value of the recovered liquid is within the set reuse range and the liquid level height exceeds the set value, control the recovered acid output control valve 401 to open and transport the recovered acid liquid to the mixed acid tank 20 for reuse; when it is detected that the pH value of the recovered liquid is not within the set reuse range or the liquid level height does not exceed the set value, close the recovered acid output control valve 401 to prevent the acid liquid from flowing back.

[0043] In this embodiment of the present invention, a solid-liquid separation device 80 is located downstream of the recovery port of the germanium oxide production unit 70 to receive the recovered liquid discharged from the germanium oxide production process. The recovered liquid typically contains a certain amount of solid impurities, such as incompletely reacted germanium compounds, precipitated byproducts, and suspended particulates. To ensure the quality of the liquid in the subsequent acid recovery tank 90 and to prevent impurities from interfering with the pH adjustment process, effective solid-liquid separation must be performed before recirculation.

[0044] The solid-liquid separation device 80 can be a conventional plate-and-frame filter press, centrifugal separator, or continuous filter device, preferably made of corrosion-resistant materials suitable for long-term stable operation in hydrochloric acid environments. The particle size separation range for solid-liquid separation is generally set between 10 and 50 microns, effectively removing most larger solid impurities. The separated liquid phase is collected and directed into the acid recovery tank 90, while the separated solid impurities are regularly discharged through the slag discharge channel to prevent system clogging.

[0045] The acid liquid recovery tank 90 is used to temporarily store the acidic liquid after solid-liquid separation. The acid liquid recovery tank 90 is usually made of acid-resistant and corrosion-resistant materials, such as polypropylene (PP), polyethylene (PE) or fiberglass. The interior of the tank body can be designed as a closed structure, with necessary ventilation holes at the top to prevent acid mist from escaping and polluting the environment. A drain port is provided at the bottom of the tank body, which is connected to the recovered acid output control valve 401. The effective volume of the acid liquid recovery tank 90 is designed according to the actual recovered liquid flow rate, generally 10% to 20% of the daily raw material processing volume, to ensure sufficient time for testing and decision-making of the recovered liquid.

[0046] To monitor the quality of the recovered acid in real time, the acid recovery tank 90 is equipped with a liquid detection module. The liquid detection module consists of two parts: an acidity detection module and a liquid level detection module. The acidity detection module uses an acid-resistant pH electrode that is directly inserted into the liquid inside the recovery tank to detect the pH value of the recovered liquid in real time. The electrode signal is sampled every 1-5 seconds, processed by the front-end signal conditioning circuit, and then sent to the control unit 50. The acidity detection module requires regular calibration to ensure the accuracy of the test data, with the calibration cycle preferably being performed every 500 hours of operation.

[0047] The liquid level detection module is used to monitor the liquid level within the acid recovery tank 90 in real time. Liquid level detection can be performed using a float level switch, ultrasonic level gauge, or hydrostatic level sensor. Corrosion-resistant, non-contact liquid level detection instruments are preferred to reduce maintenance during long-term use. Liquid level detection signals are also collected at a set frequency and transmitted to the control unit 50 for processing.

[0048] In the specific control rules, when the acidity detection module detects that the pH value of the recovered acid solution is within a pre-set reuse range, and the liquid level detection module detects that the liquid level in the tank exceeds a set threshold (e.g., 60% of the total tank height or a fixed liquid level), the control unit 50 determines that the recovered acid solution meets the reuse conditions. At this point, the control unit 50 issues a command to open the recovered acid output control valve 401, allowing the acid solution to flow through the recovery line into the mixed acid tank 20, where it mixes with the original acid or diluent and then re-enters the pH adjustment process. Conversely, if the pH value of the recovered acid solution is detected to be below or above the set reuse range, or if the liquid level does not reach the set height, the control unit 50 controls the recovered acid output control valve 401 to close, preventing the recovered acid solution from flowing back into the mixed acid tank 20. Acid solution that does not meet the conditions can subsequently be sent to a waste liquid treatment unit for treatment, preventing abnormal acid solution from affecting the acidity stability of the mixed acid tank 20.

[0049] During implementation, the pH range for reuse is typically adjusted based on process requirements. For example, if the pH of the mixed acid solution is required to be between 1.5 and 2.5, the pH range for the recovered acid solution can be set between 1.8 and 2.8. The liquid level can be set based on the designed capacity of the acid recovery tank 90 and the expected reflux volume, typically between 50% and 80% of the full tank height.

[0050] To further improve the utilization efficiency of the recovered acid solution, the acid solution recovery tank 90 can be equipped with a stirring device or a circulating pump to ensure uniform mixing of the recovered liquid within the tank, thereby avoiding pH misjudgments due to localized unevenness of the liquid. Furthermore, to prevent changes in the properties of the recovered acid solution due to prolonged retention, the control unit 50 can be configured with a maximum retention time monitoring logic. If it is detected that a batch of recovered liquid has been retained in the tank for longer than a set value (e.g., 8 or 12 hours), reflux can be prohibited and forced to drain, even if the pH and liquid level requirements are met, to ensure that the recovered liquid added to the mixed acid tank 20 is fresh and meets process requirements.

[0051] Based on the solution of the present invention, the solution of the present invention can realize the intelligent screening and dynamic reuse of the recovered acid solution, and effectively avoid the direct reflux of inferior recovered acid solution, which causes the acidity fluctuation of the mixed acid tank 20. At the same time, combined with online acidity detection and liquid level monitoring, the fully automatic control of the acid solution recovery process can be realized, without the need for frequent manual intervention, reducing operational errors, and improving the robustness and stability of the overall pH control system. Through the setting of the above-mentioned hydrochloric acid recovery device, the by-product acid solution resources in the germanium oxide production process can be fully utilized, and the recycling and reuse of the acid solution can be realized on the basis of ensuring that the liquid quality meets the set requirements, effectively reducing the original acid consumption and reducing production costs. At the same time, through intelligent detection and dynamic control of reflux conditions, the pH fluctuation of the mixed acid tank 20 caused by the reflux of inferior acid solution is avoided, the continuity and control accuracy of the subsequent pH adjustment reaction process are improved, and the stability and production efficiency of the germanium oxide product are further improved.

[0052] Preferably, the control unit 50 includes: an input membership function module, a fuzzy reasoning module and an output correction module; the input membership function module is used to fuzzify the pH deviation value and the pH deviation change rate obtained from the detection result of the pH sensor 60; wherein, the pH deviation value represents the difference between the pH set value and the detection value of the pH sensor 60; the pH deviation change rate is the rate of change of the pH deviation value over time; the fuzzy reasoning module generates correction amounts of proportional gain, integral gain and differential gain based on a preset fuzzy rule table; the output correction module is used to superimpose the correction amounts of proportional gain, integral gain and differential gain on the current PID parameters and apply them to the controller output in real time.

[0053] In this embodiment of the present invention, the control unit 50 includes an input membership function module, a fuzzy inference module, and an output correction module, which implement intelligent dynamic PID parameter adjustment control based on real-time pH detection values. To improve the stability and response speed of hydrochloric acid pH control during the germanium oxide production process, this embodiment improves on traditional PID control by introducing a fuzzy adaptive adjustment mechanism. This mechanism dynamically adjusts the proportional gain (Kp), integral gain (Ki), and differential gain (Kd) parameters based on real-time operating conditions, enhancing the adaptive capabilities of the pH adjustment process.

[0054] In the specific implementation process, the input membership function module receives the pH value detected in real time by the pH sensor 60, compares it with the set target pH value, and calculates the pH deviation value e(t). At the same time, the pH deviation value change within two consecutive sampling periods is collected to calculate the deviation change rate Δe(t), where:

[0055] ;

[0056] Wherein, Δt is the time interval between two consecutive samplings. The input membership function module performs fuzzy processing on the above-mentioned pH deviation value and deviation change rate. The fuzzification process mainly maps continuous real number inputs to a preset fuzzy set. Generally, membership functions such as trigonometric functions, trapezoidal functions or Gaussian functions can be used for processing. Usually, the pH deviation value and change rate are divided into 7 levels, such as large negative (NB), medium negative (NM), small negative (NS), zero (ZE), small positive (PS), medium positive (PM), and large positive (PB), and each level corresponds to a membership value.

[0057] After the affiliation process, the fuzzy reasoning module makes inferences and judgments based on the pre-designed fuzzy rule table. The fuzzy rule table can use the following rules as an example:

[0058] 1) IF (deviation value is PB) AND (deviation change rate is PS) THEN (proportional gain is slightly increased, integral gain is moderately increased, and differential gain is slightly increased);

[0059] 2) IF (deviation value is NB) AND (deviation change rate is NM) THEN (proportional gain is greatly increased, integral gain is greatly decreased, and differential gain is moderately increased);

[0060] 3) IF (deviation value is ZE) AND (deviation change rate is ZE) THEN (proportional gain is moderate, integral gain is moderate, and differential gain is moderate).

[0061] After the inference results are output, they are defuzzified (e.g., using the centroid method) to obtain the specific corrections for the proportional, integral, and differential parameters, recorded as ΔKp, ΔKi, and ΔKd, respectively. The output correction module adds the corrections generated by the inference to the current controller parameters. The updated PID parameters are:

[0062] ;

[0063] Finally, according to the corrected PID parameters, the valve opening control signal is output in real time. The specific PID control formula is as follows:

[0064] ;

[0065] Among them, u(t) is the output control quantity. The control unit 50 distributes u(t) proportionally to the opening adjustment quantities of the original acid addition control valve 101, the mixed acid addition control valve 201, the alkali solution addition control valve 301 and the recovered acid output control valve 401 according to the weight distribution principle set for the current operating conditions, and generates corresponding valve opening control instructions for each valve to realize multi-valve linkage adjustment of the pH value.

[0066] Example 1:

[0067] In the embodiment without an acid recovery device, the control unit 50 only dynamically adjusts the original acid addition control valve 101, the mixed acid addition control valve 201, and the alkali solution addition control valve 301. The control rules are as follows:

[0068] 1) When the pH deviation is negative and the rate of change is negative, increase the amount of alkali solution added and reduce the amount of original acid and mixed acid solution added.

[0069] 2) When the pH deviation is positive and the rate of change is positive, increase the amount of original acid or mixed acid solution and reduce the amount of alkali solution.

[0070] 3) When the pH deviation is close to zero and the deviation change rate is also close to zero, maintain the current valve opening and only slightly adjust the proportional parameters to keep the pH stable.

[0071] The valve opening adjustment is distributed based on the corrected PID output. In principle, valves that contribute most to pH changes are prioritized based on the current pH level. This embodiment significantly improves the response speed and accuracy of acid and alkali dosing and reduces pH fluctuations through intelligent adaptive PID regulation under a traditional three-valve control structure.

[0072] Example 2:

[0073] In an embodiment equipped with an acid recovery device, the control unit 50 must simultaneously control the original acid addition control valve 101, the mixed acid addition control valve 201, the alkali solution addition control valve 301, and the recovered acid output control valve 401. In addition to the three-valve basic control logic of Example 1, the following rules are added:

[0074] 1) When the pH value of the recovered acid solution is detected to be within the reusable range and the liquid level meets the set requirements, the recovered acid output control valve 401 is opened and the recovered acid solution enters the mixed acid tank 20.

[0075] 2) The recovered acid solution is regarded as one of the sources of mixed acid solution and participates in the concentration adjustment of mixed acid solution.

[0076] 3) If the pH value of the recovered acid solution is abnormal or the liquid level is insufficient, the recovered acid output control valve 401 is closed to stop the backflow.

[0077] 4) In the PID adjustment output results, add linkage control of the opening of the acid recovery valve to ensure the overall acidity supply balance.

[0078] Specifically, the control logic dynamically balances the ratio of raw acid addition to recycled acid reflux based on the acidity of the recycled acid solution, prioritizing the use of recycled acid that meets standards and reducing raw acid usage. While effectively utilizing recycled acid resources, this solution also enables intelligent, coordinated control of the four dosing valves, significantly improving the flexibility and energy efficiency of acid-base regulation while ensuring the continuity and stability of pH control and reducing resource consumption.

[0079] Figure 3 This is a flow chart of a method for controlling a hydrochloric acid pH control device in a germanium oxide production process provided by one embodiment of the present invention. Figure 3 As shown, an embodiment of the present invention provides a method for controlling a hydrochloric acid pH control device in a germanium oxide production process, the method comprising:

[0080] Step S10: The acid solution storage tank 10 delivers raw hydrochloric acid to the mixed acid tank 20 through the raw acid dosing control valve 101, and the raw hydrochloric acid is mixed with the diluent in the mixed acid tank 20 to form a mixed acid solution.

[0081] Specifically, the acid storage tank 10 stores industrial-grade raw hydrochloric acid, typically with a concentration between 28% and 32%. A raw acid dosing control valve 101 is installed at the outlet of the acid storage tank 10. This control valve controls the flow of hydrochloric acid. The valve can be opened according to a preset initial opening to ensure a reasonable initial acid mixing ratio. The diluent, typically deionized water or clean water that meets process requirements, is also delivered to the acid mixing tank 20 through a separate inlet. A stirring paddle or circulating pump is installed within the acid mixing tank 20 to continuously stir the mixed acid solution, ensuring thorough mixing of the acid and diluent and avoiding localized areas of high acid concentration. The stirring speed can be set during the mixing process, for example, at 300 rpm, to ensure a uniform mixed acid solution within 35 minutes. The initial acid mixing ratio can be adjusted as needed. For example, setting a target mixed acid pH between 1.5 and 2.0 can be achieved by controlling the volume ratio of raw acid to diluent, typically within a range of 1:2 to 1:4. A flow meter can be used to monitor the actual amounts of hydrochloric acid and diluent added, facilitating subsequent precise mixing.

[0082] Step S20 : ​​the mixed acid addition control valve 201 controls the mixed acid solution to flow into the pH adjustment reaction tank 40 , and the alkali solution addition control valve 301 adds alkali solution into the pH adjustment reaction tank 40 .

[0083] Specifically, a mixed acid injection control valve 201 is provided at the outlet of the mixed acid tank 20. By adjusting the opening of the mixed acid injection control valve 201, the volume flow rate of the mixed acid solution flowing into the pH adjustment reaction tank 40 per unit time is controlled. Initially, a constant flow rate, such as 5L / min to 20L / min, can be used, with subsequent dynamic adjustments based on the real-time pH. The pH adjustment reaction tank 40 is equipped with multiple liquid inlets: one for the mixed acid solution and one for the alkali solution. An alkali injection control valve 301 is also provided at the outlet of the alkali solution storage tank 30. The alkali solution is generally a 20% to 30% sodium hydroxide solution. The flow rate is initially set to be less than the mixed acid solution flow rate, for example, 10% to 30% of the mixed acid flow rate. A stirring unit operates continuously in the pH adjustment reaction tank 40 to ensure sufficient contact and reaction between the mixed acid solution and the alkali solution to form a unified reaction solution. The two liquid streams enter simultaneously, and the valve opening is initially set proportionally. Later, the acid and alkali injection ratio is dynamically adjusted based on real-time pH changes to achieve a precise balance.

[0084] Step S30 : The pH value of the solution in the pH adjustment reaction tank 40 is detected in real time by the pH sensor 60 , and the detected value is sent to the control unit 50 .

[0085] Specifically, an industrial pH electrode resistant to acid and alkali corrosion is installed inside the pH adjustment reaction tank 40, which is usually installed in the lower part of the tank body where the liquid turbulence is uniform to ensure the representativeness of the detection value. The pH electrode works continuously and collects data every 1 to 5 seconds. The specific sampling frequency can be adjusted according to the process volatility. The signal collected by the pH electrode is amplified and filtered by the front-end analog signal conditioning unit, and after eliminating the interference of environmental noise, it is sent to the control unit 50 in the form of a digital signal. Data transmission can use 4-20mA standard signal or RS485 bus communication. The pH detection process should ensure that the electrode is calibrated regularly. It is generally recommended to do it every 500 hours or every 30 days to avoid detection errors caused by electrode drift. Real-time pH data will serve as the basis for subsequent control algorithm calculations and judgments.

[0086] Step S40: The control unit 50 adopts an improved fuzzy adaptive PID control algorithm according to the pH detection value to dynamically adjust the openings of the original acid addition control valve 101, the mixed acid addition control valve 201 and the alkali solution addition control valve 301 to adjust the pH value of the hydrochloric acid within the target range.

[0087] Specifically, the control unit 50 first receives the real-time detection value from the pH sensor 60, compares it with the set target pH value, and calculates the current pH deviation e(t). Subsequently, the deviation change rate Δe(t) is calculated based on the deviation change in two consecutive detection cycles. These two quantities are fuzzified through the input membership function module and divided into multi-level fuzzy sets, such as large negative (NB), medium negative (NM), small negative (NS), zero (ZE), small positive (PS), medium positive (PM), large positive (PB), etc. The fuzzy reasoning module performs reasoning based on the preset fuzzy rule table to generate corrections for the proportional gain, integral gain, and differential gain. The output correction module superimposes the correction on the current PID parameters and updates the proportional, integral, and differential coefficients. Based on the new PID parameters, the total adjustment amount u(t) is calculated. In order to realize multi-valve linkage control, the total adjustment amount is distributed to each valve according to the preset distribution coefficient 𝛼𝑖. Finally, adjustment instructions are output to the original acid addition control valve 101, the mixed acid addition control valve 201 and the alkali solution addition control valve 301 respectively to achieve precise dynamic regulation of the acid and alkali flow rates, thereby quickly and stably maintaining the pH value in the reaction tank within the target setting range.

[0088] Preferably, the method further comprises: introducing the recovered liquid from the recovery port of the germanium oxide production unit 70 into the solid-liquid separation device 80 to separate the liquid phase and solid impurities; conveying the separated acidic liquid to the acid liquid recovery tank 90 for temporary storage; detecting the pH value of the acidic liquid in the acid liquid recovery tank 90 by an acidity detection module, and detecting the liquid level of the recovered liquid by a liquid level detection module; sending the detected acidity signal and liquid level signal to the control unit 50; when the control unit 50 detects that the pH value of the recovered liquid is within the set reuse range and the liquid level exceeds the set threshold, opening the recovered acid output control valve 401 to guide the recovered acid back to the mixed acid tank 20 to participate in the preparation of the mixed acid liquid; and when it is detected that the pH value or the liquid level does not meet the set conditions, closing the recovered acid output control valve 401 to prevent the recovered acid from reflux.

[0089] Preferably, the control unit 50 adopts an improved fuzzy adaptive PID control algorithm according to the pH detection value to dynamically adjust the opening of the raw acid addition control valve 101, the mixed acid addition control valve 201 and the alkali solution addition control valve 301 to adjust the pH value of the hydrochloric acid within the target range, including: collecting the pH detection value and the set value at the current moment to calculate the pH deviation value; calculating the change rate of the pH deviation value within the set time interval as the deviation change rate; inputting the pH deviation value and the deviation change rate into the input membership function module for fuzzy processing; through the fuzzy reasoning module, according to the preset fuzzy rule table, inferring the correction amount of the proportional gain, integral gain and differential gain; superimposing the correction amount to the proportional parameter, integral parameter and differential parameter of the current PID controller through the output correction module to obtain the corrected PID parameters; and applying the corrected PID parameters to real-time adjust the opening of the raw acid addition control valve 101, the mixed acid addition control valve 201 and the alkali solution addition control valve 301 to achieve closed-loop dynamic control of the pH value.

[0090] An embodiment of the present invention further provides a computer-readable storage medium having instructions stored thereon, which, when executed on a computer, enables the computer to execute the control method of the hydrochloric acid pH control device in the germanium oxide production process.

[0091] Those skilled in the art will appreciate that all or part of the steps in the methods described in the aforementioned embodiments can be performed by instructing the relevant hardware through a program. The program, stored in a storage medium, includes instructions for causing a microcontroller, chip, or processor to execute all or part of the steps in the methods described in the various embodiments of the present invention. The aforementioned storage medium includes various media capable of storing program code, such as a USB flash drive, a mobile hard drive, a read-only memory (ROM), a random access memory (RAM), a magnetic disk, or an optical disk.

[0092] The above describes in detail the optional embodiments of the present invention in conjunction with the accompanying drawings. However, the embodiments of the present invention are not limited to the specific details in the above embodiments. Within the technical concept of the embodiments of the present invention, a variety of simple modifications can be made to the technical solutions of the embodiments of the present invention, and these simple modifications all fall within the scope of protection of the embodiments of the present invention. It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner unless there is any contradiction. In order to avoid unnecessary repetition, the embodiments of the present invention will no longer describe the various possible combinations separately.

[0093] In addition, the various embodiments of the present invention may be arbitrarily combined, and as long as they do not violate the concept of the embodiments of the present invention, they should also be regarded as the contents disclosed in the embodiments of the present invention.

Claims

1. A hydrochloric acid pH control device in the germanium oxide production process, characterized in that: The device comprises: Acid storage tank, used to store raw hydrochloric acid, connected to the mixed acid tank through the raw acid dosing control valve; A mixed acid tank is used to mix the acid solution with the diluent and is connected to the pH adjustment reaction tank through a mixed acid addition control valve; Alkali liquid storage tank, used for storing alkali liquid, connected to pH adjustment reaction tank through alkali liquid addition control valve; A pH adjustment reaction tank is used to receive the mixed acid solution and the alkali solution and adjust the pH value of the reaction system, and is equipped with a pH sensor for real-time detection of the pH value; The control unit is used to dynamically adjust the opening of each valve to control the pH value within the target range based on the detection results of the pH sensor using an improved fuzzy adaptive PID control algorithm; The control unit is configured with a prediction module and a control logic module; the prediction module includes a data acquisition module, a sliding window processing module, and a trend extrapolation module; the data acquisition module is used to record the detection value and detection time of the pH sensor in real time to form a corresponding data set; the sliding window processing module is used to extract continuous pH value change data within a set time window from the data set; the trend extrapolation module uses a first-order linear extrapolation method based on the pH change rate within the sliding window to predict the expected future pH change trend, and inputs the predicted pH change trend into the control logic module, and the control logic module adjusts the opening of the original acid addition control valve and the alkali solution addition control valve at a preset time in advance according to the prediction result; The device also includes a hydrochloric acid recovery device disposed between the germanium oxide production unit and the mixed acid tank; the hydrochloric acid recovery device includes: a solid-liquid separation device connected to the recovery port of the germanium oxide production unit, used to separate solid impurities in the recovered liquid from the liquid phase; an acid recovery tank connected between the solid-liquid separation device and the mixed acid tank, the other end of the acid recovery tank being connected to the mixed acid tank via a recovered acid output control valve, and the acid recovery tank being used to collect and temporarily store the acidic liquid after solid-liquid separation; The acid liquid recovery tank is equipped with a liquid detection module; the liquid detection module includes an acidity detection module and a liquid level detection module; the acidity detection module is used to detect the pH value of the liquid recovered in the acid liquid recovery tank in real time and send a detection signal to the control unit; the liquid level detection module is used to monitor the liquid level in the acid liquid recovery tank in real time and send a liquid level signal to the control unit; The control unit is further configured to: When it is detected that the pH value of the recovered liquid is within the set reuse range and the liquid level exceeds the set value, the recovered acid output control valve is controlled to open and the recovered acid liquid is transported to the mixed acid tank for reuse; When it is detected that the pH value of the recovered liquid is not within the set reuse range or the liquid level height does not exceed the set value, the recovered acid output control valve is closed to prevent the acid from flowing back.

2. The device according to claim 1, characterized in that A temperature sensor is also provided in the pH adjustment reaction tank; The temperature sensor is used to collect temperature data of the solution in the pH adjustment reaction tank in real time; The control unit is provided with a temperature compensation module; The temperature compensation module calls a preset pH temperature compensation curve according to the temperature data of the solution; The original pH detection value is adjusted and corrected based on the pH temperature compensation curve, and the corrected pH value is transmitted to the control unit.

3. The device according to claim 1, characterized in that The control unit comprises: Input membership function module, fuzzy reasoning module and output correction module; The input membership function module is used to fuzzify the pH deviation value and pH deviation change rate obtained from the pH sensor detection result; wherein, The pH deviation value represents the difference between the pH set value and the pH sensor detection value; The pH deviation change rate is the rate of change of the pH deviation value over time; The fuzzy reasoning module generates correction values ​​of proportional gain, integral gain and differential gain based on a preset fuzzy rule table; The output correction module is used to add correction amounts of proportional gain, integral gain and differential gain to the current PID parameters and apply them to the controller output in real time.

4. A method for controlling a hydrochloric acid pH control device in a germanium oxide production process, characterized in that: The method includes a hydrochloric acid pH control device applied to the germanium oxide production process according to any one of claims 1 to 3, and the method includes: The original hydrochloric acid is transported from the acid storage tank to the mixed acid tank through the original acid dosing control valve, and is mixed with the diluent in the mixed acid tank to form a mixed acid liquid; The mixed acid addition control valve controls the mixed acid solution to flow into the pH adjustment reaction tank, and the alkali solution addition control valve adds alkali solution to the pH adjustment reaction tank. The pH value of the solution in the pH adjustment reaction tank is detected in real time by a pH sensor, and the detected value is sent to the control unit; The control unit adopts an improved fuzzy adaptive PID control algorithm according to the pH detection value to dynamically adjust the opening of the original acid addition control valve, the mixed acid addition control valve and the alkali solution addition control valve to adjust the pH value of the hydrochloric acid within the target range.

5. The method according to claim 4, characterized in that The method further comprises: The recovered liquid from the recovery port of the germanium oxide production unit is introduced into the solid-liquid separation device to separate the liquid phase and solid impurities; The separated acidic liquid is transported to the acid liquid recovery tank for temporary storage; The pH value of the acidic liquid in the acid recovery tank is detected by the acidity detection module, and the liquid level height of the recovered liquid is detected by the liquid level detection module; Sending the detected acidity signal and liquid level signal to the control unit; When the control unit detects that the pH value of the recovered liquid is within the set reuse range and the liquid level exceeds the set threshold, it opens the recovered acid output control valve to lead the recovered acid back to the mixed acid tank to participate in the preparation of the mixed acid liquid; When it is detected that the pH value or liquid level does not meet the set conditions, the recovered acid output control valve is closed to prevent the recovered acid from flowing back.

6. The method according to claim 5, characterized in that The control unit uses an improved fuzzy adaptive PID control algorithm based on the pH detection value to dynamically adjust the opening of the original acid addition control valve, the mixed acid addition control valve, and the alkali solution addition control valve to adjust the pH value of the hydrochloric acid within the target range, including: Collect the current pH detection value and the set value, and calculate the pH deviation value; Calculate the change rate of the pH deviation value within the set time interval as the deviation change rate; The pH deviation value and the deviation change rate are input into the input membership function module for fuzzy processing; Through the fuzzy reasoning module, according to the preset fuzzy rule table, the correction amount of proportional gain, integral gain and differential gain is inferred; The correction amount is added to the proportional parameter, integral parameter and differential parameter of the current PID controller through the output correction module to obtain the corrected PID parameters; The modified PID parameters are used to adjust the opening of the original acid addition control valve, mixed acid addition control valve and alkali solution addition control valve in real time to achieve closed-loop dynamic control of the pH value.

7. A computer-readable storage medium, characterized in that The computer-readable storage medium stores instructions, which, when executed on a computer, enable the computer to execute the control method of the hydrochloric acid pH control device in the germanium oxide production process according to any one of claims 4 to 6.

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