Online monitoring device for cyanide in water

Abstract

The invention relates to the technical field of cyanide monitoring, in particular to an online monitoring device for cyanide in water, which comprises lower computer analysis equipment and an upper computer analysis system, the lower computer analysis equipment comprises four treatment bins F1-F4 and six material bins C1-C6, a T pipeline is connected to the left side of the impurity removal bin F1, a B1 flow pump is arranged in the middle of the T pipeline, a G multi-parameter water quality sensor is arranged at the position, between the B1 flow pump and the impurity removal bin F1, of the T pipeline, and the G multi-parameter water quality sensor is connected with the lower computer analysis equipment. The G multi-parameter water quality sensor specifically comprises a pH sensor, a redox potential sensor, a conductivity sensor and a temperature sensor; according to the scheme, the water quality characteristics are sensed in real time by integrating the multi-parameter water quality sensor, and the intelligent dosing algorithm model is constructed based on the water quality characteristics, so that accurate and automatic dosing of a reducing agent, a precipitator, a strong acid, a complexing agent and a color developing agent is realized, and the influence of various interferents is effectively eliminated from the source; and the accuracy, efficiency and reliability of cyanide monitoring under the complex water quality background are remarkably improved.

Description

Technical Field

[0001] This invention relates to the field of cyanide monitoring technology, and in particular to an online monitoring device for cyanide in water. Background Technology

[0002] Cyanide monitoring in water is a crucial link in environmental monitoring and water pollution control, especially in areas such as industrial wastewater and surface water, where the requirements for accuracy, real-time performance, and anti-interference capabilities are extremely high.

[0003] Traditional devices are less resistant to interference from complex water quality. Common oxidants, sulfides, metal ions and organic nitrile substances in water samples can seriously interfere with the test results, leading to positive and negative deviations. Existing equipment lacks effective online pretreatment and intelligent dosing mechanisms to accurately eliminate these interferences.

[0004] To address this, the present invention proposes an online cyanide monitoring device for water quality. By integrating multi-parameter water quality sensors (pH, ORP, conductivity, and temperature) to perceive water quality characteristics in real time, and based on this, an intelligent dosing algorithm model is constructed to achieve precise and automatic dosing of reducing agents, precipitants, strong acids, complexing agents, and colorimetric agents. This effectively eliminates the influence of various interfering substances at the source and significantly improves the accuracy, efficiency, and reliability of cyanide monitoring under complex water quality conditions. Summary of the Invention

[0005] Technical problems to be solved: After testing, the water is severely affected by impurities, and existing equipment lacks effective online pretreatment and intelligent dosing mechanisms to accurately eliminate these interferences.

[0006] To address the shortcomings of existing technologies, this invention provides an online monitoring device for cyanide in water, thereby solving the technical problems mentioned in the background section.

[0007] To achieve the above objectives, the present invention provides the following technical solution: An online monitoring device for cyanide in water includes a lower-level analysis device and a higher-level analysis system; The lower-level analysis equipment includes four processing chambers (F1 to F4) and six material chambers (C1 to C6). A T-pipe is connected to the left side of the F1 impurity removal chamber. A B1 flow pump is installed in the middle of the T-pipe. A G multi-parameter water quality sensor is installed at the T-pipe between the B1 flow pump and the F1 impurity removal chamber. The G multi-parameter water quality sensor specifically includes a pH sensor, a redox potential sensor, a conductivity sensor, and a temperature sensor. The F4 processing chamber is made of glass, and it is equipped with an H light source and a K photoelectric sensor at the front and back, respectively. The host computer analysis system includes a data acquisition layer and a data analysis layer; The data acquisition layer continuously reads the values ​​of the G multi-parameter water quality sensor through the communication line, and at the same time reads the signal of the photoelectric sensor to obtain the absorbance value. The data analysis layer specifically includes analysis of reducing agent dosage, precipitant dosage, strong acid dosage, complexing agent dosage, colorimetric agent dosage, and cyanide content.

[0008] In one possible implementation, the top of the F1 impurity removal bin is connected to two material bins, C1 and C2, via a pipe. Material bin C1 contains a reducing agent, and material bin C2 contains a precipitating agent. The F1 impurity removal bin and material bin C1 are connected by a pipe, and a flow pump B2 is installed in the middle of the pipe. The F1 impurity removal bin and material bin C2 are connected by a pipe, and a flow pump B3 is installed in the middle of the pipe. The F2 filter chamber is located to the right of the F1 impurity removal chamber. The F2 filter chamber is connected to the F1 impurity removal chamber by a pipe. The F2 filter chamber is equipped with a ceramic filter element or membrane filter. The F3 distillation chamber is located above the F2 filter chamber. The F3 distillation chamber is connected to the F2 filter chamber by a pipe, and a B4 flow pump is installed in the middle of the pipe.

[0009] In one possible implementation, the top of the F3 distillation chamber is equipped with two material chambers, C3 and C4. The C3 material chamber contains a strong acid, and the C4 material chamber contains a complexing agent. The F3 distillation chamber and the C3 material chamber are connected by a pipe with a B5 flow pump installed in the middle of the pipe. The F3 distillation chamber and the C4 material chamber are also connected by a pipe with a B6 flow pump installed in the middle of the pipe.

[0010] In one possible implementation, the F3 distillation chamber and the F4 processing chamber are connected by an L inert pipe. The output end of the L inert pipe extends through the left side wall of the F4 processing chamber to the lower interior of the F4 processing chamber. The F4 processing chamber is pre-stored with an alkaline solution. Above the F4 processing chamber is a C6 material chamber, which contains a color developer. The C6 material chamber is connected to the F4 processing chamber by a pipe, and a B8 flow pump is installed in the middle of the pipe.

[0011] In one possible implementation, the reducing agent dosage analysis is based on real-time data collected by the ORP sensor to calculate the operating time of the B2 flow pump. The specific analysis logic is as follows: The reducing agent dosage analysis module presets the target ORP value for complete removal of the oxidant and the proportional coefficient Kp reduction-ORP corresponding to the ORP difference; only when the current ORP value collected by the ORP sensor is greater than the target ORP value, the dosage time is calculated according to the formula: B2 flow pump running time = (current ORP value - target ORP value) × Kp reduction-ORP; if the current ORP value is less than or equal to the target ORP value, the B2 flow pump running time is 0 seconds, and no reducing agent is added.

[0012] In one possible implementation, the precipitant dosage analysis is based on calculating the operating time of the B3 flow pump using real-time data collected by a conductivity sensor. The specific analysis logic is as follows: The precipitant dosage analysis module presets the EC precipitation threshold with low sulfide interference, the basic precipitant addition time, and the proportional coefficient Kpprecipitation-EC corresponding to the EC excess difference. If the current EC value collected by the conductivity sensor is ≤ EC precipitation threshold, then the B3 flow pump running time = basic precipitant addition time; if the current EC value is > EC precipitation threshold, then the B3 flow pump running time = basic precipitant addition time + (current EC value - EC precipitation threshold) × Kpprecipitation-EC.

[0013] In one possible implementation, the strong acid dosage analysis is based on real-time data collected by a pH sensor to calculate the operating time of the B5 flow pump. The specific analysis logic is as follows: The strong acid dosage analysis module is preset with CN. - The target pH value and the proportional coefficient Kp acid-pH corresponding to the pH difference are converted into HCN. The dosing time is calculated according to the formula: B5 flow pump running time -= (current pH value - target pH value) × Kp acid-pH only when the current pH value collected by the pH sensor is greater than the target pH value. If the current pH value is less than or equal to the target pH value, the B5 flow pump running time is 0 seconds and no strong acid is added.

[0014] In one possible implementation, the complexing agent dosage analysis is based on real-time data collected by a conductivity sensor to calculate the operating time of the B6 flow pump. The specific analysis logic is as follows: The complexing agent dosage analysis module presets a low-metal ion interference EC complexing threshold, a basic complexing agent dosage time, and a proportional coefficient Kp complexing-EC corresponding to the EC excess difference. If the current EC value collected by the conductivity sensor is ≤ EC complexing threshold, then the B6 flow pump running time = basic complexing agent dosage time; if the current EC value is > EC complexing threshold, then the B6 flow pump running time = basic complexing agent dosage time + (current EC value - EC complexing threshold) × Kp complexing-EC.

[0015] In one possible implementation, the analysis of the color developer dosage is based on calculating the running time of the B6 flow pump according to a preset fixed alkaline solution volume in the F4 treatment chamber. The specific analysis logic is as follows: The volume of alkaline solution in the F4 treatment chamber is fixed at 1000ml. The colorimetric reagent dosage analysis module is preset with a proportional coefficient Kp (colorimetric-volume) corresponding to the volume. The dosage time is calculated according to the formula: B6 flow pump running time = F4 treatment chamber alkaline solution volume × Kp (colorimetric-volume).

[0016] In one possible implementation, the cyanide content analysis is based on calculating the cyanide concentration in the water sample using the transmitted light signal collected by the K photoelectric sensor. The specific analysis logic is as follows: For data preprocessing, the cyanide content analysis module controls the K photoelectric sensor to continuously collect the transmitted light intensity 10 times, and after removing the maximum and minimum values, the average value is taken as the effective transmitted light intensity; at the same time, the transmitted light intensity of the blank alkaline solution without colorimetric reagent in the F4 treatment chamber is collected as the blank transmitted light intensity. Absorbance is calculated using the formula: Asample = -lg(Isample / I0), where "Isample / I0" is the transmittance. Concentration deduction: The cyanide content analysis module pre-stores a concentration standard curve equation, which is obtained through 5 sets of CN... - The standard solution was obtained by linear regression fitting after color development and detection. Substituting the calculated value of sample A into the equation, the cyanide concentration is obtained.

[0017] Beneficial effects compared to existing technologies: 1. In this solution, real-time monitoring by multi-parameter sensors and intelligent dosing control achieve precise removal of interfering substances and optimization of reagent dosage. The device is equipped with pH, ​​ORP, conductivity, and temperature sensors to collect key parameters of water samples in real time, and dynamically calculates the dosage of reducing agent, precipitant, strong acid, and complexing agent based on this data. The reducing agent dosage is precisely controlled based on ORP readings to eliminate oxidant interference, and the dosage of precipitant and complexing agent is adjusted based on conductivity data to address sulfides and metal ions. This intelligent dosing mechanism avoids the problems of excessive or insufficient reagents in traditional methods, significantly improving the removal efficiency of interfering substances, reducing reagent waste, ensuring the accuracy and reliability of subsequent detection steps, and lowering operating costs. 2. In this scheme, efficient separation and recovery of cyanide are achieved by combining heating distillation with carrier gas purging. The device uses a heater in the distillation chamber to provide heat energy, breaking down the metal-cyanide complex structure, releasing free cyanide ions and generating volatile HCN gas. Simultaneously, nitrogen gas is introduced as a carrier gas to continuously carry away HCN molecules, preventing gas phase saturation and ensuring a rapid and thorough volatilization process. The HCN gas is then absorbed by an alkaline solution and converted back into cyanide ions for detection. This design effectively overcomes the problem of incomplete cyanide release in complex water conditions, improves cyanide recovery rate, and avoids detection deviations caused by uneven heating or insufficient gas flow in traditional distillation methods, thereby enhancing the representativeness and accuracy of monitoring data. 3. In this solution, rapid and automated quantification of cyanide concentration is achieved through photoelectric detection and standard curve analysis. The device is equipped with an LED light source and photoelectric sensors in the treatment chamber. By measuring the absorbance of the solution after color development, the cyanide concentration is calculated based on Lambert-Beer's law. The host computer system has a pre-calibrated "absorbance-concentration" standard curve built-in, which can automatically convert sensor data into concentration values, enabling real-time back-calculation and display. This method replaces manual colorimetry and offline analysis, not only shortening the detection time (fully automated from sampling to result output) but also reducing human error, ensuring the repeatability and reliability of monitoring results. It is suitable for continuous online monitoring scenarios, greatly improving the efficiency and response speed of water quality supervision. Attached Figure Description

[0018] The above description is merely an overview of the technical solution of the present invention. In order to better understand the technical means of the present invention and to implement it in accordance with the contents of the specification, the preferred embodiments of the present invention are described in detail below with reference to the accompanying drawings.

[0019] Figure 1 This is a planar sectional view of the present invention; Figure 2 This is a schematic diagram of the F4 processing chamber of the present invention; Figure 3 This is a framework diagram of the host computer analysis system of the present invention. Detailed Implementation

[0020] Preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention can also be implemented in various different forms, and therefore the present invention is not limited to the embodiments described below. In addition, for the purpose of more clearly describing the present invention, parts not connected to the invention will be omitted from the drawings. The technical solution in this application embodiment is to solve the problems mentioned in the background art, and the overall idea is as follows: Example

[0021] Cyanide (CN) - The detection of α, especially commonly used colorimetric methods (such as the isonicotinic acid-barbituric acid method and the pyridine-barbituric acid method) and electrode methods, is easily affected by a variety of substances. These interferences are mainly divided into two categories: positive interference (leading to higher results) and negative interference (leading to lower results). Positive interferences mainly include oxidants (Cl2) and sulfides (S...). 2- ), metal ions (Ni) 2+ (etc.), the main interfering substances for negative interference include thiocyanate (SCN) - ), certain nitrile organic compounds; Based on the above, please refer to Figures 1 to 3 As shown in the figure, this embodiment introduces the specific structure of an online monitoring device for cyanide in water, including a lower-level analysis device and a higher-level analysis system; Please refer to Figure 1 , 2 As shown, the lower-level analysis equipment includes four processing chambers (F1 to F4) and six material chambers (C1 to C6). F1 is a cleaning chamber. A T-pipe is connected to the left side of the F1 cleaning chamber. The T-pipe is connected to a water source. A B1 flow pump is installed in the middle of the T-pipe. By turning on the B1 flow pump, water can be delivered to the interior of the F1 cleaning chamber. A multi-parameter water quality sensor (G) is installed at the T-pipe between the B1 flow pump and the F1 impurity removal chamber. The G multi-parameter water quality sensor specifically includes a pH sensor, an oxidation-reduction potential (ORP) sensor, a conductivity sensor, and a temperature sensor. pH sensors are primarily used to detect the acidity or alkalinity of liquids in water sources, providing an initial pH reference for subsequent distillation steps. This helps estimate the volume of strong acid that needs to be added, ensuring that CN is adequately distilled. - The process involves converting the water sample to HCN. The oxidation-reduction potential (ORP) sensor is primarily used to detect the oxidizing or reducing power of the water source. Based on the ORP readings, the volume of reducing agent to be pumped from the C1 material silo needs to be precisely calculated to ensure complete removal of the oxidant without overdosing. The conductivity sensor is mainly used to detect the approximate concentration of total dissolved ions (salt) in the water. Detecting whether it is freshwater or high-salt wastewater helps predict interference levels, as abnormally high conductivity may indicate a high concentration of other ions in the water sample, potentially causing background interference in the final colorimetric analysis. The temperature sensor is primarily used to detect the current temperature of the water sample, automatically correcting the pH, ORP, and conductivity readings to ensure accuracy. Furthermore, a heating distillation method is used subsequently, as the initial temperature can also serve as a reference for heating power or time.

[0022] The top of the F1 impurity removal chamber is connected to two material chambers, C1 and C2, via pipes. Material chamber C1 contains a reducing agent (such as sodium sulfite solution), and material chamber C2 contains a precipitating agent (such as lead acetate solution). A flow pump B2 is installed in the middle of the pipe between the F1 impurity removal chamber and material chamber C1, and a flow pump B3 is installed in the middle of the pipe between the F1 impurity removal chamber and material chamber C2. The flow pumps B2 and B3 respectively transport the reducing agent in material chamber C1 and the precipitating agent in material chamber C2 into the F1 impurity removal chamber. F2 is the filter chamber, which is located to the right of the F1 impurity removal chamber and is connected to the F1 impurity removal chamber by a pipe. The inlet of the pipe is located at the bottom of the F1 impurity removal chamber and the outlet is located on the top of the F2 filter chamber. The F2 filter chamber is equipped with a ceramic filter element or a membrane filter. F3 is the distillation chamber, which is located above the F2 filtration chamber and connected to the F2 filtration chamber by a pipe. The inlet of the pipe is located at the bottom of the F2 filtration chamber, and the outlet is located at the lower right side of the F3 distillation chamber. A B4 flow pump is installed in the middle of the pipe. The B4 flow pump draws the liquid from inside the F1 impurity removal chamber, filters it through the F2 filtration chamber, and then flows into the F3 distillation chamber. The top of the F3 distillation chamber has two material chambers, C3 and C4. The C3 material chamber contains a strong acid (such as phosphoric acid or sulfuric acid), and the C4 material chamber contains a complexing agent (such as EDTA). The F3 distillation chamber is connected to both the C3 and C4 material chambers by pipes. A B5 flow pump is installed in the middle of the pipe between the F3 distillation chamber and the C3 material chamber, and a B6 flow pump is installed in the middle of the pipe between the F3 distillation chamber and the C4 material chamber. The B5 flow pump and the B6 flow pump respectively deliver the strong acid in the C3 material chamber and the complexing agent in the C4 material chamber to the F3 distillation chamber. The F3 distillation chamber is equipped with an R heater, which provides the kinetic energy to break the chemical bonds of the metal-cyanide complex by heating. This involves converting thermal energy into molecular kinetic energy, intensifying molecular vibrations, and thus making it easier to break the complex structure and release free cyanide ions (CN). - It reacts immediately with acid to form HCN; To the left of the F3 distillation chamber is the C5 material chamber, which is a gas storage device containing high-pressure gas, specifically carrier gas (such as nitrogen). The C5 material chamber is connected to the F3 distillation chamber by a pipeline, with a B7 gas valve installed in the middle of the pipeline. When the B7 gas valve is opened, the carrier gas inside the C5 material chamber enters the F3 distillation chamber and works together with the R heater in the reaction liquid inside. The R heater heats and generates a large number of HCN gas molecules, which, with the introduced nitrogen as a carrier, form a flowing gas flow above the liquid surface. The flowing gas continuously "carries away" the escaping HCN molecules and delivers them to the subsequent detection unit. Without the flow of carrier gas, the gas phase above the liquid surface would gradually reach saturation, and the volatilization would slow down. However, the flow of carrier gas breaks this balance, allowing the volatilization process to continue continuously and rapidly to the end. The F4 processing chamber is located to the right of the F3 distillation chamber. The F3 and F4 processing chambers are connected by an inert L-shaped pipe (such as a PTFE pipe). The inlet of the inert L-shaped pipe is located on the upper right side of the F3 distillation chamber, and its outlet extends through the left side wall of the F4 processing chamber to the lower interior. The F4 processing chamber contains a pre-stored alkaline solution (such as sodium hydroxide solution) to absorb HCN gas and convert it back to CN. - ; Above the F4 processing chamber is a C6 material chamber, which contains a color developer (such as isonicotinic acid-barbituric acid). The C6 material chamber is connected to the F4 processing chamber via a pipe, in the middle of which is a B8 flow pump. The color developer is added to the absorbent liquid inside the F4 processing chamber by activating the B8 flow pump. - It undergoes a series of reactions with the color developer to generate a stable blue compound; The F4 processing chamber is made of glass and has an H light source and a K photoelectric sensor at the front and back, respectively. The H light source is an LED light source. The intensity of the transmitted light is detected by the photoelectric sensor on the other side when the H light source illuminates the solution. The darker the solution color (the higher the cyanide concentration), the greater the absorbance and the weaker the light signal received by the photoelectric sensor. Then, the concentration of cyanide can be calculated by using a pre-calibrated curve. Please refer to Figure 3 As shown, the host computer analysis system includes a data acquisition layer and a data analysis layer; The data acquisition layer continuously reads the values ​​of the multi-parameter water quality sensor (pH, ORP, conductivity, temperature) through the communication line. On the other hand, during the detection stage, it reads the signal from the photoelectric sensor to obtain the absorbance value.

[0023] The data analysis layer specifically includes analysis of reducing agent dosage, precipitant dosage, strong acid dosage, complexing agent dosage, colorimetric agent dosage, and cyanide content, as detailed below: 1. Calculate the dosage of reducing agent based on ORP readings: The time for adding the reducing agent (i.e., the running time of the B2 flow pump) is directly proportional to the difference between the current ORP reading and the target ORP value. That is, the larger the difference, the stronger the oxidizing power of the water sample, the more oxidant is needed for reduction, the longer the running time of the B2 flow pump, and the more sodium sulfite is added. If the current ORP value is less than or equal to the target ORP value, it means that the oxidizing power of the water sample meets the standard, and the B2 flow pump does not run to avoid excessive reducing agent.

[0024] Key parameter definitions: Current ORP: The ORP value of the water sample read in real time by the system from the G multi-parameter water quality sensor (ORP module) (unit: mV, collected once every 1 second, data is retained in integer places, the sensor needs to be calibrated in advance to ensure that the error is ≤ ±5mV). Target ORP: The system's preset ORP threshold for complete oxidant removal (fixed at 0mV, which can be recalibrated through reduction experiments on oxidant-containing water samples in the laboratory; for example, it can be adjusted to +20mV for high-chlorine water samples). Kp reduction-ORP: The reducing agent addition ratio coefficient corresponding to the ORP difference (unit: seconds / mV, determined experimentally, such as 0.03 seconds / mV, which means that for every 1mV exceeding the target ORP value, 0.03 seconds of reducing agent needs to be added. The coefficient needs to be calibrated monthly to avoid the influence of sensor drift). Quantitative calculation: The running time of the B2 flow pump is calculated only when "current ORP > target ORP". The running time of the B2 flow pump (seconds) = (current ORP - target ORP) × Kp reduction - ORP; if "current ORP ≤ target ORP", the running time of the B2 flow pump = 0 seconds (no reducing agent is added). Example: Assume the system reads the current ORP of the water sample as +250mV in real time, the target ORP is set to 0mV, and the Kp reduction-ORP calibrated by the laboratory is 0.03 seconds / mV; first determine the direction of the ORP difference: the current ORP (+250mV) > the target ORP (0mV), so a reducing agent needs to be added; then calculate the ORP difference (reflecting the degree of oxidant excess) = current ORP - target ORP = 250mV - 0mV = 250mV; then calculate the running time of the B2 flow pump (quantifying the amount of reducing agent added) = 250mV × 0.03 seconds / mV = 7.5 seconds; subsequently, the host computer sends a "run for 7.5 seconds" command to the B2 flow pump, and the sodium sulfite solution is transported from the C1 material silo to the F1 impurity removal silo, completing the addition.

[0025] 2. Calculate the amount of precipitant to be added based on conductivity data: The total time for adding precipitant = the basic precipitant addition time + the additional precipitant addition time corresponding to the excess conductivity. The "additional addition time" is directly proportional to the difference between "actual conductivity - conductivity threshold." That is, the larger the difference, the higher the potential sulfide content, and the more additional precipitant is needed to ensure complete sulfide precipitation. If the conductivity is below the threshold, it indicates a low sulfide content, and only a fixed basic amount needs to be added to avoid precipitant waste or overdose (excessive lead acetate will react with the subsequent complexing agent EDTA, affecting the metal ion chelation effect). Key parameter definitions: Current EC: The system reads the conductivity value of water samples in real time from the G multi-parameter water quality sensor (unit: μS / cm, collected once every 1 second, data retained in integer places); EC sedimentation threshold: The system's preset critical value for low sulfide interference conductivity (fixed at 1000 μS / cm, which can be recalibrated and adjusted in the laboratory according to the actual water quality characteristics of the monitoring area; for example, it can be increased to 1200 μS / cm in high-salt background areas). Kp precipitation-EC: The precipitant addition ratio coefficient corresponding to conductivity (unit: seconds / μS / cm, determined experimentally, e.g., 0.02 seconds / μS / cm means that for every 1μS / cm exceeding the EC precipitation threshold, an additional 0.02 seconds of precipitant needs to be added). Basic precipitant addition time: When the current EC ≤ EC precipitation threshold, the sulfide content in the water sample is low, ensuring the fixed precipitant addition time for basic interference removal (experimental calibration, such as 5 seconds, at which time sulfides with a concentration ≤0.1mg / L can be removed). Quantitative calculation: If the current EC ≤ EC precipitation threshold (1000 μS / cm): B3 flow pump running time = basic precipitant addition time (no additional addition required to avoid overdose); If the current EC > EC precipitation threshold (1000 μS / cm): B3 flow pump running time = basic precipitant addition time + (current EC - EC precipitation threshold) × Kp precipitation - EC (matching high sulfide requirements through additional addition); Example: Assume the system reads the current EC of the water sample in real time as 1300 μS / cm, the EC sedimentation threshold is set to 1000 μS / cm, the Kp sedimentation-EC is calibrated in the laboratory to be 0.02 s / μS / cm, and the basic precipitant addition time is 5 seconds; first calculate the excess conductivity value (reflecting the risk of excess sulfide) = current EC - EC sedimentation threshold = 300 μS / cm; then calculate the additional precipitant addition time (to match the excess sulfide removal requirements) = excess conductivity value × Kp sedimentation-EC = 6 seconds; then calculate the total running time of the B3 flow pump = basic precipitant addition time + additional precipitant addition time = 11 seconds; finally, the host computer sends a "run for 11 seconds" command to the B3 flow pump, the sulfide reacts fully with lead acetate to generate PbS precipitate, which is then intercepted by the ceramic filter element of the F2 filter chamber, completely eliminating sulfide interference.

[0026] 3. Calculate the dosage of strong acid based on pH readings: CN - It needs to react with H under acidic conditions. + Combined to generate HCN (CN) - +H + =HCN↑) can only be carried out by the carrier gas through distillation, therefore the pH of the water sample in the F3 distillation chamber needs to be stably controlled within the target range of 1.5~2.0; the higher the initial pH of the water sample, the higher the OH content. - The more alkaline substances there are, the greater the amount of strong acid required for neutralization; conversely, the less acid is required. The control algorithm quantifies the alkalinity that needs to be neutralized by the difference between the current pH and the target pH. The greater the difference, the more strong acid is added to ensure that the pH is accurately reduced to the target range. Key parameter definitions: Current pH: The pH value of the water sample from the F3 distillation chamber is read in real time by the system from the G multi-parameter sensor (sampling once every 1 second, and the reading is retained to 1 decimal place). Target pH: The system's preset target pH for acidic distillation (fixed at 2.0, but can be fine-tuned depending on the type of acid; for example, it can be set to 1.8 when using sulfuric acid). Kp acid-pH: Acid addition ratio coefficient corresponding to pH (unit: seconds / pH unit, determined experimentally, e.g., 0.8 seconds / pH unit means that 0.8 seconds of acid needs to be added for every 1 unit exceeding the target pH). Note: If the current pH is less than or equal to the target pH, it means that the water sample has reached the acidity requirement and no acid needs to be added. The B5 flow pump will not run. Quantitative calculation: When the current pH > the target pH, the running time of the B5 flow pump = (current pH - target pH) × Kp acid - pH.

[0027] Example: Assume the system reads the current pH as 4.5, the target pH as 2.0, and the Kp acid-pH ratio as 0.8 seconds / pH unit. First, calculate the pH difference = 4.5 - 2.0 = 2.5 pH units; then calculate the B5 flow pump running time = 2.5 pH units × 0.8 seconds / pH unit = 2.0 seconds; finally, the host computer sends a "run for 2.0 seconds" command to the B5 flow pump.

[0028] 4. Calculate the dosage of the complexing agent based on conductivity data: Metal ions (such as Ni) 2+ It will form a stable metal-cyanide complex with CN⁻, hindering HCN formation. Therefore, EDTA is needed to chelate metal ions to release free CN. - Conductivity is positively correlated with the concentration of metal ions in water: the higher the conductivity, the more dissolved ions (including metal ions) are in the water sample, and the more abundant the metal-cyanide complex may be, requiring a larger amount of EDTA; conversely, the lower the conductivity, the smaller the amount required. The system has a preset "low metal ion conductivity threshold" (e.g., 1500 μS / cm, experimentally calibrated). Below the threshold, the baseline amount is used; above the threshold, the amount is increased proportionally to ensure sufficient complex disruption. Key parameter definitions: Current EC: The water sample conductivity value (unit: μS / cm, collected once every 1 second) is read in real time from the G multi-parameter sensor by the system. EC complexation threshold: The system's preset critical value for low metal ion conductivity (fixed at 1500 μS / cm, which can be recalibrated experimentally). Kp complexation-EC: The ratio of complexing agent dosage to conductivity (unit: seconds / μS / cm, determined experimentally, e.g., 0.01 seconds / μS / cm). Basic chelating agent addition time: When the current EC ≤ EC chelation threshold, the water sample has few metal ions, and the required fixed EDTA addition time (experimental calibration, such as 8 seconds).

[0029] Note: If the current EC is less than or equal to the EC complexation threshold, only the basic amount of EDTA needs to be added; if the current EC is greater than the threshold, additional EDTA needs to be added.

[0030] Quantitative calculation: If the current EC ≤ EC complexation threshold (1500 μS / cm): B6 flow pump running time = basic complexing agent dosing time; If the current EC > EC complexation threshold (1500 μS / cm): B6 flow pump running time = basic complexing agent dosing time + (current EC - EC complexation threshold) × Kp complexation - EC; Example: Assume the system reads the current EC value as 1800 μS / cm, the EC complexation threshold as 1500 μS / cm, the Kp complexation-EC time as 0.01 s / μS / cm, and the basic complexing agent addition time as 8 seconds. First, calculate the excess conductivity value as 300 μS / cm. Then, calculate the additional complexing agent addition time as 300 μS / cm × 0.01 s / μS / cm = 3 seconds. Next, calculate the total running time of the B6 flow pump as 8 seconds + 3 seconds = 11 seconds. Finally, the host computer sends a "run for 11 seconds" command to the B6 flow pump to ensure that EDTA sufficiently chelates metal ions and releases free CN. - .

[0031] 5. Calculate the dosage of colorimetric reagent based on the volume of liquid received in the F4 treatment tank: In the F4 treatment chamber, HCN is absorbed by the alkaline solution and converted into CN. - Afterwards, it needs to fully react with the isonicotinic acid-barbituric acid colorimetric reagent to generate a blue compound (used for photoelectric detection); the colorimetric reagent needs to be "sufficient but not excessive," otherwise CN will be detected. - Incomplete reaction leads to lower detection results; excessive amounts increase background absorbance, interfering with readings; while CN... - The total amount is positively correlated with the volume of the alkaline solution (the larger the volume of the alkaline solution, the more HCN and CN are absorbed). - The more total amount, the greater the amount of color developer needed. Therefore, the amount of color developer added must be proportional to the volume of the alkaline solution to ensure that there is a sufficient amount of color developer in each unit volume of alkaline solution. Key parameter definitions: The volume of alkaline solution in the F4 treatment chamber is a fixed value, set at 1000ml. Kp colorimetric-volume: The ratio coefficient of colorimetric reagent addition corresponding to the volume of liquid collected (unit: seconds / mL, determined experimentally, e.g., 0.3 seconds / mL means that 0.3 seconds of colorimetric reagent needs to be added for every 1 mL of liquid collected). Quantitative calculation: B8 flow pump running time = F4 treatment chamber alkaline solution volume × Kp color development - volume; Example: Kp color development - volume is 0.1 seconds / 100mL; first calculate the running time of B8 flow pump = 1000mL × 0.1 seconds / 100mL = 10 seconds; finally, the host computer sends a "run for 10 seconds" command to B8 flow pump to add color developer.

[0032] 6. Cyanide content analysis based on K photoelectric sensor data: F4 processing warehouse, CN - It reacts with isonicotinic acid-barbituric acid to form a stable blue compound, CN. - The higher the concentration, the deeper the blue color, the stronger the absorption of 600nm light by the solution, the weaker the intensity of transmitted light received by the K photoelectric sensor, and the greater the calculated absorbance; conversely, the lower the concentration, the weaker the blue color, the stronger the absorption of 600nm light by the solution, the weaker the intensity of transmitted light received by the K photoelectric sensor, and the greater the calculated absorbance; conversely, the lower the concentration, the weaker the absorbance ... - The lower the concentration, the stronger the transmitted light intensity and the lower the absorbance. By establishing a standard curve of "absorbance-cyanide concentration", CN can be inversely calculated from the K photoelectric sensor data. - content; Absorbance is calculated using the derivation of Lambert-Beer's Law. The absorbance of the solution (Asample) is derived from the effective transmitted light intensity (Isample) and the blank transmitted light intensity (I0), with the formula: Asample = -lg(Isample / I0). Isample / I0 represents the transmittance (T), which is the proportion of light transmitted through the solution to the blank light. Absorbance is the negative logarithm of transmittance, converting the exponential change in light intensity into a linear change in concentration, facilitating subsequent correlation with CN. - Establish a linear relationship based on concentration; for example, I0 = 500 μW / cm 2 Isample = 250 μW / cm2 2 Then the transmittance T = 250 / 500 = 0.5, and the absorbance A sample = -lg0.5 ≈ 0.301.

[0033] Cyanide concentration deduction (based on a standard curve): The core of concentration calculation is a "preset standard curve"—using known concentrations of CN in the laboratory. - To prepare a standard solution, a linear regression equation of absorbance-concentration was established. Then, the absorbance of the sample (sample A) was substituted into the equation to calculate CN. - concentration, The standard curve was prepared by mixing five groups of CN at different concentrations. -Standard solutions (e.g., 0.001 mg / L, 0.01 mg / L, 0.1 mg / L, 0.5 mg / L, 1.0 mg / L, covering the system's detection range of 0.001~1.0 mg / L); each set of standard solutions was operated according to the detection procedure of the F4 processing chamber: add 1000 ml of alkaline solution for absorption, add an equal amount of colorimetric reagent, stir for 10 minutes for color development; use an H light source and a K photoelectric sensor to detect the absorbance of each set of solutions (A standard 1~A standard 5), and record the corresponding data of "standard concentration (c standard) - absorbance (A standard)"; then, with c standard as the abscissa and A standard as the ordinate, perform linear regression fitting to obtain the standard curve equation: c = k × A + b (k is the slope of the curve, b is the intercept, stored in the host computer system after experimental calibration, and calibrated once a month); for example, the standard curve equation obtained after calibration is c = 1.6 × A - 0.002 (unit: mg / L), where k = 1.6 (mg·L -1 ·A -1 b = -0.002 (mg / L, close to 0, indicating minimal blank interference). The sample concentration is calculated by substituting the sample absorbance (sample A) into the standard curve equation to obtain the actual concentration of cyanide in the F4 treatment chamber (sample c). The calculation formula is csample = k × Asample + b. For example, if sample A = 0.301 (corresponding to the case of sample I = 250 μW / cm² mentioned above), substituting into the standard curve equation, csample = 0.48 mg / L, meaning that the cyanide concentration in the current water sample is approximately 0.48 mg / L.

[0034] Finally, it should be noted that the above embodiments are merely examples for clearly illustrating the present invention and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. An online monitoring device for cyanide in water, comprising a lower-level analysis device and a higher-level analysis system; characterized in that: The lower-level analysis equipment includes four processing chambers (F1 to F4) and six material chambers (C1 to C6). A T-pipe is connected to the left side of the F1 impurity removal chamber. A B1 flow pump is installed in the middle of the T-pipe. A G multi-parameter water quality sensor is installed at the T-pipe between the B1 flow pump and the F1 impurity removal chamber. The G multi-parameter water quality sensor specifically includes a pH sensor, a redox potential sensor, a conductivity sensor, and a temperature sensor. The F4 processing chamber is made of glass, and it is equipped with an H light source and a K photoelectric sensor at the front and back, respectively. The host computer analysis system includes a data acquisition layer and a data analysis layer; The data acquisition layer continuously reads the values ​​of the G multi-parameter water quality sensor through the communication line, and also reads the signal of the photoelectric sensor to obtain the absorbance value. The data analysis layer specifically includes analysis of reducing agent dosage, precipitant dosage, strong acid dosage, complexing agent dosage, colorimetric agent dosage, and cyanide content.

2. The online monitoring device for cyanide in water as described in claim 1, characterized in that, The top of the F1 impurity removal bin is connected to two material bins, C1 and C2, via a pipe. Material bin C1 contains a reducing agent, and material bin C2 contains a precipitant. The F1 impurity removal bin and material bin C1 are connected by a pipe, and a flow pump B2 is installed in the middle of the pipe. The F1 impurity removal bin and material bin C2 are connected by a pipe, and a flow pump B3 is installed in the middle of the pipe. The F2 filter chamber is located to the right of the F1 impurity removal chamber. The F2 filter chamber is connected to the F1 impurity removal chamber by a pipe. The F2 filter chamber is equipped with a ceramic filter element or membrane filter. The F3 distillation chamber is located above the F2 filter chamber. The F3 distillation chamber is connected to the F2 filter chamber by a pipe, and a B4 flow pump is installed in the middle of the pipe.

3. The online monitoring device for cyanide in water as described in claim 1, characterized in that, The top of the F3 distillation chamber has two material chambers, C3 and C4. The C3 material chamber contains a strong acid, and the C4 material chamber contains a complexing agent. The F3 distillation chamber and the C3 material chamber are connected by a pipe with a B5 flow pump installed in the middle of the pipe. The F3 distillation chamber and the C4 material chamber are connected by a pipe with a B6 flow pump installed in the middle of the pipe.

4. The online monitoring device for cyanide in water as described in claim 1, characterized in that, The F3 distillation chamber and the F4 processing chamber are connected by an L inert pipe. The output end of the L inert pipe extends through the left side wall of the F4 processing chamber to the lower interior of the F4 processing chamber. The F4 processing chamber is pre-stored with an alkaline solution. Above the F4 processing chamber is a C6 material chamber, which contains a color developer. The C6 material chamber is connected to the F4 processing chamber by a pipe, and a B8 flow pump is installed in the middle of the pipe.

5. The online monitoring device for cyanide in water as described in claim 1, characterized in that, The analysis of the reducing agent dosage is based on the calculation of the running time of the B2 flow pump using real-time data collected by the ORP sensor. The specific analysis logic is as follows: The reducing agent dosage analysis module presets the target ORP value for complete removal of the oxidant and the proportional coefficient Kp reduction-ORP corresponding to the ORP difference; only when the current ORP value collected by the ORP sensor is greater than the target ORP value, the dosage time is calculated according to the formula: B2 flow pump running time = (current ORP value - target ORP value) × Kp reduction-ORP; if the current ORP value is less than or equal to the target ORP value, the B2 flow pump running time is 0 seconds, and no reducing agent is added.

6. The online monitoring device for cyanide in water as described in claim 1, characterized in that, The precipitant dosage analysis is based on the calculation of the running time of the B3 flow pump using real-time data collected by the conductivity sensor. The specific analysis logic is as follows: The precipitant dosage analysis module presets the EC precipitation threshold with low sulfide interference, the basic precipitant addition time, and the proportional coefficient Kp precipitation-EC corresponding to the EC excess difference; if the current EC value collected by the conductivity sensor is ≤ EC precipitation threshold, then the B3 flow pump running time = basic precipitant addition time. If the current EC value is greater than the EC precipitation threshold, then the B3 flow pump running time = basic precipitant addition time + (current EC value - EC precipitation threshold) × Kp precipitation - EC.

7. The online monitoring device for cyanide in water as described in claim 1, characterized in that, The strong acid dosage analysis is based on the calculation of the B5 flow pump's operating time using real-time data collected by the pH sensor. The specific analysis logic is as follows: The strong acid dosage analysis module is preset with CN. - The target pH value and the proportional coefficient Kp acid-pH corresponding to the pH difference are converted into HCN. The dosing time is calculated according to the formula: B5 flow pump running time -= (current pH value - target pH value) × Kp acid-pH only when the current pH value collected by the pH sensor is greater than the target pH value. If the current pH value is less than or equal to the target pH value, the B5 flow pump running time is 0 seconds and no strong acid is added.

8. The online monitoring device for cyanide in water as described in claim 1, characterized in that, The analysis of the complexing agent dosage is based on the calculation of the running time of the B6 flow pump using real-time data collected by the conductivity sensor. The specific analysis logic is as follows: The complexing agent dosage analysis module is preset with a low metal ion interference EC complexing threshold, a basic complexing agent dosage time, and a proportional coefficient Kp complexing-EC corresponding to the EC excess difference. If the current EC value collected by the conductivity sensor is less than or equal to the EC complexation threshold, then the running time of the B6 flow pump is equal to the basic complexing agent addition time. If the current EC value is greater than the EC complexation threshold, then the B6 flow pump running time = basic complexing agent dosing time + (current EC value - EC complexation threshold) × Kp complexation - EC.

9. The online monitoring device for cyanide in water as described in claim 1, characterized in that, The analysis of the colorimetric reagent dosage is based on the calculation of the running time of the B6 flow pump according to the preset fixed alkaline solution volume in the F4 treatment chamber. The specific analysis logic is as follows: The volume of alkaline solution in the F4 treatment chamber is fixed at 1000ml. The colorimetric reagent dosage analysis module is preset with a proportional coefficient Kp (colorimetric-volume) corresponding to the volume. The dosage time is calculated according to the formula: B6 flow pump running time = F4 treatment chamber alkaline solution volume × Kp (colorimetric-volume).

10. The online monitoring device for cyanide in water as described in claim 1, characterized in that, The cyanide content analysis is based on the transmitted light signal collected by the K photoelectric sensor to calculate the cyanide concentration in the water sample. The specific analysis logic is as follows: For data preprocessing, the cyanide content analysis module controls the K photoelectric sensor to continuously collect the transmitted light intensity 10 times, and after removing the maximum and minimum values, the average value is taken as the effective transmitted light intensity; at the same time, the transmitted light intensity of the blank alkaline solution without colorimetric reagent in the F4 treatment chamber is collected as the blank transmitted light intensity. Absorbance is calculated using the formula: Asample = -lg(Isample / I0), where "Isample / I0" is the transmittance. Concentration deduction: The cyanide content analysis module pre-stores a concentration standard curve equation, which is obtained through 5 sets of CN... - The standard solution was obtained by linear regression fitting after color development and detection. Substituting the calculated value of sample A into the equation, the cyanide concentration is obtained.

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