Multi-stage treatment method and system for lead smelting wastewater

Abstract

The invention relates to the technical field of wastewater treatment, in particular to a multi-stage treatment method and system for lead smelting wastewater. The method comprises the following steps: acquiring water quality data of the multi-source lead-acid storage battery smelting wastewater, and based on the water quality data, analyzing to obtain a battery wastewater multiphase feature set; on the basis, the information of the stabilized intermediate water body is obtained by dynamically adjusting the hydrogen ion concentration, breaking a complexing structure and preferentially separating fluoride; on the basis, the antimony valence state and the antimony concentration are monitored in real time, the oxidizing agent type and the reaction intensity are matched in a self-adaptive mode, oriented efficient conversion of antimony is achieved, and low-antimony pre-sedimentation water outlet information is obtained; on the basis, according to the dynamic proportion of the inlet water hydrogen ion concentration to the lead and antimony ions, a precipitation path control instruction is automatically switched, a purified water body with lead and antimony synchronously and deeply removed is obtained, and a lead smelting wastewater multi-stage treatment log is output. Harmful pollutants in the lead smelting wastewater process are efficiently removed, the method adapts to water quality fluctuation, consumption reduction and cost saving are achieved, compliance treatment of wastewater is achieved, and environment-friendly and economic values are achieved.

Description

Technical Field

[0001] This application relates to the field of wastewater treatment technology, and in particular to a multi-stage treatment method and system for lead smelting wastewater. Background Technology

[0002] In the lead smelting wastewater process, the treatment of smelting wastewater from lead-acid batteries is a crucial aspect of environmental protection. This type of wastewater mainly originates from the crushing, sorting, smelting, and refining processes of discarded lead-acid batteries. It has a complex composition, with characteristic pollutants including antimony introduced as an alloy hardening agent, fluorine from the electrolyte, and the main metal, lead. Currently, the widely used wastewater treatment process in this field is a chemical precipitation method based on fixed parameters. For example, this involves uniformly adding alkali to adjust the pH value and using a precipitant to remove heavy metal ions.

[0003] However, existing technologies have significant shortcomings. Due to differences in raw material sources, battery models, and production batches, the actual wastewater produced exhibits strong dynamic fluctuations and multiphase characteristics in terms of water quality and pollutant morphology. Fixed treatment parameters and processes cannot adapt to this complexity, leading to problems such as incomplete removal of complex structures, severe fluoride ion interference, low conversion efficiency of trivalent antimony, and competitive inhibition of lead-antimony precipitation in actual operation. Therefore, there is an urgent need to develop a multi-stage treatment method that can intelligently sense water quality characteristics and dynamically optimize treatment strategies. Summary of the Invention

[0004] This application provides a multi-stage treatment method and system for lead smelting wastewater to solve the above-mentioned problems.

[0005] In a first aspect, this application provides a multi-stage treatment method for lead smelting wastewater. The method includes: acquiring water quality data of multi-source lead-acid battery smelting wastewater; analyzing the concentration and speciation differences of antimony, fluoride, and lead in the wastewater based on the water quality data to obtain a multi-phase characteristic set of battery wastewater; based on the multi-phase characteristic set of battery wastewater, breaking the complex structure and preferentially separating fluorides by dynamically adjusting the hydrogen ion concentration to obtain information on stabilized intermediate water bodies; based on the information on stabilized intermediate water bodies, monitoring the antimony valence state and antimony concentration in real time, adaptively matching the type of oxidant and reaction intensity to achieve directional and efficient conversion of antimony, and obtaining information on low-antimony pre-precipitated effluent; based on the information on low-antimony pre-precipitated effluent, autonomously switching the precipitation path control command according to the influent hydrogen ion concentration and the dynamic ratio of lead and antimony ions to obtain purified water with simultaneous deep removal of lead and antimony, and outputting a multi-stage treatment log of lead smelting wastewater.

[0006] Through the above technical solutions, intelligent analysis of water quality characteristics and dynamic adjustment of treatment parameters can efficiently break down complex structures, preferentially separate fluorides, and achieve directional oxidation of antimony and simultaneous deep removal of lead and antimony. This improves treatment efficiency and stability, enhances adaptability, and can cope with fluctuations in wastewater quality. It also reduces chemical reagent consumption and sludge production, lowers operating costs, and provides a high degree of automation, reducing the burden of manual operation. Furthermore, the process is traceable through treatment logs, providing support for optimized management. Ultimately, it ensures that wastewater meets discharge standards or is reused, demonstrating significant environmental and economic value.

[0007] Optionally, the water quality data includes antimony concentration, trivalent antimony ratio, fluoride ion concentration, and lead concentration. Based on the fluoride ion concentration, the interference effect of fluoride on heavy metal precipitation during lead smelting wastewater treatment is analyzed using fluoride ion complexometric titration to obtain fluoride separation priority. Based on the antimony concentration and the trivalent antimony ratio, the existing forms and transformation difficulty of antimony are analyzed using high-performance liquid chromatography-atomic fluorescence spectrometry to obtain a primary judgment factor for antimony treatment. Based on the lead concentration and the fluoride separation priority and the primary judgment factor for antimony treatment, the competitive and synergistic relationships among lead, antimony, and fluoride affecting precipitation are analyzed to obtain the multiphase characteristic set of the battery wastewater.

[0008] Optionally, based on the fluoride separation priority and the primary judgment factor for antimony treatment, the intensity of complexation interference of fluoride ions on the precipitation reaction of lead and antimony, and the inhibitory effect of trivalent antimony on the precipitation efficiency of lead, are analyzed using complexometric titration technology to obtain pretreatment guidance information prioritizing the elimination of fluoride interference. The complexation refers to the coordination binding between molecules or ions in wastewater and metal ions. Based on the pretreatment guidance information, the optimal reaction conditions required for fluoride precipitation are analyzed by adding acid to the wastewater to adjust the hydrogen ion concentration, thus obtaining fluoride separation process parameters. Based on the fluoride separation process parameters, the final precipitation information of lead and antimony ions after the elimination of fluoride interference is analyzed by sequentially adding oxidant and precipitant, thus obtaining the competitive and synergistic relationship for achieving simultaneous deep removal of lead and antimony.

[0009] Optionally, based on the fluoride separation priority and the primary judgment factor for antimony treatment, the initial hydrogen ion complex-breaking concentration boundary corresponding to the target complex structure is determined; based on the initial hydrogen ion complex-breaking concentration boundary, acid is added to the wastewater, and the dynamic process of complex structure breaking is analyzed by linking the changes in hydrogen ion concentration and the response of fluoride ion concentration, thus obtaining a hydrogen ion-fluoride concentration response curve; based on the hydrogen ion-fluoride concentration response curve, the inflection point of efficient fluoride precipitation and the critical point of side reaction risk are analyzed by chemical precipitation method to determine the hydrogen ion regulation threshold for dynamic addition control; based on the hydrogen ion regulation threshold, the form and concentration of residual heavy metals in the water after the reaction and solid-liquid separation are analyzed by spectral detection to obtain the information of the stabilized intermediate water for subsequent processes.

[0010] Optionally, based on the initial hydrogen ion concentration boundary for breaking down the complex, an acid addition gradient is used to analyze the acid addition gradient required to initially loosen the complex structure, thus obtaining step-by-step addition control information. Based on the step-by-step addition control information, acid is sequentially added to the wastewater by real-time monitoring of hydrogen ion concentration, and fluoride ion concentration is simultaneously detected after each addition step. The correlation between changes in hydrogen ion concentration and fluoride ion release is analyzed to obtain a linked monitoring dataset. Based on the linked monitoring dataset, the transition interval where the fluoride ion release rate increases stepwise with increasing hydrogen ion concentration is analyzed to obtain information on the transition of the complex breaking down stage. Based on the information on the transition of the complex breaking down stage, the hydrogen ion-fluoride concentration response curve is constructed by dynamically tracking the entire process from the critical point to the plateau period of fluoride ion concentration.

[0011] Optionally, based on the hydrogen ion-fluoride concentration response curve corresponding to the water body after fluoride separation, the total antimony concentration and the ratio of trivalent antimony in the current water body are analyzed by atomic fluorescence spectrometry to obtain the antimony concentration ratio; based on the antimony concentration ratio and combined with the pretreatment guidance information, an oxidant addition strategy for preferentially converting trivalent antimony to pentavalent antimony is matched using chemical oxidation technology; based on the oxidant addition strategy, the dynamic changes of oxidation-reduction potential and residual antimony concentration are analyzed by controlling the oxidant addition rate and the mixing energy of the reaction tank, and the oxidation stage is adaptively adjusted to the reaction endpoint to obtain antimony high-efficiency conversion control information; based on the antimony high-efficiency conversion control information, a precipitant is added to the oxidized water body and solid-liquid separation is performed, and the residual antimony concentration in the supernatant is analyzed to determine whether it reaches a preset threshold to obtain the low-antimony pre-precipitated effluent information.

[0012] Optionally, based on the antimony concentration ratio and the pretreatment guidance information, the composition of oxidants and substances affecting oxidation efficiency in the current water body, excluding antimony, is analyzed to obtain oxidant compatibility constraints. Based on the oxidant compatibility constraints, by comparing the oxidation potential and reaction selectivity of different oxidants under different hydrogen ion concentration conditions, the optimal type of oxidant that avoids harmful side reactions while ensuring oxidation efficiency is analyzed to obtain primary oxidant screening results. Based on the primary oxidant screening results, by analyzing the hydrogen ion concentration buffering capacity and exothermic characteristics of the reaction process of the target water body, the initial addition concentration, addition rate, and reaction temperature control range of the selected oxidant are dynamically determined to obtain the oxidant addition strategy for preferentially converting trivalent antimony to pentavalent antimony.

[0013] Optionally, based on the hydrogen ion-fluorine concentration response curve, atomic absorption spectrometry is used to analyze the current hydrogen ion concentration and the dynamic ratio of lead and antimony ions in the water body to obtain a working condition judgment factor. Based on the working condition judgment factor, different chemical environments required to achieve deep removal of lead and antimony are analyzed, and a precipitation path control instruction sequence is executed. The precipitation path control instruction sequence includes a priority precipitation path control instruction and a co-precipitation path control instruction. The priority precipitation path control instruction specifically includes: adding a lead-specific precipitant to the water body first and separating the precipitate, then adding an antimony-specific precipitant, analyzing the stepwise removal effect of lead and antimony, and obtaining first purified water body information. The co-precipitation path control instruction specifically includes: adding a lead-antimony composite precipitant to the water body all at once and controlling the reaction conditions, analyzing the simultaneous co-precipitation effect of lead and antimony, and obtaining second purified water body information. The first purified water body information and the second purified water body information are integrated to construct a multi-stage treatment log for the lead smelting wastewater.

[0014] Optionally, based on the influent hydrogen ion concentration and the dynamic ratio of lead and antimony ions, chemical equilibrium simulation technology is used to analyze the differences in chemical equilibrium conditions and precipitant selectivity of lead and antimony precipitation reactions when using the preferential precipitation path and the co-precipitation path, respectively, to obtain path reaction characteristic comparison information. Based on the path reaction characteristic comparison information and the information of the stabilized intermediate water body, precipitation separation technology is used to analyze the types, dosage ranges, and reaction conditions of the specific precipitant or composite precipitant required for each of the two paths to achieve the deep removal target, to obtain the path switching decision logic. Based on the path switching decision logic, autonomous switching is performed: when the dynamic ratio of lead and antimony ions is greater than a preset lead dominance threshold, the control command for initiating the preferential precipitation path with the goal of preferential lead precipitation is executed; when the dynamic ratio of lead and antimony ions is less than or equal to the lead dominance threshold and greater than the preset antimony dominance threshold, the control command for initiating the co-precipitation path with the goal of achieving lead and antimony co-precipitation is executed.

[0015] Secondly, this application provides a multi-stage treatment system for lead smelting wastewater. The system includes: a multiphase analysis module for acquiring water quality data of multi-source lead-acid battery smelting wastewater, analyzing the concentration and speciation differences of antimony, fluoride, and lead in the wastewater based on the water quality data, and obtaining a multiphase feature set of battery wastewater; a dynamic adjustment module for dynamically adjusting the hydrogen ion concentration based on the multiphase feature set of battery wastewater, breaking the complex structure and preferentially separating fluorides to obtain information on stabilized intermediate water; an adaptive matching module for monitoring the antimony valence state and concentration in real time based on the stabilized intermediate water information, adaptively matching the type of oxidant and reaction intensity to achieve directional and efficient conversion of antimony, and obtaining information on low-antimony pre-precipitated effluent; and an instruction switching module for autonomously switching the precipitation path control instruction based on the low-antimony pre-precipitated effluent information and the dynamic ratio of influent hydrogen ion concentration and lead-antimony ions to obtain purified water with simultaneous deep removal of lead and antimony, and outputting a multi-stage treatment log of lead smelting wastewater. Attached Figure Description

[0016] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0017] Figure 1 This is a schematic diagram illustrating an application scenario provided in one embodiment of this application; Figure 2 A flowchart of a multi-stage treatment method for lead smelting wastewater provided in one embodiment of this application; Figure 3 This is a schematic diagram of a multi-stage treatment system for lead smelting wastewater provided in one embodiment of this application. Detailed Implementation

[0018] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of this application. All other embodiments obtained by those skilled in the art based on the embodiments of this application without creative effort are within the scope of protection of this application.

[0019] Furthermore, the term "and / or" in this article is merely a description of the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, or B existing alone. Additionally, the character " / " in this article, unless otherwise specified, generally indicates that the preceding and following related objects have an "or" relationship.

[0020] The embodiments of this application will now be described in further detail with reference to the accompanying drawings.

[0021] In the recycling and smelting process of lead-acid batteries, existing wastewater treatment technologies are difficult to adapt to fixed parameters and processes due to the dynamic fluctuations and multiphase characteristics of water quality. This results in unstable treatment effects, high costs, and secondary risks, and there is an urgent need for intelligent and dynamically optimized multi-stage treatment technologies.

[0022] Based on this, this application provides a multi-stage treatment method and system for lead smelting wastewater. Through intelligent analysis of water quality and dynamic parameter adjustment, it efficiently breaks down complexes to remove fluoride, removes antimony in a targeted manner, and simultaneously removes lead and antimony at a deep level. It is adaptable to water quality fluctuations, saves on chemicals and reduces costs, is automated and traceable, and ensures that the wastewater meets discharge standards or can be reused, thus possessing both environmental and economic value.

[0023] Figure 1 This application provides an schematic diagram of an application scenario. In the process of recycling and smelting lead-acid batteries, the method provided in this application is used to selectively remove pollutants such as fluoride, antimony, and lead from wastewater, thereby improving the stability and reliability of lead smelting wastewater treatment and ensuring that the effluent meets the standards.

[0024] Specifically, the method provided in this application can be applied to any server. The server interacts with the monitoring equipment of the wastewater treatment station to obtain water quality data of multi-source lead-acid battery smelting wastewater provided by the monitoring equipment. It can intelligently adapt to water quality fluctuations, dynamically adjust treatment parameters, and output multi-level treatment logs of lead smelting wastewater to wastewater smelting staff, thereby achieving process traceability and providing support for optimized management.

[0025] For specific implementation details, please refer to the following examples.

[0026] Figure 2 This is a flowchart illustrating a multi-stage treatment method for lead smelting wastewater according to an embodiment of this application. The method of this embodiment can be applied to the server in the above scenario. Figure 2 As shown, the method includes: S201. Obtain water quality data of multi-source lead-acid battery smelting wastewater. Based on the water quality data, analyze the differences in concentration and speciation of antimony, fluorine, and lead in the wastewater to obtain a multiphase characteristic set of battery wastewater.

[0027] Multi-source lead-acid battery smelting wastewater can be mixed wastewater from the lead-acid battery recycling and smelting process, and the data source can be the monitoring equipment of the wastewater treatment station of the lead-acid battery smelting enterprise. Water quality data can include the physicochemical parameters and pollutant information of the wastewater. The concentrations of antimony, fluorine, and lead can represent the content of pollutants in the wastewater (e.g., antimony concentration 0.5-10 mg / L, fluorine concentration 20-100 mg / L, lead concentration 5-50 mg / L). The differences in the speciation of antimony, fluorine, and lead can represent their chemical states (e.g., antimony exists as trivalent or pentavalent, lead exists as free ions or in a complexed state). The multiphase characteristic set of battery wastewater can be a comprehensive dataset of the complex characteristics of the wastewater.

[0028] Specifically, the wastewater generated during the recycling and smelting process of lead-acid batteries has diverse sources and complex composition. Among them, the concentrations of pollutants such as antimony, fluorine, and lead fluctuate greatly and have different forms. For example, antimony may exist in trivalent or pentavalent states, and lead may exist in free or complexed states. This makes it difficult for existing treatment processes using fixed parameters to operate stably and efficiently. By collecting and analyzing water quality data from multiple wastewater sources, a multiphase characteristic set of battery wastewater that can accurately reflect the concentration range, form distribution, and interaction of pollutants can be obtained, providing a core data foundation for subsequent targeted graded treatment.

[0029] S202. Based on the multiphase characteristic set of battery wastewater, by dynamically adjusting the hydrogen ion concentration, breaking the complex structure and preferentially separating fluoride, information on the stabilized intermediate water body is obtained.

[0030] Dynamically adjusting hydrogen ion concentration can be a process of adjusting wastewater pH. Breaking complex structures can involve disrupting stable bonds between heavy metals and ligands. Preferentially separating fluorides can mean removing fluoride ions before other pollutants. Stabilized intermediate water body information can be the state parameters of the water body after fluoride removal and complex breaking.

[0031] Specifically, fluoride ions in wastewater readily form stable complexes with heavy metals, severely hindering the effective precipitation and removal of heavy metals. Direct subsequent treatment not only consumes a large amount of reagents but also makes it difficult to guarantee the removal effect. Based on the multiphase characteristics of battery wastewater, automatic dosing and real-time pH feedback control are adopted to dynamically adjust the hydrogen ion concentration in the system. For example, the pH is precisely adjusted to a strongly acidic range. Under this condition, on the one hand, calcium salt is added to preferentially form calcium fluoride precipitate to separate fluoride. On the other hand, the acidic environment is used to effectively break the complex structure between heavy metals and organic ligands, releasing free heavy metal ions. This results in a stabilized intermediate water body where interfering factors are removed in advance and the activity of heavy metals is enhanced, creating favorable conditions for subsequent advanced treatment.

[0032] S203. Based on the information of the stabilized intermediate water body, the antimony valence state and antimony concentration are monitored in real time, and the type of oxidant and reaction intensity are adaptively matched to achieve the directional and efficient conversion of antimony and obtain information on low antimony pre-precipitated effluent.

[0033] Real-time monitoring of antimony valence state and concentration allows for online detection of antimony oxidation state and content. Adaptive oxidant matching enables intelligent selection of oxidants based on monitoring results. Targeted and efficient conversion allows for the selective oxidation of antimony to easily precipitated valence states. Low-antimony pre-precipitation effluent information provides data on the water body after preliminary antimony removal.

[0034] Specifically, antimony in different valence states exhibits significantly different precipitation properties. Pentavalent antimony is easier to precipitate and remove, while trivalent antimony, commonly found in wastewater, is more difficult to treat. If a uniform oxidation or precipitation method is used, efficient and deep removal of antimony cannot be achieved. By targeting the valence state sensitivity of antimony treatment and based on information from stabilized intermediate water bodies, online spectral monitoring and other methods are used to track the valence state distribution and concentration changes of antimony in the water body in real time. The intelligent algorithm model adaptively matches the type of oxidant. For example, hydrogen peroxide is automatically selected for systems dominated by trivalent antimony, while potassium permanganate is selected for complex systems. At the same time, the dosage of oxidant is dynamically calculated and controlled based on the real-time concentration to achieve the directional and efficient conversion of trivalent antimony to pentavalent antimony. After conversion, pre-precipitated effluent with a significantly reduced antimony concentration is obtained through preliminary precipitation.

[0035] S204. Based on the low antimony pre-precipitation effluent information, according to the dynamic ratio of influent hydrogen ion concentration and lead-antimony ion concentration, the sedimentation path control command is automatically switched to obtain purified water with simultaneous deep removal of lead and antimony, and outputs a multi-stage treatment log of lead smelting wastewater.

[0036] The influent hydrogen ion concentration and lead-antimony ratio can be defined as the influent pH and lead-antimony content ratio during the precipitation step. The autonomous sedimentation path switching control command can automatically select the sedimentation method based on conditions. Simultaneous deep removal of lead and antimony can simultaneously remove lead and antimony contaminants at a deep level. Purified water refers to wastewater that meets treatment standards. The multi-stage treatment log for lead smelting wastewater can be a file recording the entire process operation and data.

[0037] Specifically, in the deep sedimentation stage, lead and antimony exhibit both competitive and synergistic precipitation effects. The optimal sedimentation path dynamically changes with parameters such as influent pH and the lead-antimony ion ratio. Using a single precipitant cannot simultaneously achieve deep removal of both under varying conditions. To address this co-precipitation challenge, based on low-antimony pre-precipitated effluent information, the system acquires real-time data on influent hydrogen ion concentration and the dynamic ratio of lead and antimony ions. Through a pre-defined decision rule base, the system autonomously switches sedimentation paths. For example, when the lead-antimony ratio is high and the pH is suitable, it automatically switches to the sulfide precipitation path with sodium sulfide addition; when the lead-antimony ratio is low, it switches to the hydroxide precipitation path with sodium hydroxide addition, thereby achieving simultaneous deep removal of lead and antimony and obtaining purified water. All key parameters, equipment status, and water quality changes throughout the multi-stage treatment process are automatically recorded by the central control system, forming a complete treatment log for process traceability and optimization.

[0038] The method provided in this embodiment intelligently analyzes water quality characteristics and dynamically adjusts treatment parameters, which can efficiently break down complex structures, preferentially separate fluorides, and achieve directional oxidation of antimony and simultaneous deep removal of lead and antimony. This improves treatment efficiency and stability, has strong adaptability, can cope with fluctuations in wastewater quality, reduce chemical reagent consumption and sludge production, and lower operating costs. At the same time, it has a high degree of automation, reducing the burden of manual operation, and achieves process traceability through treatment logs, providing support for optimized management. Ultimately, it ensures that wastewater meets discharge standards or is reused, which has significant environmental and economic value.

[0039] In some embodiments, water quality data include antimony concentration, trivalent antimony ratio, fluoride ion concentration, and lead concentration. Based on fluoride ion concentration, the interference effect of fluoride on heavy metal precipitation during lead smelting wastewater treatment is analyzed using fluoride ion complexometric titration to obtain fluoride separation priority. Based on antimony concentration and trivalent antimony ratio, the existing forms and transformation difficulty of antimony are analyzed using high-performance liquid chromatography-atomic fluorescence spectrometry to obtain a primary judgment factor for antimony treatment. Based on lead concentration, combined with fluoride separation priority and the primary judgment factor for antimony treatment, the competitive and synergistic relationships among lead, antimony, and fluoride affecting precipitation are analyzed to obtain a multiphase characteristic set of battery wastewater.

[0040] Antimony concentration can be the total amount of antimony in wastewater. The trivalent antimony ratio can be the percentage of the more toxic and difficult-to-precipitate trivalent antimony form (Sb(III)) in the total antimony content. Fluoride ion concentration can be the content of free fluoride ions in wastewater. Lead concentration can be the total amount of lead in wastewater. Fluoride ion complexometric titration is a classic analytical chemistry method that uses indicators and titrants (such as lanthanum or zirconium salt solutions) that selectively react with fluoride ions to accurately determine the fluoride ion concentration. High-performance liquid chromatography-atomic fluorescence spectrometry (HPLC-AQFII) is an advanced speciation analysis technique; HPLC is used to separate antimony compounds of different valence states and forms, while atomic fluorescence spectrometry provides extremely high detection sensitivity and specificity. Fluoride separation priority can be a qualitative or semi-quantitative indicator based on the analysis of fluoride ion concentration and its complexation interference intensity. The primary antimony treatment judgment factor can be a parameter that integrates information on total antimony and the trivalent antimony ratio.

[0041] Specifically, lead-acid battery smelting wastewater is a typical example of complex and difficult-to-treat industrial wastewater containing multiple pollutants. Antimony (introduced as a hardening agent), fluoride (from battery electrolytes and smelting auxiliary materials), and lead (the main smelting target) are the three key characteristic pollutants. Existing wastewater treatment processes often treat these pollutants as independent removal targets, employing fixed processes (such as neutralization-precipitation). However, the actual results are often unsatisfactory, and the effluent fails to consistently meet standards. The fundamental reason is that these pollutants are not simply mixed in the wastewater but exhibit complex chemical interactions. To address this problem: First, mixed samples of multi-source wastewater from lead smelting processes (such as crushing and washing, and flue gas purification) were collected. Initial water quality data were obtained using standard water quality analysis methods. For example, the total antimony concentration was measured to be 2.5 mg / L, with trivalent antimony accounting for 60%, the fluoride ion concentration to be 150 mg / L, and the lead concentration to be 50 mg / L. Next, to address the interference of fluoride ions, a fluoride ion complexation titration technique was employed: a certain volume of water sample was taken, and sodium alizarin sulfonate-zirconium salt was added as an indicator. Titration was performed using lanthanum nitrate standard solution. The endpoint, where the solution faded from pink to yellow, indicated that fluoride ions were quantitatively complexed. The accurate concentration of fluoride ions was calculated based on the volume of titrant consumed, and a comparative experiment was designed—at the same lead and antimony concentrations, the precipitation rate of heavy metals was measured with and without fluoride, thereby quantifying the degree of inhibition of precipitation by fluoride ions (e.g., a 40% reduction in lead precipitation rate in the presence of fluoride). Based on this, a fluoride separation priority index was generated to guide process sequencing. Simultaneously, for the speciation analysis of antimony, high-performance liquid chromatography-atomic fluorescence spectrometry was used: the water sample was passed through an anion exchange column, eluted using a phosphate buffer gradient, to separate trivalent antimony (Sb(II)). I) is separated from pentavalent antimony (Sb(V)); the effluent is introduced into an atomic fluorescence spectrometer, reduced by potassium borohydride to produce hydrides, and detected by excitation at a specific wavelength to obtain the chromatographic peak area of ​​each form of antimony, thereby accurately calculating the proportion of trivalent antimony (e.g., confirming 60% as Sb(III)) and assessing its oxidation difficulty (Sb(III) requires a strong oxidant), forming a primary judgment factor for antimony treatment. Finally, by combining lead concentration data with the above two analytical results, through laboratory simulation and theoretical calculation, the differences in the complexation stability constants of fluoride ions with lead and antimony, as well as the influence of trivalent antimony on the pH window for lead precipitation, are analyzed, thus fully revealing the synergistic competitive mechanism of "fluoride complexation masking heavy metals and trivalent antimony competitively inhibiting lead precipitation", and integrating all information to construct a multiphase characteristic set of battery wastewater for customizing subsequent multi-stage treatment processes.

[0042] The method provided in this embodiment accurately captures the characteristics of multi-source lead-acid battery smelting wastewater, clarifies the concentration, form, and interaction patterns of antimony, fluorine, and lead, provides a scientific basis for subsequent treatment, effectively avoids blind treatment, improves the targeting and efficiency of complex breaking, fluoride removal, and lead and antimony removal, avoids problems such as incomplete pollutant removal, ensures that the effluent meets standards, and lays a solid foundation for the efficient purification of lead smelting wastewater.

[0043] In some embodiments, based on the priority of fluoride separation and combined with the primary judgment factor for antimony treatment, the complexation interference intensity of fluoride ions on the precipitation reaction of lead and antimony, as well as the inhibitory effect of trivalent antimony on the precipitation efficiency of lead, are analyzed using complexometric titration technology to obtain pretreatment guidance information prioritizing the elimination of fluoride interference. Complexation is the coordination binding that occurs when molecules or ions in wastewater combine with metal ions. Based on the pretreatment guidance information, the optimal reaction conditions required for fluoride precipitation are analyzed by adding acid to the wastewater to adjust the hydrogen ion concentration, thus obtaining the fluoride separation process parameters. Based on the fluoride separation process parameters, the final precipitation information of lead and antimony ions after the elimination of fluoride interference is analyzed by sequentially adding oxidant and precipitant, thus obtaining the competitive and synergistic relationship for achieving simultaneous deep removal of lead and antimony.

[0044] Pretreatment guidance information can be derived from analyzing the intensity of fluoride ion complexation interference and the inhibitory effect of trivalent antimony, with the core objective of eliminating fluoride interference. Fluoride separation process parameters can be the optimal reaction conditions required for efficient precipitation of fluorides. The competitive and synergistic relationships can refer to the interfering (competitive) or promoting (synergistic) effects of lead, antimony, and fluorine during precipitation, such as the complexation interference of fluorine on lead and antimony, the inhibition of lead precipitation by trivalent antimony, and the synergistic precipitation effect of lead and antimony after eliminating fluoride interference.

[0045] Specifically, in the process of lead-acid battery smelting wastewater, fluoride ions form stable soluble complexes with lead and antimony ions, severely masking heavy metal ions and rendering conventional precipitants ineffective. Directly adding precipitants results in waste and poor precipitation. Furthermore, the presence of trivalent antimony not only hinders its own precipitation but also inhibits lead precipitation, creating a "mutual inhibition" effect. To address these issues: First, complexometric titration is used as the core analytical method. A known concentration of metal ion indicator (such as lanthanide ion solution) is precisely added to a representative wastewater sample under a specific pH buffer system. By monitoring the abrupt change in titration endpoint potential or color, the intensity of fluoride ion complexation interference with lead and antimony ions is quantitatively analyzed, and its apparent complexation stability constant is calculated. Simultaneously, by comparing the lead precipitation rate in simulated water samples containing and without trivalent antimony, the degree of inhibition of lead precipitation efficiency by trivalent antimony is assessed. Based on the quantitative analysis results above, a clear pretreatment guidance message is automatically generated. This message explicitly states, for example, that when the fluoride ion concentration exceeds a certain threshold (e.g., 50 mg / L) and the trivalent antimony ratio is higher than 30%, the fluoride complex must be broken first. Subsequently, based on this guidance message, the process parameter determination stage begins: by adding acid (e.g., 10% sulfuric acid) to the actual wastewater reaction tank, and using an online pH meter and a fluoride ion selective electrode for linked monitoring, the hydrogen ion concentration is dynamically adjusted. The inflection point where the fluoride ion concentration begins to release rapidly as the pH value decreases is recorded. For example, when the pH value is adjusted to around 3.5, the fluoride ion concentration reaches a plateau, at which point it is determined to be fluoride release. The optimal reaction conditions were determined to establish specific fluorine separation process parameters (such as the target pH control range and acid dosage curve). After the preferential separation of fluorine was completed, specific chemical agents were added sequentially according to a predetermined procedure: first, an oxidant (such as hydrogen peroxide, with the dosage dynamically calculated based on the residual antimony concentration) was added to directionally oxidize trivalent antimony to pentavalent antimony; then, a precipitant (such as lime milk) was added, and under an optimized pH environment (such as adjusting back to 8.5-9.0), lead ions and pentavalent antimony ions were encouraged to form hydroxyl precipitates together. By monitoring the residual concentrations of lead and antimony in the supernatant after precipitation, the competitive and synergistic relationship of simultaneous deep removal of lead and antimony was finally verified and confirmed, transforming the theoretical process into a stable and realized process result.

[0046] The method provided in this embodiment accurately clarifies the competitive and synergistic relationship between lead, antimony, and fluoride precipitation, effectively eliminates interference from fluoride ion complexation, reduces the inhibitory effect of trivalent antimony, provides scientific guidance and key parameters for subsequent processes, makes the treatment process more targeted, improves the stability and reliability of lead smelting wastewater treatment, ensures that the effluent meets standards, reduces the risk of secondary pollution, and at the same time reduces the consumption of reagents and energy, taking into account both environmental benefits and economic efficiency.

[0047] In some embodiments, based on fluoride separation priority and combined with the primary judgment factor for antimony treatment, the initial hydrogen ion complex-breaking concentration boundary corresponding to the target complex structure is determined. Based on the initial hydrogen ion complex-breaking concentration boundary, acid is added to the wastewater, and the dynamic process of complex structure breaking is analyzed by linking the changes in hydrogen ion concentration and the response of fluoride ion concentration, resulting in a hydrogen ion-fluoride concentration response curve. Based on the hydrogen ion-fluoride concentration response curve, the inflection point of efficient fluoride precipitation and the critical point of side reaction risk are analyzed by chemical precipitation method to determine the hydrogen ion regulation threshold for dynamic addition control. Based on the hydrogen ion regulation threshold, the form and concentration of residual heavy metals in the water after the reaction and solid-liquid separation are analyzed by spectral detection to obtain information on the stabilized intermediate water for subsequent processes.

[0048] The initial hydrogen ion concentration boundary can be considered the initial theoretical boundary of the range of hydrogen ion concentrations required to effectively break down stable complex structures formed by fluoride, lead, and antimony in wastewater. The hydrogen ion-fluoride concentration response curve is a curve constructed by monitoring the real-time hydrogen ion concentration and the corresponding released fluoride ion concentration during dynamic adjustment of the hydrogen ion concentration to describe their dynamic correlation. The hydrogen ion regulation threshold is the optimal hydrogen ion concentration control point determined based on the hydrogen ion-fluoride concentration response curve analysis, ensuring efficient precipitation of fluorides while avoiding harmful side reactions caused by excessive acidification (such as the redissolution of certain heavy metals).

[0049] Specifically, in the smelting wastewater of multi-source lead-acid batteries, fluoride ions interfere with subsequent heavy metal removal. Existing fixed hydrogen ion concentration adjustments cannot adapt to water quality fluctuations, easily leading to incomplete complex breakdown and frequent side reactions. To address these issues: Building upon upstream analysis results, for example, when the "fluoride separation priority" is high and the "antimony treatment primary judgment factor" indicates a large proportion of trivalent antimony, the "initial hydrogen ion complex breakdown concentration boundary" is calculated. The initial pH target for the reaction tank is then set within a relatively wide range (e.g., 2.5-4.0). Subsequently, a refined acid addition procedure is initiated: using gradient dosing technology, concentrated sulfuric acid is added to the reaction tank in steps and small doses via a metering pump (e.g., each addition lowers the pH by approximately 0.2 units). After each addition step, brief mixing is allowed to allow the reaction to reach equilibrium. At this point, an online pH meter and a fluoride ion selective electrode (or an ion chromatograph coupled with an automatic sampler) are used for linked monitoring, simultaneously collecting hydrogen ion concentration (pH value) and fluoride ion concentration data points at this equilibrium point. Through continuous monitoring across multiple steps, a series of data points (pH, [F]) are collected. -The data were compared, and a hydrogen ion-fluorine concentration response curve was plotted. Technicians analyzed the curve's shape: In the initial stage, the fluorine ion concentration slowly increased as the pH decreased, which was the loosening stage of the complex structure; when the pH dropped to a certain critical range (e.g., 3.2-3.0), the slope of the curve increased sharply, and the fluorine ion release rate increased in a stepwise manner. This marked the "inflection point" when the complex structure was broken down on a large scale and fluorides began to dissociate in large quantities; after continuing to add acid to cross the inflection point, the increase in fluorine ion concentration slowed down again and entered the precipitation plateau period. However, it is necessary to be wary that if the pH is too low (e.g., <2.5), the curve may show a "risk threshold" where the concentration of heavy metal ions rebounds. Based on this analysis, a specific pH value (e.g., 3.0) after the "inflection point" and at the beginning of the plateau period is established as the optimal hydrogen ion control threshold. Then, using this as a set point, the pH of the reaction system is precisely maintained near this threshold through feedback adjustment. Under this precisely controlled acidity environment, a calcium salt precipitant (such as calcium chloride solution) is added, and the free fluoride ions are efficiently precipitated in the form of calcium fluoride using chemical precipitation. After completing the precipitation reaction and subsequent flocculation, sedimentation, and solid-liquid separation, the supernatant is subjected to atomic absorption spectrometry (AAS) or inductively coupled plasma optical emission spectrometry (ICP-OES) for spectral detection to quantitatively analyze the total amount of residual lead and antimony. Its speciation can also be evaluated through valence state analysis. Finally, a stable intermediate water body information report containing specific concentrations and speciation descriptions of each indicator is generated and passed to the next process.

[0050] The method provided in this embodiment enables precise dynamic control of hydrogen ion concentration, completely breaks down complex structures, efficiently separates fluorides, avoids side reactions and equipment corrosion risks, and produces stable intermediate water with controllable water quality, laying the foundation for subsequent treatment. It solves the problems of unstable treatment effect and prominent fluoride interference in existing processes, improves the continuity and reliability of lead smelting wastewater treatment, and provides key support for antimony-oriented conversion and simultaneous deep removal of lead and antimony.

[0051] In some embodiments, based on the initial hydrogen ion concentration boundary for breaking down the complex, the acid addition gradient required to initially loosen the complex structure is analyzed using gradient addition technology to obtain step-by-step addition control information. Based on the step-by-step addition control information, acid is sequentially added to the wastewater by real-time monitoring of hydrogen ion concentration, and fluoride ion concentration is simultaneously detected after each addition step. The correspondence between changes in hydrogen ion concentration and fluoride ion release is analyzed to obtain a linked monitoring dataset. Based on the linked monitoring dataset, the transition interval where the fluoride ion release rate increases stepwise with increasing hydrogen ion concentration is analyzed to obtain information on the transition of the complex breaking down stage. Based on the information on the transition of the complex breaking down stage, the entire process from the critical point to the plateau period of fluoride ion concentration is dynamically tracked to construct a hydrogen ion-fluoride concentration response curve.

[0052] Gradient dosing technology can be a technique that divides the acid dosing process into multiple gradients and performs them step by step. Step-by-step dosing control information can be a set of information derived from gradient dosing technology, including key parameters such as acid dosing gradient, dosing interval, and dosage per dose. The linked monitoring dataset can be a set of data on hydrogen ion concentration changes and fluoride ion release rates collected synchronously during the step-by-step acid dosing process. Information on the transition of the complexation-breaking stage can be related to the inflection point where the fluoride ion concentration increases dramatically with increasing hydrogen ion concentration, indicating a step increase in its release rate. The critical point can be the hydrogen ion concentration node where the fluoride ion release rate begins to show a step increase. The plateau period can be the stable stage where the fluoride ion concentration no longer changes significantly with further increases in hydrogen ion concentration.

[0053] Specifically, in the multi-stage treatment of lead smelting wastewater, the targeted and efficient conversion of antimony is a key prerequisite for achieving simultaneous and deep removal of lead and antimony. Trivalent antimony is highly stable, difficult to precipitate, and easily interacts with other ions, affecting the treatment effect. Existing oxidation methods suffer from problems such as improper oxidant matching and uncontrolled reaction intensity, leading to incomplete antimony conversion and excessive residual concentration. To address these issues, a precise stepwise acid addition strategy is developed based on the initial hydrogen ion complex-breaking concentration boundary, using gradient dosing technology. For example, the initial acid addition amount is determined to be a basic amount per liter of wastewater (e.g., a few milliliters). The acid solution is added sequentially and intermittently to the reactor using a precision metering pump according to this strategy. Simultaneously, a linked monitoring system is constructed using an online hydrogen ion concentration meter (e.g., pH meter) and an online fluoride ion analyzer (e.g., ion chromatograph or fluoride ion selective electrode). After each addition and reaching reaction equilibrium (e.g., after waiting for a specific period), the hydrogen ion concentration (or pH value) and the corresponding fluoride ion concentration data points at that moment are simultaneously collected and recorded, thus accumulating a series of data. For the linked monitoring dataset, after obtaining the data, chemical kinetic analysis methods (such as calculating the rate of change of fluoride ion concentration between adjacent data points) are used to process the dataset. The core objective is to identify the abrupt inflection point interval of fluoride ion release kinetics. Its typical characteristic is that within a narrow range of hydrogen ion concentration changes (such as during a pH decrease of a few tenths of a unit), the release rate of fluoride ion concentration will suddenly show an order-of-magnitude jump (such as the increase in fluoride ion concentration per unit pH change jumping from a steady single digit to tens or even hundreds of milligrams per liter). This inflection point interval is accurately determined as the information indicating the transition of the complex structure from a slow dissociation stage to a rapid disintegration stage. Finally, based on the dynamic tracking data of the entire process from the reaction initiation point to the fluoride ion concentration reaching a stable plateau, data fitting techniques (such as using polynomial or nonlinear function models) are used to fit the discrete monitoring data points into a continuous and smooth hydrogen ion-fluoride concentration response curve. This curve intuitively reveals the optimal hydrogen ion concentration control range and clear critical threshold required to achieve the target fluoride separation efficiency (such as the removal rate reaching a certain high standard percentage).

[0054] The method provided in this embodiment enables precise control and visual management of the fluoride complex removal process. It can quickly determine the optimal acid consumption for complex removal for wastewater with different characteristics. While ensuring efficient separation of fluorides, it minimizes the side effects and operating costs caused by excessive acid addition. It provides intermediate water with stable water quality and significantly reduced interference factors for subsequent processes, thereby improving the adaptability of the entire wastewater treatment process to complex water quality fluctuations, treatment efficiency, and the stability and reliability of the final effluent quality.

[0055] In some embodiments, based on the hydrogen ion-fluorine concentration response curve corresponding to the water body after fluorine separation, the total antimony concentration and the ratio of trivalent antimony in the current water body are analyzed by atomic fluorescence spectrometry to obtain the antimony concentration ratio. Based on the antimony concentration ratio and combined with pretreatment guidance information, an oxidant addition strategy for preferentially converting trivalent antimony to pentavalent antimony is matched using chemical oxidation technology. Based on the oxidant addition strategy, by controlling the oxidant addition rate and the mixing energy of the reaction tank, the dynamic changes of oxidation-reduction potential and residual antimony concentration are analyzed, and the oxidation stage is adaptively adjusted to the reaction endpoint to obtain antimony high-efficiency conversion control information. Based on the antimony high-efficiency conversion control information, by adding a precipitant to the oxidized water body and performing solid-liquid separation, the residual antimony concentration in the supernatant is analyzed to determine whether it reaches a preset threshold, thus obtaining low-antimony pre-precipitated effluent information.

[0056] Chemical oxidation technology is a chemical treatment method that oxidizes difficult-to-treat trivalent antimony in water to easily precipitated pentavalent antimony by adding an oxidant. The oxidant dosing strategy is a plan that determines parameters such as the type of oxidant, dosage, and dosing rate based on the antimony concentration ratio and pretreatment guidelines. The oxidant dosing rate can be the amount of oxidant added to the reaction tank per unit time (e.g., 2 L / h), and can be a key operational parameter for controlling the oxidation reaction rate and avoiding side reactions. The mixing energy of the reaction tank can be the energy used to maintain sufficient contact and mixing between the water and the oxidant in the reaction tank (e.g., 40 W / m³). 3 Redox potential (RPP) can be a physicochemical indicator reflecting the redox state of water (e.g., 300 mV). Residual antimony concentration can be the amount of antimony in the water that has not been converted or removed during or after the oxidation reaction. The reaction endpoint can be the time point at which the oxidation reaction reaches the preset oxidation effect (i.e., trivalent antimony is essentially converted to pentavalent antimony). Antimony efficient conversion control information can be a control scheme formed by integrating oxidant dosing parameters, reaction process monitoring data, and reaction endpoint judgment results. A precipitant can be a chemical agent (e.g., calcium hydroxide) that can react with pentavalent antimony to form a poorly soluble precipitate. Solid-liquid separation can be a technique that separates the antimony precipitate generated in the water from the supernatant through methods such as sedimentation and filtration (e.g., plate and frame filtration). The supernatant can be the clarified water at the top after solid-liquid separation and is the object of subsequent antimony residual concentration detection. The residual antimony concentration can be the total amount of remaining antimony in the supernatant. The preset threshold can be the upper limit of the antimony residual concentration set according to environmental emission standards or subsequent treatment process requirements.

[0057] Specifically, in the multi-stage treatment process of lead smelting wastewater, the trivalent antimony contained in the wastewater is highly toxic and difficult to precipitate. Directly entering subsequent processes will interfere with lead removal, leading to excessive heavy metals in the effluent and violating environmental standards. The antimony concentration and valence ratio vary greatly among different wastewaters (e.g., total antimony concentration 2-8 mg / L, trivalent antimony ratio 40%-80%). Fixed treatment schemes are prone to waste of reagents or incomplete conversion. This process is the key to connecting fluoride separation and deep removal of lead and antimony. It can directionally convert the antimony valence state, creating conditions for subsequent treatment, and is the core link to ensure that wastewater meets discharge standards. To address the aforementioned issues: After completing fluoride separation and obtaining the corresponding "hydrogen ion-fluoride concentration response curve" (this curve originates from the linkage monitoring of hydrogen ion concentration and fluoride ion release concentration, used to confirm that fluoride has been efficiently precipitated), firstly, an appropriate amount of intermediate water after fluoride separation is taken, and the total antimony concentration (e.g., a detection value of 5.2 mg / L) and the proportion of trivalent antimony (e.g., 72%) are accurately determined using the highly sensitive detection method "atomic fluorescence spectrometry (AFS)," thereby quantifying the key "antimony concentration ratio." Based on this real-time data, and combined with the "pretreatment guidance information" obtained from previous steps, which focuses on eliminating fluoride interference, the most suitable type of oxidant is adaptively matched through the built-in "chemical oxidation technology" decision model (e.g., for high proportions of trivalent antimony, sodium hypochlorite, which has strong oxidizing properties and controllable byproducts, is preferred), and the specific "oxidant addition strategy" is calculated (e.g., the addition amount is 1.3 times the theoretical oxygen demand, i.e., approximately 8.5 mg / L). During the oxidation reaction, the oxidant dosing rate is controlled by a precision metering pump (e.g., initially increasing at a rate of 0.5 mg / L per minute), while the stirring speed of the reaction tank is adjusted (e.g., maintained at 200 rpm) to control the "mixing energy" and ensure sufficient contact of the reactants. During the process, an online oxidation-reduction potential (ORP) sensor combined with intermittent AFS sampling is used to dynamically monitor the ORP value (e.g., from an initial +200 mg / L). The oxidation reaction is considered to have reached its endpoint when the ORP value rises to and stabilizes at the target plateau (e.g., +450mV) and the residual total antimony concentration drops below the preset threshold (e.g., 0.15mg / L). This generates "antimony high-efficiency conversion control information" to guide subsequent operations. Finally, based on this control information, a precipitant (e.g., polyferric sulfate, dosage 80mg / L) is quantitatively added to the oxidized water. After sufficient flocculation (e.g., slow stirring for 15 minutes) and sedimentation (e.g., static sedimentation for 40 minutes) for solid-liquid separation, the supernatant is checked for final antimony concentration to confirm that it meets the requirements for deep treatment inlet (e.g., total antimony concentration below 0.1mg / L). Then, "low antimony pre-sedimentation effluent information" is formally constructed and output for use in the next process.

[0058] The method provided in this embodiment achieves directional, efficient and stable conversion of trivalent antimony, providing water quality assurance for subsequent deep synergistic precipitation of lead and antimony. It overcomes the shortcomings of existing methods, such as unstable treatment effect, waste of reagents or high risk of secondary pollution, due to the extensive oxidation process and inability to dynamically adapt to changes in water quality.

[0059] In some embodiments, based on the antimony concentration ratio and combined with pretreatment guidance information, the composition of oxidants and substances affecting oxidation efficiency in the current water body, excluding antimony, is analyzed to obtain oxidant compatibility constraints. Based on oxidant compatibility constraints, by comparing the oxidation potential and reaction selectivity of different oxidants under different hydrogen ion concentration conditions, the optimal type of oxidant that avoids harmful side reactions while ensuring oxidation efficiency is analyzed to obtain primary oxidant screening results. Based on the primary oxidant screening results, by analyzing the hydrogen ion concentration buffering capacity and exothermic characteristics of the reaction process in the target water body, the initial addition concentration, addition rate, and reaction temperature control range of the selected oxidant are dynamically determined to obtain an oxidant addition strategy for preferentially converting trivalent antimony to pentavalent antimony.

[0060] Oxidant compatibility constraints can be defined by the presence of substances in the water body, other than antimony, that consume the oxidant or affect its oxidation efficiency, thus limiting the selection of oxidants. Oxidation potential reflects the oxidant's ability to gain or lose electrons and is a key parameter for oxidant selection. Reaction selectivity refers to the characteristic of an oxidant in complex water bodies to preferentially react with the target substance (trivalent antimony) rather than reacting extensively with other impurities. Harmful side reactions can refer to reactions between the oxidant and impurities in the water body that produce toxic or harmful substances (such as toxic gases, persistent pollutants, etc.). Primary oxidant screening results can be obtained by comparing the performance of different oxidants to identify those that meet oxidation efficiency requirements and have no risk of harmful side reactions. Hydrogen ion concentration buffering capacity refers to the water body's ability to resist changes in hydrogen ion concentration, i.e., the stability of the pH value after the addition of acid or alkali. The exothermic characteristics of the reaction process refer to the intensity and rate of heat release during the oxidation reaction of the oxidant with trivalent antimony. Initial dosage concentration refers to the concentration of oxidant added to the water body per unit volume for the first time. Dosing acceleration rate refers to the volume of oxidant added to the reaction system per unit time. The reaction temperature control range can be the water temperature range that maintains the oxidation reaction in a highly efficient and stable manner.

[0061] Specifically, in the multi-stage treatment of lead smelting wastewater, the wastewater has a complex composition, containing impurities that consume oxidants. Different oxidants exhibit significant performance differences under varying water qualities, and the water's buffering capacity and exothermic reaction characteristics affect the oxidation effect. The lack of this strategy leads to low oxidation efficiency, high risk of side reactions, increased costs, and an inability to guarantee subsequent deep removal of lead and antimony. To address these issues: First, precise data from upstream is received, specifically the "antimony concentration ratio" determined by atomic fluorescence spectrometry (e.g., the total antimony concentration is detected to be at a high level, with trivalent antimony accounting for more than half). This is combined with "pretreatment guidance information" reflecting whether fluoride interference has been effectively eliminated, and then a comprehensive approach is adopted. Water quality analysis technology systematically screens and quantifies a list of "interfering substances" in the current water body that could potentially consume oxidants or inhibit the target reaction (e.g., confirming the presence of significant concentrations of ferrous ions and trace amounts of organic complexing agents). This allows for precise definition of the "oxidant compatibility constraint" that must be followed in this oxidation operation—that is, the selected oxidant must have the ability to preferentially attack trivalent antimony while remaining inert to identified interfering substances. Subsequently, the scientific comparison and screening of oxidants begins. This involves accessing a built-in chemical database and initiating parallel verification experiments at a laboratory scale to systematically evaluate various candidate oxidants (such as potassium permanganate, sodium hypochlorite, and persulfate). The core of the evaluation is comparing their "oxidation potential" and "reaction selectivity" under conditions simulating the actual pH of the current wastewater (e.g., a slightly acidic environment). Experiments may reveal that, at the target pH, oxidant A, while possessing strong oxidizing power, reacts violently with ferrous ions and produces a large amount of precipitate; oxidant B requires stringent activation conditions and its exothermic reaction is difficult to control; while oxidant C exhibits good selectivity for antimony trivalent and has a low risk of side reactions, thus being initially selected as the "primary oxidant screening result." Finally, by refining and dynamically determining the addition parameters, the "hydrogen ion concentration buffering capacity" of the water body will be further tested (e.g., small-scale tests show that a considerable amount of acid needs to be added to significantly change its pH, indicating a strong buffering capacity), and the "exothermic characteristics of the oxidation reaction process" will be evaluated (e.g., monitoring confirms it is a moderately exothermic reaction). Based on all the above analysis conclusions, a customized "oxidant addition strategy" was finally generated, which clearly indicates that: the selected oxidant C should be used, and its "initial addition concentration" should be controlled within a moderate range that can both start the reaction and avoid waste (such as starting with a medium concentration value); the "acceleration rate" should adopt a gradient mode of fast at first and slow later to ensure that the reaction proceeds smoothly; the entire oxidation process must be completed within a controllable "reaction temperature control range" (such as a relatively mild temperature range) to ensure the high efficiency, stability and safety of the entire oxidation stage.

[0062] The method provided in this embodiment achieves precise matching between the oxidant and the wastewater quality, reduces the consumption of the oxidant by non-target substances, improves the efficiency and selectivity of trivalent antimony oxidation conversion, avoids harmful side reactions, and the optimized addition parameters avoid problems such as violent local reactions and waste of oxidant, reduce treatment costs, provide high-quality pretreatment for subsequent lead and antimony removal, enhance the stability and shock resistance of the treatment system, ensure that the effluent meets the standards, and provide reliable technical support for the efficient treatment of lead smelting wastewater.

[0063] In some embodiments, based on the hydrogen ion-fluorine concentration response curve, atomic absorption spectrometry is used to analyze the dynamic ratio of hydrogen ion concentration and lead-antimony ion concentration in the current water body to obtain the operating condition judgment factor. Based on the operating condition judgment factor, different chemical environments required to achieve deep removal of lead and antimony are analyzed, and a precipitation path control instruction sequence is executed. The precipitation path control instruction sequence includes a priority precipitation path control instruction and a co-precipitation path control instruction. The priority precipitation path control instruction specifically includes: adding a lead-specific precipitant to the water body first and separating the precipitate, then adding an antimony-specific precipitant, analyzing the stepwise removal effect of lead and antimony, and obtaining the first purified water body information. The co-precipitation path control instruction specifically includes: adding a lead-antimony composite precipitant to the water body all at once and controlling the reaction conditions, analyzing the simultaneous co-precipitation effect of lead and antimony, and obtaining the second purified water body information. The first purified water body information and the second purified water body information are integrated to construct a multi-stage treatment log for lead smelting wastewater.

[0064] Atomic absorption spectrometry (AAS) is an analytical technique for the precise detection of water quality parameters, used to determine the ratio of hydrogen ion concentration to lead and antimony ion concentration in water. Operating condition judgment factors are quantitative indicators obtained through AAS analysis, characterizing the current chemical environment and lead and antimony ion distribution in the water. The sedimentation path control command sequence is a set of instructions guiding the deep removal of lead and antimony. Priority sedimentation path control commands can be sub-commands of the sedimentation path control command sequence, and can be operational commands for sequentially removing lead and antimony by adding specific precipitants in stages; the type of precipitant is selected based on the characteristics of lead and antimony ions. Co-precipitation path control commands can be sub-commands of the sedimentation path control command sequence, and can be operational commands for simultaneously removing lead and antimony by adding a composite precipitant in a single step; the composite precipitant must also meet the precipitation reaction requirements of lead and antimony ions. First purified water information can be water information obtained through water quality testing after executing the priority sedimentation path control command, including parameters such as residual lead and antimony concentration and sedimentation reaction conditions. Second purified water information can be water information obtained through water quality testing after executing the co-precipitation path control command, including residual lead and antimony concentration and reaction environment parameters.

[0065] Specifically, lead smelting wastewater has a complex and dynamic composition. The concentration ratio of lead and antimony ions fluctuates depending on the treatment effects of preceding processes such as fluoride separation and antimony oxidation. The precipitation characteristics and reaction conditions required for lead and antimony ions differ significantly under different ratios. If a single precipitation path is used, problems such as incomplete precipitation, waste of reagents, or the generation of harmful byproducts are likely to occur. In actual treatment scenarios, without a clear control logic for the precipitation path, operators cannot easily select the optimal removal method based on real-time water quality conditions, which may lead to residual lead and antimony concentrations exceeding discharge standards and posing an environmental pollution risk. To address these issues, atomic absorption spectrometry (AAS) is used to monitor the water after fluoride separation and antimony pre-oxidation in real time, accurately measuring the hydrogen ion concentration (e.g., pH value) and the instantaneous concentrations of lead and antimony ions, and calculating the dynamic lead-antimony ion ratio (e.g., if the monitored lead ion concentration is 15 mg / L and the antimony ion concentration is 3 mg / L, the ratio is 5:1), forming a quantified operating condition. The decision factor is then used, followed by the in-house chemical equilibrium model to simulate and analyze the theoretical precipitation efficiency, reagent consumption, and side reaction risks of two precipitation paths under the current hydrogen ion concentration and specific ratio: a preferential precipitation path (adding a lead-specific precipitant such as sodium sulfide first, followed by an antimony precipitant such as polyferric sulfate) and a co-precipitation path (adding a lead-antimony composite precipitant, such as a calcium-iron based reagent in a specific ratio, all at once). This generates comparative information on path reaction characteristics. Based on this, and combined with a preset switching threshold (e.g., when the dynamic ratio of lead and antimony ions is greater than the set lead dominance threshold of 5:1), the path switching decision logic is executed: if the path is determined to be lead dominant... If the reaction proceeds as planned, a priority sedimentation path control command is triggered. First, sodium sulfide solution is added to the reaction tank at a calculated dosage (e.g., to achieve a sulfur ion concentration 1.2 times the theoretical requirement). Under mechanical stirring, the solution reacts fully to form lead sulfide precipitate. After solid-liquid separation, polyferric sulfate solution (e.g., 50 mg / L based on residual antimony concentration) is added to the clarified liquid for coagulation and sedimentation to remove antimony. After separation, the first purified water information is obtained. If it is determined that the co-precipitation ratio is suitable (e.g., lead-antimony ratio between 1:1 and 2:1), a co-precipitation path control command is triggered, and a pre-prepared calcium-iron composite precipitate is added in one go. The flocculant suspension is automatically adjusted to the optimal co-precipitation range (e.g., 8.0-8.5) and reacted under controlled stirring speed to form a composite precipitate containing lead and antimony. After sedimentation and separation, the second purified water information is obtained. Finally, the selected path of this operation, all real-time monitoring data (e.g., initial ratio, real-time pH), control command parameters (e.g., type and dosage of flocculant), reaction conditions (e.g., reaction time, stirring intensity), and final effluent water quality indicators (e.g., residual concentration of lead and antimony) are automatically correlated, timestamped, and formatted and stored to generate a structured multi-stage treatment log for lead smelting wastewater.

[0066] The method provided in this embodiment accurately analyzes water quality characteristics, dynamically adjusts reaction conditions, adaptively matches treatment strategies, and autonomously switches sedimentation paths to achieve efficient separation and deep removal of antimony, fluorine, and lead. Real-time monitoring and log recording throughout the process ensure compliance and traceability, significantly reducing reagent waste and by-product risks. It meets stringent environmental standards while improving treatment efficiency and reducing operating costs, providing a reliable solution for the industrial and standardized treatment of multi-source lead-acid battery smelting wastewater.

[0067] In some embodiments, based on the influent hydrogen ion concentration and the dynamic ratio of lead and antimony ions, chemical equilibrium simulation technology is used to analyze the differences in chemical equilibrium conditions and precipitant selectivity of lead and antimony precipitation reactions when using the preferential precipitation path and the co-precipitation path, respectively, to obtain comparative information on path reaction characteristics. Based on the comparative information on path reaction characteristics and combined with information on the stabilized intermediate water body, precipitation separation technology is used to analyze the types, dosage ranges, and reaction conditions of the specific precipitant or composite precipitant required for each of the two paths to achieve the goal of deep removal, to obtain the path switching decision logic. Based on the path switching decision logic, autonomous switching is executed: when the dynamic ratio of lead and antimony ions is greater than the preset lead dominance threshold, a control command for initiating the preferential precipitation path with the goal of preferential lead precipitation is executed; when the dynamic ratio of lead and antimony ions is less than or equal to the lead dominance threshold and greater than the preset antimony dominance threshold, a control command for initiating the co-precipitation path with the goal of achieving lead and antimony co-precipitation is executed.

[0068] Deep lead and antimony removal aims to reduce the residual concentrations of lead and antimony ions in wastewater to environmental emission standards. The chemical environment can be the sum of factors influencing the precipitation reactions of lead and antimony, such as pH and ionic composition. The dynamic ratio of lead and antimony ions can be the real-time ratio of lead to antimony ion concentrations in wastewater. The lead dominance threshold can be a preset critical value for determining whether lead ions are dominant. The antimony dominance threshold can be a preset critical value for determining whether antimony ions are relatively dominant.

[0069] Specifically, the lead and antimony ion concentration ratio in lead smelting wastewater fluctuates easily with raw materials and processes, and their precipitation characteristics differ significantly. If a single precipitation path is used, when lead ions are dominant, antimony ions will interfere with the lead precipitation reaction, leading to incomplete lead removal. When the ratio is moderate, stepwise precipitation increases the risk of side reactions, while co-precipitation may lead to excessive heavy metal residues due to insufficient selectivity of the precipitant. Furthermore, a fixed path cannot adapt to different chemical environments, easily causing precipitant waste, a surge in sludge production, and even secondary water pollution, seriously affecting wastewater treatment compliance rates and violating environmental protection requirements. To address these issues, the solution begins with real-time monitoring of the "stabilized intermediate water body," using atomic absorption spectrometry to accurately determine the hydrogen ion concentration (e.g., pH 3.5) and the real-time concentrations of lead and antimony ions in the influent, and calculating the crucial "dynamic ratio of lead and antimony ions" (e.g., [Pb]).2+ (Sb=5:1) Subsequently, the system calls the embedded chemical equilibrium simulation technology, using the current water quality parameters as input, to perform virtual reaction simulations for two preset paths: For the "preferred sedimentation path", the model will simulate the completeness of lead ions forming lead sulfide precipitates when lead-specific precipitants such as sodium sulfide (Na2S) are added first (e.g., the concentration is 0.5 g per liter of wastewater), and predict the potential impact of residual antimony ions (e.g., residual concentration is higher than 1 mg / L) on subsequent antimony precipitation steps; For the "co-precipitation path", the model simulates the chemical equilibrium conditions and competition relationship of lead and antimony ions forming co-precipitates simultaneously when composite precipitants such as hydroxyapatite are added at one time (e.g., calcium to heavy metal ion molar ratio is 2:1). Based on the "path reaction characteristic comparison information" generated by the simulation, and combined with the "stabilized intermediate water body information" (e.g., residual fluoride ion concentration is lower than 10 mg per liter), the precipitation separation technology is executed to form a specific "path switching decision logic". For example, if the dynamic ratio of lead to antimony is set to exceed a preset threshold (e.g., a lead dominance threshold of 4), it is determined that lead is significantly excessive, and a "preferred precipitation path control command" will be automatically executed: First, a calculated dose of sodium sulfide solution (e.g., 120% of the theoretical amount) is added to the reaction tank. Under a specific stirring intensity (e.g., using a stirrer with a speed of 200 rpm), lead is preferentially precipitated. After solid-liquid separation, an iron salt precipitant (e.g., polyferric sulfate, at a dosage of 50 mg per liter) is added to the supernatant to remove antimony. Conversely, if the ratio is detected to be within another range (e.g., in...), the command will be executed. If the concentration is between 1 and 4, the ion concentration is determined to be relatively balanced, and the "co-precipitation path control instruction" is executed: a composite precipitant with an appropriate formula is added at once, and the pH value of the reaction tank (e.g., adjusting the pH to 8.5) and the stirring speed are precisely controlled to promote the synchronous and efficient generation of lead-antimony hydroxyphosphate co-precipitates. Finally, after precipitation and separation, purified water with lead and antimony concentrations lower than the preset standard (e.g., lower than 0.5 mg per liter) is produced. The entire process is automatically completed by the central controller in conjunction with online monitoring instruments and dosing pump valves, realizing closed-loop control from dynamic perception and intelligent decision-making to precise execution.

[0070] By introducing operating condition judgment factors and chemical balance simulation, the method provided in this embodiment realizes intelligent prediction and adaptive switching of sedimentation path, enabling the treatment process to flexibly respond to fluctuations in influent water quality, improving the stability and reliability of deep removal of lead and antimony. At the same time, by accurately matching the type and dosage of precipitant, the consumption of reagents and sludge production are reduced, thereby lowering the overall operating cost.

[0071] Figure 3 This is a schematic diagram of a multi-stage treatment system for lead smelting wastewater provided in an embodiment of this application, as shown below. Figure 3As shown, the multi-stage treatment system 300 for lead smelting wastewater in this embodiment includes: a multiphase analysis module 301, a dynamic adjustment module 302, an adaptive matching module 303, and an instruction switching module 304.

[0072] The multiphase analysis module 301 is used to acquire water quality data of multi-source lead-acid battery smelting wastewater, and based on the water quality data, analyze the differences in concentration and speciation of antimony, fluoride, and lead in the wastewater to obtain a multiphase feature set of battery wastewater. The dynamic adjustment module 302 is used to obtain stable intermediate water body information by dynamically adjusting the hydrogen ion concentration based on the multiphase feature set of battery wastewater, breaking the complex structure and preferentially separating fluorides. The adaptive matching module 303 is used to monitor the antimony valence state and antimony concentration in real time based on the stable intermediate water body information, adaptively match the type of oxidant and reaction intensity to achieve directional and efficient conversion of antimony, and obtain low-antimony pre-precipitation effluent information. The instruction switching module 304 is used to autonomously switch the precipitation path control instruction based on the low-antimony pre-precipitation effluent information and the dynamic ratio of influent hydrogen ion concentration and lead-antimony ions to obtain purified water body with simultaneous deep removal of lead and antimony, and output multi-stage treatment log of lead smelting wastewater.

[0073] Optionally, when the multiphase analysis module 301 analyzes the differences in concentration and speciation of antimony, fluoride, and lead in wastewater based on the water quality data to obtain a multiphase characteristic set of battery wastewater, it is specifically used for: the water quality data including antimony concentration, trivalent antimony ratio, fluoride ion concentration, and lead concentration; based on the fluoride ion concentration, using fluoride ion complexometric titration technology, analyzing the interference effect of fluoride on heavy metal precipitation during lead smelting wastewater treatment to obtain fluoride separation priority; based on the antimony concentration, combined with the trivalent antimony ratio, using high-performance liquid chromatography-atomic fluorescence spectrometry to analyze the existing speciation and transformation difficulty of antimony element to obtain a primary judgment factor for antimony treatment; based on the lead concentration, combined with the fluoride separation priority and the primary judgment factor for antimony treatment, analyzing the competitive and synergistic relationship among lead, antimony, and fluoride influencing precipitation to obtain the multiphase characteristic set of battery wastewater.

[0074] Optionally, when analyzing the competitive and synergistic relationship among lead, antimony, and fluorine affecting precipitation, the multiphase analysis module 301 is specifically used for: based on the fluorine separation priority and combined with the primary judgment factor for antimony treatment, analyzing the complexation interference intensity of fluoride ions on the precipitation reaction of lead and antimony, and the inhibitory effect of trivalent antimony on the precipitation efficiency of lead, based on complexometric titration technology, to obtain pretreatment guidance information prioritizing the elimination of fluoride interference; the complexation is the coordination binding that occurs when molecules or ions in wastewater combine with metal ions; based on the pretreatment guidance information, analyzing the optimal reaction conditions required for fluoride precipitation by adding acid to the wastewater to adjust the hydrogen ion concentration, to obtain fluoride separation process parameters; based on the fluoride separation process parameters, analyzing the final precipitation information of lead and antimony ions after the elimination of fluoride interference by sequentially adding oxidant and precipitant, to obtain the competitive and synergistic relationship for achieving simultaneous deep removal of lead and antimony.

[0075] Optionally, the dynamic adjustment module 302, during the construction of the stabilized intermediate water information, is specifically used for: determining the initial hydrogen ion complex-breaking concentration boundary corresponding to the target complex structure to be broken based on the fluoride separation priority and the primary judgment factor for antimony treatment; adding acid to the wastewater based on the initial hydrogen ion complex-breaking concentration boundary, and analyzing the dynamic process of complex structure breaking by monitoring the changes in hydrogen ion concentration and fluoride ion concentration response, thereby obtaining a hydrogen ion-fluoride concentration response curve; analyzing the inflection point of efficient fluoride precipitation and the critical point of side reaction risk by using chemical precipitation method, thereby determining the hydrogen ion regulation threshold for dynamic addition control; and analyzing the form and concentration of residual heavy metals in the water after the reaction and solid-liquid separation by using spectral detection, thereby obtaining the stabilized intermediate water information for subsequent processes.

[0076] Optionally, the dynamic adjustment module 302, during the construction of the hydrogen ion-fluoride concentration response curve, is specifically used for: based on the initial hydrogen ion complex-breaking concentration boundary, analyzing the acid addition gradient required to achieve initial loosening of the complex structure through gradient addition technology, and obtaining step-by-step addition control information; based on the step-by-step addition control information, sequentially adding acid to the wastewater by real-time monitoring of hydrogen ion concentration, and synchronously detecting fluoride ion concentration after each addition step, analyzing the correspondence between hydrogen ion concentration changes and fluoride ion concentration release, and obtaining a linkage monitoring dataset; based on the linkage monitoring dataset, analyzing the transition interval where the fluoride ion concentration release rate increases stepwise with increasing hydrogen ion concentration, and obtaining complex-breaking stage transition information; based on the complex-breaking stage transition information, constructing the hydrogen ion-fluoride concentration response curve by dynamically tracking the entire process from the critical point to the plateau period of fluoride ion concentration.

[0077] Optionally, the adaptive matching module 303, during the construction of the low-antimony pre-precipitation effluent information, is specifically used for: based on the water body after fluoride separation corresponding to the hydrogen ion-fluoride concentration response curve, analyzing the total antimony concentration and the ratio of trivalent antimony in the current water body using atomic fluorescence spectrometry to obtain the antimony concentration ratio; based on the antimony concentration ratio, combined with the pretreatment guidance information, matching an oxidant addition strategy for preferentially converting trivalent antimony to pentavalent antimony using chemical oxidation technology; based on the oxidant addition strategy, analyzing the dynamic changes of oxidation-reduction potential and residual antimony concentration by controlling the oxidant addition rate and the mixing energy of the reaction tank, adaptively adjusting the oxidation stage to the reaction endpoint to obtain antimony high-efficiency conversion control information; based on the antimony high-efficiency conversion control information, adding a precipitant to the oxidized water body and performing solid-liquid separation, analyzing whether the residual antimony concentration in the supernatant reaches a preset threshold to obtain the low-antimony pre-precipitation effluent information.

[0078] Optionally, the adaptive matching module 303, during the construction of the oxidant dosing strategy, is specifically used for: based on the antimony concentration ratio and combined with the pretreatment guidance information, analyzing the composition of oxidants consuming other than antimony and substances affecting oxidation efficiency in the current water body to obtain oxidant compatibility constraints; based on the oxidant compatibility constraints, by comparing the oxidation potential and reaction selectivity of different oxidants under different hydrogen ion concentration conditions, analyzing the optimal type of oxidant that avoids harmful side reactions while ensuring oxidation efficiency, and obtaining primary oxidant screening results; based on the primary oxidant screening results, by analyzing the hydrogen ion concentration buffering capacity and exothermic characteristics of the reaction process of the target water body, dynamically determining the initial dosing concentration, dosing rate, and reaction temperature control range of the selected oxidant, and obtaining the oxidant dosing strategy for preferentially converting trivalent antimony into pentavalent antimony.

[0079] Optionally, during the construction of the multi-stage treatment log for lead smelting wastewater, the instruction switching module 304 is specifically used for: based on the hydrogen ion-fluoride concentration response curve, analyzing the dynamic ratio of hydrogen ion concentration and lead-antimony ion concentration in the current water body using atomic absorption spectrometry to obtain a working condition judgment factor; based on the working condition judgment factor, analyzing the different chemical environments required to achieve deep removal of lead and antimony, and executing a precipitation path control instruction sequence; the precipitation path control instruction sequence includes a priority precipitation path control instruction and a co-precipitation path control instruction; the priority precipitation path control instruction specifically includes: by preferentially adding a lead-specific precipitant to the water body and separating the precipitate, and then adding an antimony-specific precipitant, analyzing the stepwise removal effect of lead and antimony to obtain first purified water body information; the co-precipitation path control instruction specifically includes: by adding a lead-antimony composite precipitant to the water body at one time and controlling the reaction conditions, analyzing the synchronous co-precipitation effect of lead and antimony to obtain second purified water body information; integrating the first purified water body information and the second purified water body information to construct the multi-stage treatment log for lead smelting wastewater.

[0080] Optionally, when the instruction switching module 304 analyzes the different chemical environments required for deep removal of lead and antimony based on the operating condition determination factors and executes the precipitation path control instruction sequence, it is specifically used for: based on the influent hydrogen ion concentration and combined with the dynamic ratio of lead and antimony ions, using chemical equilibrium simulation technology, analyzing the differences in chemical equilibrium conditions and precipitant selectivity of lead and antimony precipitation reactions when using the preferred precipitation path and the co-precipitation path respectively, and obtaining path reaction characteristic comparison information; based on the path reaction characteristic comparison information and combined with the information of the stabilized intermediate water body, using precipitation separation technology, analyzing the types, dosage ranges, and reaction conditions of the specific precipitant or composite precipitant required for each of the two paths to achieve the deep removal target, and obtaining path switching decision logic; based on the path switching decision logic, performing autonomous switching: when the dynamic ratio of lead and antimony ions is greater than a preset lead dominance threshold, executing the preferred precipitation path control instruction aimed at prioritizing lead precipitation; when the dynamic ratio of lead and antimony ions is less than or equal to the lead dominance threshold and greater than a preset antimony dominance threshold, executing the co-precipitation path control instruction aimed at achieving lead and antimony co-precipitation.

[0081] The system in this embodiment can be used to execute the methods of any of the above embodiments, and its implementation principle and technical effect are similar, so they will not be described again here.

Claims

1. A multi-stage treatment method of lead smelting wastewater, characterized by, The application relates to a lead smelting wastewater treatment method and device. The method comprises the following steps: acquiring water quality data of multi-source lead-acid battery smelting wastewater; based on the water quality data, analyzing the concentration and form difference of antimony, fluorine and lead in the wastewater to obtain a battery wastewater multi-phase characteristic set; based on the battery wastewater multi-phase characteristic set, breaking the complex structure and preferentially separating fluorides by dynamically adjusting the hydrogen ion concentration to obtain stable intermediate water body information; based on the stable intermediate water body information, real-time monitoring of the valence state and concentration of antimony, adaptive matching of the type and reaction intensity of the oxidizing agent, realization of directional and efficient conversion of antimony, and obtaining of low-antimony pre-sedimentation effluent information; based on the low-antimony pre-sedimentation effluent information, automatically switching the precipitation path control instruction according to the hydrogen ion concentration and the dynamic proportion of lead and antimony ions in the influent to obtain purified water body with synchronous and deep removal of lead and antimony, and outputting lead smelting wastewater multi-stage treatment log. The method comprises the following steps: acquiring water quality data of multi-source lead-acid battery smelting wastewater; based on the water quality data, analyzing the concentration and form difference of antimony, fluorine and lead in the wastewater to obtain a battery wastewater multi-phase characteristic set; based on the battery wastewater multi-phase characteristic set, breaking the complex structure and preferentially separating fluorides by dynamically adjusting the hydrogen ion concentration to obtain stable intermediate water body information; based on the stable intermediate water body information, real-time monitoring of the valence state and concentration of antimony, adaptive matching of the type and reaction intensity of the oxidizing agent, realization of directional and efficient conversion of antimony, and obtaining of low-antimony pre-sedimentation effluent information; based on the low-antimony pre-sedimentation effluent information, automatically switching the precipitation path control instruction according to the hydrogen ion concentration and the dynamic proportion of lead and antimony ions in the influent to obtain purified water body with synchronous and deep removal of lead and antimony, and outputting lead smelting wastewater multi-stage treatment log. The water quality data comprises the concentration of antimony, the proportion of trivalent antimony, the concentration of fluoride ions and the concentration of lead. Based on the concentration of fluoride ions, the interference influence of fluorides on heavy metal precipitation in the lead smelting wastewater treatment process is analyzed by using a fluoride ion complex titration technology to obtain a fluorine separation priority.

2. The method of claim 1, wherein, Based on the concentration of antimony, the proportion of trivalent antimony and the high-performance liquid chromatography-atomic fluorescence spectrometry technology, the existing form and conversion difficulty of antimony elements are analyzed to obtain an antimony treatment primary judgment factor. Based on the concentration of lead, the fluorine separation priority and the antimony treatment primary judgment factor, the competitive and synergistic relationship among lead, antimony and fluorine in influencing precipitation is analyzed to obtain the battery wastewater multi-phase characteristic set. The analysis of the competitive and synergistic relationship among lead, antimony and fluorine in influencing precipitation comprises the following steps: based on the fluorine separation priority and the antimony treatment primary judgment factor, the complexing interference intensity of fluoride ions on the precipitation reaction of lead and antimony and the inhibition effect of trivalent antimony on the lead precipitation efficiency are analyzed by using a complex titration technology to obtain pretreatment guidance information with the priority of breaking the fluorine interference; The complexing is the coordination combination of molecules or ions in wastewater and metal ions; Based on the pretreatment guidance information, the optimal reaction conditions required for fluoride precipitation are analyzed by adding acid into the wastewater to adjust the hydrogen ion concentration, and fluorine separation process parameters are obtained; 3. The method of claim 2, wherein, Based on the fluorine separation process parameters, the final precipitation information of lead and antimony ions after the elimination of fluorine interference is analyzed by sequentially adding oxidizing agents and precipitants to obtain the competitive and synergistic relationship for realizing the synchronous and deep removal of lead and antimony. The construction process of the stable intermediate water body information comprises the following steps: based on the fluorine separation priority and the antimony treatment primary judgment factor, the initial hydrogen ion complex breaking concentration boundary corresponding to the breaking of the target complex structure is determined; Based on the initial hydrogen ion complex breaking concentration boundary, acid liquid is added into the wastewater, and the dynamic progress of the complex structure breaking is analyzed by monitoring the hydrogen ion concentration change and the fluoride ion concentration response to obtain a hydrogen ion-fluoride concentration response curve; ​ ​ 4. The method of claim 3, wherein, ​ ​ ​ Based on the hydrogen ion-fluoride concentration response curve, through chemical precipitation method, the inflection point of efficient precipitation of fluoride and the critical point of side reaction risk are analyzed to determine the hydrogen ion control threshold for dynamic dosing control; Based on the hydrogen ion control threshold, through spectral detection, the form and concentration of residual heavy metals in the water body after the completion of the reaction and solid-liquid separation are analyzed to obtain the stabilization intermediate water body information for subsequent processes.

5. The method of claim 4, wherein, The construction process of the hydrogen ion-fluoride concentration response curve includes: Based on the initial hydrogen ion complex breaking concentration boundary, through gradient dosing technology, the acid liquid dosing gradient required to achieve preliminary loosening of the complex structure is analyzed to obtain stepwise dosing control information; Based on the stepwise dosing control information, through real-time monitoring of hydrogen ion concentration, acid liquid is sequentially dosed into the wastewater, and fluoride ion concentration is detected synchronously after each dosing step to analyze the corresponding relationship between hydrogen ion concentration change and fluoride ion concentration release to obtain a linkage monitoring data set; Based on the linkage monitoring data set, the turning interval of the fluoride ion concentration release rate stepwise increase with the increase of hydrogen ion concentration is analyzed to obtain complex breaking stage transition information; Based on the complex breaking stage transition information, through dynamic tracking of the whole process from the critical point to the platform period of fluoride ion concentration, the hydrogen ion-fluoride concentration response curve is constructed.

6. The method of claim 5, wherein, The construction process of the low-antimony pre-sedimentation effluent information includes: Based on the water body after the completion of fluoride separation corresponding to the hydrogen ion-fluoride concentration response curve, through atomic fluorescence spectrometry, the total antimony concentration and the proportion of trivalent antimony in the current water body are analyzed to obtain the antimony concentration ratio; Based on the antimony concentration ratio, combined with the pretreatment guidance information, through chemical oxidation technology, the oxidant dosing strategy for preferentially converting trivalent antimony to pentavalent antimony is matched; Based on the oxidant dosing strategy, by controlling the oxidant dosing rate and the mixing energy of the reaction tank, the dynamic changes of oxidation-reduction potential and residual antimony concentration are analyzed to adaptively adjust the oxidation stage to the reaction endpoint to obtain antimony efficient conversion control information; Based on the antimony efficient conversion control information, by adding a precipitant to the water body after oxidation and performing solid-liquid separation, it is analyzed whether the residual concentration of antimony in the supernatant reaches the preset threshold to obtain the low-antimony pre-sedimentation effluent information.

7. The method of claim 6, wherein, The construction process of the oxidant dosing strategy includes: Based on the antimony concentration ratio, combined with the pretreatment guidance information, the composition of substances in the current water body other than antimony that consume oxidants and affect oxidation efficiency is analyzed to obtain the oxidant adaptability constraint; Based on the oxidant adaptability constraint, by comparing the oxidation potential and reaction selectivity of different oxidants under different hydrogen ion concentrations, the optimal oxidant type that ensures oxidation efficiency while avoiding harmful side reactions is analyzed to obtain a primary oxidant screening result; Based on the primary oxidant screening result, by analyzing the hydrogen ion concentration buffering capacity and reaction process heat release characteristics of the target water body, the initial dosing concentration, dosing rate, and reaction temperature control range of the selected oxidant are dynamically determined to obtain the oxidant dosing strategy for preferentially converting trivalent antimony to pentavalent antimony.

8. The method of claim 6, wherein, The construction process of the lead smelting wastewater multi-stage treatment log comprises: Based on the hydrogen ion-fluorine concentration response curve, the hydrogen ion concentration and lead-antimony ion dynamic ratio of the current water body are analyzed by atomic absorption spectrometry to obtain a working condition judgment factor; Based on the working condition judgment factor, different chemical environments required to achieve deep removal of lead and antimony are analyzed, and a precipitation path control instruction sequence is executed; The precipitation path control instruction sequence includes a preferential precipitation path control instruction and a co-precipitation path control instruction; The preferential precipitation path control instruction specifically includes: preferentially adding a lead-specific precipitant to the water body, separating the precipitate, then adding an antimony-specific precipitant, analyzing the step-by-step removal effect of lead and antimony, and obtaining first purified water body information; The co-precipitation path control instruction specifically includes: adding a lead-antimony composite precipitant to the water body at one time and controlling the reaction conditions, analyzing the synchronous co-precipitation effect of lead and antimony, and obtaining second purified water body information; The first purified water body information and the second purified water body information are integrated to construct the lead smelting wastewater multi-stage treatment log.

9. The method of claim 8, wherein, Based on the working condition judgment factor, different chemical environments required to achieve deep removal of lead and antimony are analyzed, and a precipitation path control instruction sequence is executed, comprising: Based on the hydrogen ion concentration of the influent, combined with the lead-antimony ion dynamic ratio, the chemical equilibrium conditions and precipitant selectivity differences of lead and antimony precipitation reactions through preferential precipitation path and co-precipitation path are analyzed by chemical equilibrium simulation technology to obtain path reaction characteristic comparison information; Based on the path reaction characteristic comparison information, combined with the stabilized intermediate water body information, the types, dosage ranges and reaction conditions of the specific precipitants or composite precipitants required for each path to achieve deep removal are analyzed by precipitation separation technology to obtain path switching decision logic; Based on the path switching decision logic, autonomous switching is performed: When the lead-antimony ion dynamic ratio is greater than a preset lead advantage threshold, the preferential precipitation path control instruction for starting the preferential precipitation of lead is executed; When the lead-antimony ion dynamic ratio is less than or equal to the lead advantage threshold and greater than a preset antimony advantage threshold, the co-precipitation path control instruction for starting the co-precipitation of lead and antimony is executed.

10. A multi-stage treatment system for lead smelting wastewater, characterized by, Applied to the method of any one of claims 1-9, comprising: A multi-phase analysis module is used to obtain water quality data of multi-source lead-acid battery smelting wastewater, based on the water quality data, the concentration and form difference of antimony, fluorine and lead in the wastewater are analyzed, and a battery wastewater multi-phase feature set is obtained; A dynamic adjustment module is used to break the complex structure and preferentially separate fluorides by dynamically adjusting the hydrogen ion concentration based on the battery wastewater multi-phase feature set to obtain stabilized intermediate water body information; An adaptive matching module is used to monitor the antimony valence and antimony concentration in real time based on the stabilized intermediate water body information, and to adaptively match the type and reaction intensity of the oxidizing agent to achieve directional and efficient conversion of antimony to obtain low-antimony pre-sediment effluent information; The instruction switching module is used for switching the precipitation path control instruction autonomously based on the low-antimony pre-sedimentation effluent information according to the dynamic ratio of the inlet water hydrogen ion concentration to lead-antimony ions, obtaining the purified water body with synchronous deep removal of lead and antimony, and outputting the multi-stage lead smelting wastewater treatment log.

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