Comprehensive recovery treatment method for zinc anode slime

Abstract

The invention relates to the field of metallurgical engineering, and discloses a zinc anode slime comprehensive recovery treatment method which comprises the following steps: pretreating zinc anode slime to remove impurities; determining optimal operation parameters in the recovery process based on an optimal control method; metal components are leached under the optimal condition, and a metal ion solution is formed; zinc, copper, lead and silver are sequentially recycled in an electrolysis mode; the waste residues are subjected to high-temperature roasting treatment, residual metal is recycled, and resource utilization is achieved; and carrying out chemical precipitation treatment on the waste liquid, and after metal ions are removed, discharging the waste liquid up to standard or recycling the waste liquid. By means of the multi-stage waste liquid chemical precipitation and ion exchange combined process, various harmful metal ions in complex waste liquid generated in the zinc anode slime leaching process are efficiently removed, the treatment effect that the waste liquid can be stably discharged is achieved, and compared with the prior art, the purification degree and the process stability are improved.

Description

Technical Field

[0001] The present invention relates to the technical field of metallurgical engineering, and particularly to a comprehensive recovery and treatment method for zinc anode slime. Background Art

[0002] Zinc anode slime is a by-product deposited at the bottom of the electrolytic cell during the zinc electrolysis process. It usually contains various valuable metal components such as lead, copper, and silver, and is also mixed with impurities such as silicon, fluorine, and iron. Its composition is complex, structure is loose, and water content is high. It has long been regarded as a difficult-to-treat secondary resource in the metallurgical field. Traditional treatment methods mostly directly extract the main metals after acid leaching or preliminarily enrich them by physical separation methods. Some processes also attempt to use roasting reduction, electrolytic deposition, etc. to recover multiple metals. These processes have a certain technical basis in practice and the process is relatively mature, so they have been preliminarily applied in industry.

[0003] However, in the face of the unique high-impurity and multi-component coexistence system in zinc anode slime, the existing technologies still have certain limitations in aspects such as the selective control of multi-metal separation, the complete removal of metal ions in the slag liquid, and the resource utilization of the final residue. A single chemical precipitation process is often affected by the pH control fluctuation and the selectivity of the precipitant when treating waste liquid with complex impurities, and it is difficult to stably achieve the complete removal of heavy metal ions; the residue after roasting is often directly stockpiled, and the potential inorganic component resources in it have not been fully developed, with a low overall utilization rate. In addition, in the metal oxide reduction stage, the traditional general reduction atmosphere method is difficult to deal with the complex situation of the coexistence of multiple metal oxides in zinc anode slime, and it is easy to cause cross-interference in the metal reduction reaction, affecting the extraction efficiency and metal purity. Therefore, there is an urgent need to provide a comprehensive treatment method applicable to the zinc anode slime system, with high metal recovery efficiency, thorough waste liquid purification, and the residue being recyclable. Summary of the Invention

[0004] In view of the deficiencies of the existing technology, the present invention provides a comprehensive recovery and treatment method for zinc anode slime, which solves the problems of difficult recovery of valuable metals in zinc anode slime, poor separation selectivity due to many impurities, and incomplete treatment of residual slag liquid.

[0005] To achieve the above objectives, the present invention is realized through the following technical solutions: A comprehensive recovery and treatment method for zinc anode slime, comprising the following steps:

[0006] S1. Material pretreatment: Screen and float the zinc anode slime to remove the non-metallic impurities therein, and obtain metal ore materials suitable for further recovery;

[0007] S2. Optimal control: Based on the optimal control theory, the metal ore materials are put into acidic solution or alkaline solution, and at the same time, an optimization objective function for the recovery process is constructed. Using machine learning and through multi-dimensional data analysis, the optimal operating temperature, pH value, and current density are solved;

[0008] S3. Metal dissolution and leaching: Adjust the acidic solution and alkaline solution according to the calculated optimal operating temperature, pH value, and current density. Dissolve metal zinc, copper, lead, and silver through the leaching reaction to form metal ions;

[0009] S4. Electrolytic deposition: Pass the separated metal solution through the electrolytic deposition process to precipitate metal zinc, copper, lead, and silver in sequence. Collect the precipitated metals separately, and store the final remaining waste residue and waste liquid separately after the precipitation is completed;

[0010] S5. Waste residue treatment and metal recovery: Chemically reduce and roast the waste residue at high temperature to further recover the residual metals in it, and treat the remaining waste residue as industrial raw materials;

[0011] S6. Waste liquid treatment and recovery: Treat the waste liquid through chemical precipitation to recover the metal ions in it, and make the waste liquid meet the environmental protection discharge standards for discharge.

[0012] Preferably, in the step S1, the non-metallic impurities include:

[0013] Silicate minerals: including quartz and feldspar. These minerals do not contain metals with recovery value and usually have no direct impact on the metal recovery process, but will affect the recovery efficiency;

[0014] Oxides: including iron oxide and aluminum oxide. These oxides belong to non-metallic components and do not participate in the metal dissolution and deposition processes;

[0015] Chlorides and sulfates: including sodium chloride, calcium chloride compounds, and calcium sulfate minerals. These salts are often not dissolved during the recovery process and need to be removed in the pretreatment stage;

[0016] Organic substances: including residual grease, resin, and cinder such organic substances. These organic impurities have no positive effect on metal recovery;

[0017] Heavy metal impurities: including cadmium and mercury, etc. Although these elements are metals, they may need to be screened or floated first during the recovery process;

[0018] The screening is carried out through different pore sizes of the sieve mesh and the sieve bed, and the operation method is as follows:

[0019] After the zinc anode slime is crushed, it is fed into the screening equipment;

[0020] The screen aperture is selected according to the size of the impurity particles;

[0021] Large particle impurities and larger mineral particles will be retained on the screen, while smaller particles will pass through the screen and enter the next processing step;

[0022] The screening particle size of the screen and the screen bed is 0.1 mm to 10 mm.

[0023] Preferably, in the step S2, the optimization objective function of the recovery process adjusts the temperature, pH value, and current density of the solution based on real-time data feedback, and automatically adjusts the temperature, pH value, and current density through sensors and a control system;

[0024] The sensors include a temperature sensor, a pH sensor, a current density sensor, an ion concentration sensor, and a redox potential sensor;

[0025] In the step S2, the acidic solution is a sulfuric acid solution, and the alkaline solution is a sodium hydroxide solution.

[0026] Preferably, in the step S2, machine learning includes:

[0027] By combining historical data with real-time data, a prediction model in the recovery process is established. These models help identify the key factors affecting metal recovery efficiency and predict the recovery effect under different operating conditions;

[0028] Through regression analysis and neural network technology, multiple parameters such as temperature, pH value, and current density are modeled to obtain the most suitable recovery conditions;

[0029] The multi-dimensional data analysis specifically includes:

[0030] By analyzing and combining sensor data from different sources, joint analysis of each parameter is carried out to determine its influence degree on metal recovery rate;

[0031] Using time series data analysis, the change trends of different parameters in the solution are mined, potential deviations in the recovery process are predicted, and operating conditions are provided for subsequent adjustment.

[0032] Preferably, in the step S3, the leaching temperature of the acidic solution is controlled at 50 °C to 80 °C, and the pH value is controlled at 1 to 3; the leaching temperature of the alkaline solution is controlled at 60 °C to 90 °C, and the pH value is controlled at 9 to 11.

[0033] Preferably, in the step S4, the electrolytic deposition process includes:

[0034] By adjusting the current density, voltage, and temperature of the electrolytic cell, zinc metal is first precipitated, and its precipitation voltage is -1.0 V to -0.7 V;

[0035] Then copper metal is precipitated, and the precipitation voltage is -0.4V to -0.2V;

[0036] Finally, lead and silver are precipitated, and the precipitation voltages are -0.2V to +0.1V and +0.7V to +0.9V respectively;

[0037] The current density is between 50 A / m 2 and 150 A / m 2 when zinc is precipitated; between 100 A / m 2 and 200 A / m 2 when copper is precipitated; and between 30 A / m 2 and 80 A / m 2 when lead and silver are precipitated.

[0038] Preferably, in the step S5, the waste residue is treated by high-temperature roasting, the roasting temperature is 800°C to 1000°C, the roasting time is 2h to 4h, copper and lead in it are recovered, and the remaining waste residue is treated by physical and chemical methods and used as building materials or road fillers.

[0039] Preferably, in the step S5, the chemical reduction roasting includes:

[0040] Roasting process: Feed the waste residue into a high-temperature furnace, and control the temperature within the range of 600°C to 1200°C; the high temperature causes the metal oxides in the waste residue to undergo a reduction reaction and transform into the metal form;

[0041] Reducing atmosphere: During the roasting process, provide a reducing atmosphere to reduce the oxidation state of the metal oxides in the waste residue and transform them into metals;

[0042] The reducing atmosphere is selected according to the remaining metals, and specifically includes:

[0043] Carbon monoxide, usually used to reduce zinc, copper and lead;

[0044] Hydrogen, usually used to reduce lead, copper and silver;

[0045] Methane, usually used to reduce iron;

[0046] A mixed gas of carbon monoxide and hydrogen, usually used to reduce iron, copper, zinc and lead;

[0047] Ammonia, usually used to reduce aluminum, titanium, magnesium, tantalum and tungsten;

[0048] The remaining metals include:

[0049] Zinc: Zinc in the waste residue usually exists in the form of oxides and can be reduced to metallic zinc by high-temperature roasting;

[0050] Copper: Copper in the waste residue also exists in the form of oxides and can be reduced to metallic copper through a reduction reaction;

[0051] Lead: Lead in the waste residue exists in the form of lead oxides and can be reduced to metallic lead through a reduction roasting process;

[0052] Silver: A small amount of silver and silver oxides in the waste residue can also be reduced to metallic silver under a reducing atmosphere.

[0053] Preferably, in the step S5, the treatment of industrial raw materials specifically includes:

[0054] Preliminary screening and classification of waste residue: The waste residue is screened through a sieve and divided into particles of different particle sizes. The large-particle waste residue is crushed, and the small-particle waste residue is used for subsequent treatment;

[0055] Crushing and grinding: The larger-particle waste residue is crushed into small particles by a crusher, and then the waste residue is further ground into a powder by a grinding device to increase the surface area;

[0056] High-temperature roasting treatment: The waste residue is heated to 600°C - 1200°C in a high-temperature roasting furnace for metal reduction and removal of harmful components;

[0057] Chemical treatment and modification: The waste residue is treated by pickling or alkali washing to remove impurities and heavy metals, and stabilizers are added if necessary to improve the performance;

[0058] Physical processing and mixing of waste residue: The waste residue is mixed with cement, sand or lime;

[0059] Shaping and solidification of waste residue: The mixed waste residue is shaped into bricks, plates and concrete, and solidification treatment is carried out to enhance the strength;

[0060] Quality inspection and standardization: The formed waste residue products are subjected to quality inspection to ensure that they meet the relevant standards, mainly testing the compressive strength and particle size;

[0061] Final application: The treated waste residue can be used as building materials or road fillers.

[0062] Preferably, in the step S6, the waste liquid is chemically precipitated by adding sodium hydroxide, and after precipitation, zinc, copper and lead metal ions in the waste liquid are recovered by the ion exchange method, and the recovery rate reaches more than 90%, and the treated waste liquid meets the environmental protection discharge standards.

[0063] The present invention provides a comprehensive recovery and treatment method for zinc anode slime. It has the following beneficial effects:

[0064] 1. The present invention adopts a combined process of multi-stage chemical precipitation of waste liquid + ion exchange, aiming at the complex waste liquid generated during the leaching process of zinc anode slime, and realizes the efficient removal of various harmful metal ions therein, achieving the treatment effect that the waste liquid can be stably discharged. Compared with the prior art, in which a single precipitation method is used to treat electrolytic by-product waste liquid, resulting in difficulties in pH control and metal residue problems, this solution significantly improves the purification degree and process stability.

[0065] 2. The present invention further resources the residue obtained after roasting zinc anode slime, and through modification and shaping, it is used to prepare road fillers or building raw materials, so that the waste residue is not only stably disposed of, but also transformed into materials with practical application value. Different from the prior art, in which only landfill or stacking methods are used, this solution effectively reduces the post-treatment burden and at the same time expands the reuse path of electrolytic zinc by-products.

[0066] 3. The present invention realizes the step-by-step reduction of various metal oxides in zinc anode slime by controlling the type and ratio of reducing atmosphere, effectively improving the selectivity of metal extraction and the flexibility of process control. Compared with the prior art, in which a unified atmosphere reduction strategy leads to cross-interference of metal reactions, this solution overcomes the problems of low extraction efficiency and component mixing, and is particularly suitable for the fine recovery of coexisting systems such as zinc, lead, and silver. BRIEF DESCRIPTION OF THE DRAWINGS

[0067] Figure 1 It is a flow chart of the method steps of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0068] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the drawings of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0069] Please refer to the appendix Figure 1 , the embodiment of the present invention provides a comprehensive recovery and treatment method for zinc anode slime, including the following steps:

[0070] S1. Material pretreatment: Screen and float the zinc anode slime to remove the non-metallic impurities therein, and obtain metal ore materials suitable for further recovery;

[0071] Specifically, in the comprehensive recovery and treatment of zinc anode slime, the material pretreatment step is the key to ensuring the smooth progress of the subsequent recovery process. The main purpose of this step is to remove non-metallic impurities in the zinc anode slime through screening and flotation to obtain metal ore materials suitable for further recovery. The pretreatment of the material is directly related to the metal recovery efficiency and the treatment effect of the waste residue. Therefore, appropriate pretreatment methods need to be adopted according to the composition and properties of the zinc anode slime. The optimized design of this step will ensure the efficient progress of metal dissolution, electrolytic deposition, waste liquid and waste residue treatment and other links in the subsequent recovery process.

[0072] In this embodiment, in the material pretreatment step, non-metallic impurities in the zinc anode slime are first removed through screening and flotation. During the screening process, different pore-sized sieves and sieve beds are used to separate large-particle impurities and larger mineral particles in the zinc anode slime. By controlling the sieve pore size and the screening particle size of the sieve bed, generally, the screening particle size is selected in the range of 0.1 mm to 10 mm to ensure that large-particle impurities and mineral particles that do not meet the recovery requirements are effectively removed. After the zinc anode slime is crushed, it is fed into the screening equipment. During the screening process, larger-particle impurities and mineral particles are isolated on the sieve, while smaller particles pass through the sieve and enter the next treatment link.

[0073] As an option, non-metallic impurities include but are not limited to silicate minerals, oxides, chlorides and sulfates, organic substances, and heavy metal impurities, etc. Silicate minerals such as quartz and feldspar, these minerals do not contain metals with recovery value and usually have no direct impact on the metal recovery process, but will reduce the recovery efficiency; oxides such as iron oxide and aluminum oxide, these oxides do not participate in the metal dissolution and deposition processes; chlorides and sulfates, such as sodium chloride, calcium chloride compounds, and calcium sulfate minerals, are often not dissolved during the recovery process and need to be removed in the pretreatment stage; organic substances, such as residual grease, resin, and cinder, etc., these organic impurities have no positive effect on metal recovery; heavy metal impurities, such as cadmium and mercury, although these elements are metals, they need to be removed by screening or flotation during the recovery process.

[0074] In a possible implementation manner, the screening equipment removes impurities of different particle sizes through a combination of multi-stage sieves and sieve beds. After the large-particle impurities are physically crushed, they can be further refined to ensure that the metal minerals meeting the recovery standards are further processed.

[0075] In this embodiment, after screening is completed, flotation treatment is further carried out to remove the light minerals and some impurities therein. During the flotation process, by introducing flotation reagents and bubbles, the minerals without recovery value float up and are taken away, while the metal minerals settle to the bottom and are retained as materials suitable for recovery. The types and dosages of the flotation reagents can be adjusted according to the actual composition of the zinc anode slime.

[0076] Specifically, in the flotation process, the selection of flotation reagents is one of the key factors. Flotation agents generally include collectors, inhibitors, and frothers, etc. Among them, collectors are used to promote the attachment of metal minerals to bubbles, inhibitors are used to inhibit the impurity minerals that do not need to float, and frothers are used to form a stable bubble layer. In actual operation, by adjusting the dosage of flotation reagents, the generation rate of bubbles, and the flotation time, the recovery rate of metal minerals can be effectively increased and impurities can be removed.

[0077] In some embodiments, the specific parameters of screening and flotation may need to be adjusted according to the physicochemical properties of zinc anode mud. For example, the selection of the screen aperture may vary depending on the composition and particle size of the material, and the dosage of reagents and the generation rate of bubbles during flotation also need to be precisely adjusted according to experimental data.

[0078] In this embodiment, during the screening and flotation process, the quality of the metal ore material is optimized, providing a basis for the subsequent metal dissolution and recovery processes. The optimization of this step not only improves the metal recovery rate but also lays a foundation for the smooth progress of the waste residue and waste liquid treatment links.

[0079] In a possible implementation, by screening and flotation to remove different types of impurities, the metal components in zinc anode mud can be made purer, thereby improving the efficiency in the subsequent metal dissolution process.

[0080] S2. Optimal control: Based on the optimal control theory, the metal ore material is put into an acidic solution or an alkaline solution, and at the same time, an optimization objective function for the recovery process is constructed. Using machine learning and through multi-dimensional data analysis, the optimal operating temperature, pH value, and current density are solved.

[0081] Specifically, in the comprehensive recovery process of zinc anode mud, the optimal control step is one of the core links to achieve efficient recovery. This step mainly adjusts various operating conditions (such as temperature, pH value, current density) in the recovery process through the optimal control theory to achieve the best metal recovery effect. To ensure the efficient operation of the entire recovery process, this step makes full use of the real-time data feedback mechanism and machine learning technology to dynamically adjust the process conditions, thereby achieving precise control of each link.

[0082] In this embodiment, in the optimal control step, first, by constructing an optimization objective function for the recovery process, the metal ore material is put into an acidic solution or an alkaline solution. During this process, the temperature, pH value, and current density of the solution are the key factors affecting the recovery efficiency. Therefore, the construction of the optimization objective function focuses on the influence of these factors on the recovery effect, and through machine learning technology, analyzes and predicts the recovery efficiency under different operating conditions. Generally, by combining historical data and real-time data, machine learning algorithms can identify the most suitable operating parameters to ensure the maximization of metal recovery rate.

[0083] Specifically, during the operation process, first, the solution temperature is controlled. According to the properties of the recovered material and the dissolution characteristics of the target metal, the control system adjusts the temperature in real time to ensure the optimal reaction rate. For the acidic solution, sulfuric acid solution is usually selected as the solvent, while for the alkaline solution, sodium hydroxide solution is used. The reaction conditions of each solution are carefully adjusted according to the real-time feedback of the recovery process. The pH value is controlled within an ideal range, which not only avoids unnecessary side reactions but also promotes the dissolution and deposition of the target metal.

[0084] As an option, this step also introduces real-time sensors and a control system, which can monitor parameters such as temperature, pH value, current density, and ion concentration in real time. The types of sensors include temperature sensors, pH sensors, current density sensors, ion concentration sensors, etc. The combination of these sensors can provide comprehensive feedback information to ensure that the parameters in the recovery process fluctuate within the set range and are adjusted by the automated control system when necessary.

[0085] In a possible implementation, through multi-dimensional data analysis and combining the data obtained from each sensor, the control system can dynamically adjust the operating conditions and optimize the process in real time. Specifically, the system uses machine learning technologies such as regression analysis and neural networks to model multiple process parameters such as temperature, pH value, and current density to obtain the most suitable operating conditions. Through these technologies, the system can not only adjust the operating conditions in real time but also predict possible deviations and take remedial measures in advance.

[0086] In some embodiments, the influence degree of various parameters (such as temperature, pH value, current density) in the recovery process on the metal recovery rate is evaluated by jointly analyzing sensor data from different sources. Through time series data analysis, the change trends of different parameters in the solution can be mined, and possible process deviations can be predicted, providing a basis for adjusting the operating conditions. These adjustments can improve the metal recovery rate while reducing energy consumption and solvent waste.

[0087] In this embodiment, during the recycling process, the machine learning model helps analyze and evaluate the recycling effect under different operating conditions. The optimized operating conditions can significantly improve the recycling efficiency. In addition, by using real-time data feedback, the system can continuously optimize the operating conditions to ensure that the metal recycling in each link can achieve the optimal effect.

[0088] Specifically, the obtained optimization objective function takes into account multiple factors such as operating cost, energy efficiency, and metal recovery rate. During the optimization process, the objective function can be expressed in the following form:

[0089]

[0090] where T is the temperature; pH is the acidity and alkalinity; I is the current density; R i (T, pH, I) represents the recovery rate of the i-th metal; C(T, pH, I) represents the operating cost under this condition; α i and β are weight coefficients; n is a constant. By optimizing this objective function, the optimal recycling effect can be achieved.

[0091] In some embodiments, the optimization scheme of this step can also be adjusted according to the specific composition of the zinc anode slime. Different minerals have different dissolution rates under different solution conditions. Therefore, the objective function of optimal control will be dynamically adjusted according to the specific characteristics of the minerals. This adaptive control method ensures the high efficiency and flexibility of the recycling process.

[0092] In this embodiment, through intelligent optimization control, the operating conditions of the entire recycling process are precisely regulated, ensuring the maximum recovery of metal components in the zinc anode slime and greatly improving the resource utilization rate. The synergistic effect of each link has improved the overall efficiency of the recycling process.

[0093] S3. Metal dissolution and leaching: Adjust the acidic solution and alkaline solution according to the calculated optimal operating temperature, pH value, and current density, and dissolve metal zinc, copper, lead, and silver through the leaching reaction to form metal ions.

[0094] Specifically, in the aforementioned steps S1 and S2, the pretreatment of the zinc anode slime and the optimization operation of the recycling process have laid the foundation for metal dissolution and leaching. Impurities are removed through screening and flotation, and the temperature, pH value, and current density of the solution are adjusted using optimal control to ensure that the dissolution process can be carried out under ideal conditions. The subsequent metal dissolution and leaching steps aim to leach metal zinc, copper, lead, and silver through acidic or alkaline solutions to form metal ions for subsequent metal recycling.

[0095] In this embodiment, in the metal dissolution and leaching step, first, according to the optimal control results of the foregoing step S2, the temperatures, pH values, and other key parameters of the acidic solution and the alkaline solution are precisely adjusted. The acidic solution is a sulfuric acid solution, and the alkaline solution is a sodium hydroxide solution. By adjusting the temperatures and pH values of these two solutions, metal ions (such as zinc, copper, lead, and silver) in the metal anode mud can be effectively dissolved in the solution.

[0096] Specifically, the leaching temperature of the acidic solution is usually controlled between 50°C and 80°C, and the pH value is controlled between 1 and 3. Under these conditions, metals such as zinc and copper can dissolve rapidly, while impurities such as oxides will precipitate. At this time, the dissolution reactions of zinc and copper are as follows:

[0097] ZnO + H2SO4 → ZnSO4 + H2O;

[0098] For the alkaline solution, the leaching temperature is usually controlled between 60°C and 90°C, and the pH value is controlled between 9 and 11. Within this pH range, metal ions such as lead and silver can also dissolve relatively smoothly and be converted into corresponding metal ions. According to the different dissolution characteristics of metals, the concentration of the solution and the operation time can be further adjusted to ensure the full dissolution of various metals.

[0099] Generally, the contact time between the acid-base solution and the metal anode mud during the dissolution process needs to be optimized to achieve the best leaching effect. Too short a leaching time may result in incomplete dissolution of metal ions, while too long a leaching time may cause the dissolution of impurities in the solution, affecting the purity of the metal. Therefore, by controlling the dissolution time, maximum metal recovery can be achieved while avoiding the introduction of impurities into the solution.

[0100] As an option, to further improve the metal dissolution efficiency, appropriate complexing agents or catalysts can be used during the leaching process. For example, by adding a small amount of complexing agents, the dissolution rate of metal ions can be promoted, thereby increasing the metal recovery rate. These complexing agents can be selected such as amino acid-based, acetic acid-based compounds, etc., which can form soluble complexes with metal ions, thus enhancing the dissolution rate.

[0101] In a possible implementation, by using an efficient stirring system, the contact between the solution and the metal minerals can be enhanced, and the dissolution rate can be increased. At this time, by dynamically monitoring the metal ion concentration in the solution, the stirring speed and the temperature of the solution can be adjusted in real time to ensure the efficiency of the dissolution process.

[0102] In some embodiments, during the leaching process, the dynamic adjustment of the pH value and temperature in the solution is controlled by a real-time monitoring system. The system collects data such as the temperature, pH value, and metal ion concentration in the solution through sensors, provides real-time feedback, and adjusts the reaction conditions. Through this control method, the stability and efficiency of metal dissolution can be ensured, while the occurrence of side reactions is reduced, and the recovery rate is increased.

[0103] In this embodiment, during the metal dissolution and leaching process, the obtained metal solution usually contains various metal ions, including zinc, copper, lead, silver, etc. In the subsequent electrolytic deposition step, these metal ions will be separated one by one and precipitated in the form of metals. Therefore, the optimization of the metal dissolution and leaching steps is crucial for ensuring the metal recovery efficiency in the subsequent steps.

[0104] By precisely adjusting key factors such as the temperature, pH value, and leaching time of the solution, metal ions can be fully dissolved in the metal dissolution and leaching stage, and the recovery efficiency can be maximized. In addition, the operation parameter settings in this embodiment can effectively avoid excessive dissolution of impurities, ensure the high purity of the metal solution, and thus provide ideal solution conditions for the subsequent electrolytic deposition step.

[0105] S4. Electrolytic deposition: Pass the separated metal solution through the electrolytic deposition process to precipitate metals such as zinc, copper, lead, and silver in sequence, collect the precipitated metals separately, and store the final remaining waste residue and waste liquid separately after the precipitation is completed.

[0106] Specifically, in the aforementioned step S3, the metal ions in the zinc anode slime have been successfully dissolved and converted into a metal ion solution in the metal dissolution and leaching link. The subsequent electrolytic deposition step is a key metal recovery link. Through electrolytic deposition technology, the metal ions in the solution will be precipitated in sequence and converted into metal forms. The core goal of this step is to achieve the separation and purification of different metals and ensure the efficiency and operability of the recovery process.

[0107] In this embodiment, during the electrolytic deposition process, first, according to conditions such as the composition, temperature, and pH value of the solution, precisely adjust the current density, voltage, and temperature of the electrolytic cell to ensure the step-by-step precipitation of metals. According to the precipitation potentials of different metals, metals such as zinc, copper, lead, and silver are precipitated from the solution in sequence. Specifically, the precipitation voltage range of metal zinc is -1.0V to -0.7V; the precipitation voltage range of copper is -0.4V to -0.2V; the precipitation voltage range of lead is -0.2V to +0.1V; the precipitation voltage range of silver is +0.7V to +0.9V.

[0108] Specifically, at the beginning of the electrolytic deposition, zinc ions are first reduced on the cathode and precipitated as metallic zinc. The precipitation current density in this process is usually controlled at 50A / m 2 ~150A / m 2to ensure the efficient deposition of zinc and avoid side reactions. Then, copper ions are deposited at a relatively high voltage, and the deposition current density is usually controlled between 100 A / m 2 ~200 A / m 2 to ensure the deposition efficiency of copper. Lead and silver are deposited at a relatively low voltage, and the deposition current density is controlled between 30 A / m 2 ~80 A / m 2 The deposition sequence of each metal is closely related to the metal ion concentration in the electrolyte, the temperature of the solution, and the current density.

[0109] Generally, during the electrolytic deposition process, the adjustment of the pH value, temperature, and current density in the solution is crucial. To avoid the co-deposition of metal impurities, the pH value in the solution should be maintained within an appropriate range, usually between 1 and 3, to ensure the preferential deposition of metals such as zinc and copper, while other impurity metals will not be deposited simultaneously. The control of temperature helps to increase the deposition rate of metals and avoid unnecessary side reactions.

[0110] As an option, during the electrolysis process, the electrolytic cell can be configured as a multi-chamber structure to separately control the deposition process of each metal. This can precisely control the deposition sequence of different metals and further improve the metal recovery rate and purity. Through the real-time monitoring of the electrolysis process, the control system can automatically adjust parameters such as the current density and voltage to optimize the metal deposition process.

[0111] In a possible implementation, when depositing metals, through precise current control, the metals in the electrolytic cell can be deposited in layers. For example, after initially depositing zinc, the current density is adjusted to deposit copper, and finally lead and silver are deposited. This step-by-step deposition method can not only ensure the high purity of each metal but also reduce the cross-contamination of impurities and improve the recovery effect.

[0112] In some embodiments, to ensure the efficient progress of the metal deposition process, a forced stirring device can be provided in the electrolytic deposition cell to enhance the contact between the solution and the electrode and promote the reduction process of metal ions. The intensity and frequency of stirring need to be optimized according to the composition and temperature of the electrolyte to avoid the accumulation of deposits on the electrode surface and affect the deposition quality.

[0113] In this embodiment, the deposition process of each metal can be independently adjusted. By optimizing conditions such as the current density, the design of the electrolytic cell, the pH value, and the temperature of the solution, the efficient separation of metals can be achieved. Finally, the deposited metals will be collected and further purified. After electrolytic deposition, the remaining solution and waste residue will be further processed and resource recovered according to the requirements of step S5.

[0114] Specifically, the metallic zinc, copper, lead, and silver after electrolytic deposition can be collected in their respective deposition tanks. The deposited metals will be sent to subsequent refining processes to remove surface impurities and obtain metal products with higher purity. These metals can be used in industrial production or further processed into other products to complete the entire recycling chain.

[0115] By precisely controlling various parameters during the electrolytic deposition process, not only can the metal recovery rate be increased, but also the purity of each metal can be improved, minimizing the influence of side reactions and impurities. The optimization of this step is crucial for the efficiency and resource utilization rate of the comprehensive recycling treatment method for zinc anode slime.

[0116] S5. Waste residue treatment and metal recovery: Chemically reduce and roast the waste residue at high temperature to further recover the residual metals therein, and treat the remaining waste residue as industrial raw materials.

[0117] Specifically, in the aforementioned step S4, through the electrolytic deposition process, metals such as zinc, copper, lead, and silver have been successfully separated from the metal solution. During this process, the remaining waste residue and waste liquid may still contain small amounts of metal elements and other harmful substances. Therefore, the subsequent treatment and further recovery of the waste residue have become key steps. The recovery of the waste residue not only helps to improve the overall resource utilization efficiency but also ensures the environmental friendliness of the treatment process.

[0118] In this embodiment, the treatment of the waste residue is first carried out through high-temperature roasting treatment. This process mainly reduces the metal oxides in the waste residue to the metallic form by heating the waste residue. The roasting temperature is usually controlled between 800°C and 1000°C, and the roasting time is controlled between 2 hours and 4 hours. The specific roasting conditions are appropriately adjusted according to the composition of the waste residue. At high temperatures, the metal oxides are transformed into the metallic form through reduction reactions, while removing the harmful components in the waste residue. During the roasting process, the control of oxygen or other atmospheres is very important. Excessive oxidation may cause some metals to not be reduced to the metallic state.

[0119] Specifically, during the roasting process, metal oxides such as copper and lead in the waste residue will be transformed into metallic copper and metallic lead, and these metals can be further recovered. Taking copper as an example, copper oxide reacts with carbon monoxide in a high-temperature reducing atmosphere to form metallic copper:

[0120] CuO + CO → Cu + CO2;

[0121] For lead, it will also be transformed into metallic lead through a similar reduction reaction:

[0122] PbO + CO → Pb + CO2;

[0123] Generally, there may still be a small amount of metals remaining in the waste residue after high-temperature roasting, especially metal oxides that are difficult to reduce. To further improve the metal recovery rate, metal particles can be separated from the waste residue through physical methods (such as screening and flotation). After the residual metals are recovered, their purity can be improved through refining techniques.

[0124] As an option, during the roasting process, different metals can be reduced by adjusting the reducing atmosphere (such as using hydrogen, carbon monoxide, or ammonia, etc.). The choice of the reducing atmosphere depends on the types of metals in the waste residue. For example, carbon monoxide is commonly used to reduce copper, zinc, and lead, while ammonia is commonly used to reduce aluminum and titanium. Through this atmosphere control, metals can be accurately reduced while avoiding the release of other harmful gases.

[0125] In a possible implementation, the atmosphere control during the reduction process can be achieved through precise gas flow meters and an atmosphere regulation system. The flow rate and proportion of the gas will be adjusted in real time according to the working state of the roasting furnace to ensure the smooth progress of the reduction reaction and avoid overreaction.

[0126] In this embodiment, during the roasting process of the waste residue, the further metal extraction process also includes removing residual impurities through pickling or other chemical treatment methods. For example, lead and copper can be leached with sulfuric acid or hydrochloric acid solution to remove surface oxides and other impurities, thereby improving the purity of the metals.

[0127] In some embodiments, after the waste residue after the roasting process is further processed, the remaining inorganic part can be utilized as an industrial raw material. After these waste residues are screened, crushed, and modified, they can be used as building materials or road fillers, etc., which not only reduces the stacking of waste residues but also improves the resource utilization rate. Such waste residues can achieve the strength and stability that meet engineering requirements through physical treatment, chemical modification, or mixing with other additives.

[0128] Specifically, during the treatment process, the waste residue is first classified through screening and crushing, breaking the large-particle waste residue into smaller particles to increase its surface area, thereby improving the efficiency of subsequent treatment. Then, after modification and mixing treatment, the waste residue is mixed with cement, lime, or sand, etc., and through the solidification and shaping process, building materials such as bricks and plates are formed. Through quality inspection, it is ensured that these solidified products meet the relevant engineering standards, and the main inspection contents include compressive strength, durability, and particle size.

[0129] In this embodiment, the treatment process of the waste residue not only optimizes the effect of metal recovery but also realizes the resource utilization of the waste residue. Through steps such as roasting, reduction, and post-treatment, not only can valuable metals in it be recovered, but the remaining waste residue can also be converted into useful building materials, providing a more effective solution for environmental protection and resource recovery.

[0130] Through this series of treatment processes, the metals in the waste residue are maximally recovered, and at the same time, the remaining waste residue is reasonably recycled. This step effectively improves the overall metal recovery rate and ensures the environmental protection treatment of the waste, meeting the requirements of sustainable development.

[0131] S6. Waste liquid treatment and recovery: The waste liquid is treated by chemical precipitation to recover the metal ions therein, and the waste liquid is discharged to meet the environmental protection discharge standards.

[0132] Specifically, in the aforementioned step S5, the waste residue has been treated by high-temperature roasting to reduce the metals therein to the metallic form and recover them. However, waste liquid treatment remains a key link in waste management. The waste liquid may still contain a certain amount of harmful metal ions and chemical substances. How to treat it and ensure compliance with the environmental protection discharge standards is the core goal of this step. Waste liquid treatment not only needs to remove metal ions, but also takes into account the efficiency of chemical reactions and the drainability of the waste liquid.

[0133] In this embodiment, the waste liquid treatment first removes the metal ions in the solution by the chemical precipitation method. Specifically, the metal ions contained in the waste liquid, such as zinc, copper, lead, etc., first generate metal hydroxide precipitates by adding sodium hydroxide or other appropriate precipitants. These precipitates can be separated from the liquid by physical methods such as filtration or centrifugation. The precipitated metal oxides can be further recovered to increase the resource utilization rate.

[0134] Specifically, for example, when treating zinc-containing waste liquid, after adding sodium hydroxide, it will react with zinc ions to generate zinc hydroxide precipitate:

[0135] Zn 2+ +2OH - →Zn(OH)2↓;

[0136] The zinc hydroxide generated by this reaction can be removed by centrifugation, filtration, etc., and the remaining waste liquid is further treated.

[0137] Generally, the conditions of the precipitation reaction need to be strictly controlled. An excessive amount of precipitant will cause the formation of additional precipitates, while insufficient precipitation may result in incomplete removal of metal ions. By precisely adjusting the pH value, the effect of the precipitation reaction can be controlled to ensure complete precipitation of metal ions without forming other unwanted compounds.

[0138] As an alternative, metal ions in the waste liquid can be recovered by further ion exchange method. During the ion exchange process, the waste liquid passes through an ion exchange resin bed to exchange the metal ions therein, thereby achieving the recovery of metals. Especially for metals such as zinc, copper, and lead, ion exchange technology has been proven to be able to efficiently recover these metals, and the recovery rate can usually reach more than 90%.

[0139] In one possible implementation, during the ion exchange process, selecting a suitable resin or membrane material can effectively improve the recovery efficiency. The resin material is designed according to the selectivity of metal ions to ensure that specific metal ions can be preferentially adsorbed, and other impurities are effectively filtered. The advantage of this technology is that it can be continuously used, and only needs to be regenerated or replaced periodically.

[0140] In some embodiments, the treatment of the waste liquid may also involve other advanced oxidation technologies (AOPs), such as ozone oxidation or photocatalytic oxidation, to further degrade the organic matter or non-metal pollutants in the waste liquid. By using ozone, hydrogen peroxide, or photocatalyst, etc., the organic impurities and harmful substances in the waste liquid can be effectively decomposed, improving the treatment effect and reducing secondary pollution.

[0141] In this embodiment, after the waste liquid is treated by chemical precipitation and ion exchange, the concentration of metal ions is reduced and meets the environmental protection discharge standards. The waste liquid undergoes final filtration and impurity removal treatment, and can be safely discharged or used for other industrial purposes after reaching the discharge standards.

[0142] Specifically, the treated waste liquid not only meets the environmental protection standards, but also realizes efficient metal recovery through advanced treatment technologies. The treated waste liquid can be further utilized as recycled water, or used for purposes such as irrigation that do not involve heavy metal accumulation. In this way, the metal elements and other harmful substances in the waste liquid are completely removed, further reducing the waste of resources in the production process.

[0143] In one possible implementation, after the waste liquid is treated, if there is still a small amount of metal residue, it can be further purified and recovered by methods such as adding the precipitant again, adjusting the solution again, and concentrating. In this way, not only the waste water discharge is reduced, but also the metal recovery and resource utilization are maximized.

[0144] Through the precise treatment of this step, the metal elements in the waste liquid are completely removed, and the treated waste liquid meets the environmental protection discharge standards, ensuring that all environmental protection requirements in the entire recovery and treatment process are met. This step effectively reduces environmental pollution, improves the recovery rate of resources, and provides a safe and stable treatment environment for subsequent processes.

[0145] In step S1, the non-metal impurities include:

[0146] Silicate minerals: including quartz and feldspar, these minerals do not contain metals with recycling value and usually have no direct impact on the metal recycling process, but will affect the recycling efficiency;

[0147] Oxides: including iron oxide and aluminum oxide, these oxides belong to non-metallic components and do not participate in the metal dissolution and deposition processes;

[0148] Chlorides and sulfates: including sodium chloride, calcium chloride compounds and calcium sulfate minerals, these salts are often not dissolved during the recycling process and need to be removed in the pretreatment stage;

[0149] Organic substances: including residual oils, resins and cinders, these organic impurities have no positive effect on metal recycling;

[0150] Heavy metal impurities: including cadmium and mercury, although these elements are metals, they need to be removed by screening or flotation first during the recycling process;

[0151] Screening is carried out through different pore sizes of the screen mesh and the screen bed, and the operation method is as follows:

[0152] After the zinc anode slime is crushed, it is fed into the screening equipment;

[0153] The pore size of the screen mesh is selected according to the size of the impurity particles;

[0154] Large particle impurities and larger mineral particles will be retained in the screen mesh, while smaller particles will pass through the screen mesh and enter the next treatment process;

[0155] The screening particle size of the screen mesh and the screen bed is 0.1mm - 10mm;

[0156] In step S2, the optimization objective function of the recycling process adjusts the temperature, pH value and current density of the solution based on real-time data feedback, and automatically adjusts the temperature, pH value and current density through sensors and control systems;

[0157] The sensors include temperature sensors, pH sensors, current density sensors, ion concentration sensors and redox potential sensors;

[0158] In step S2, the acidic solution is sulfuric acid solution and the alkaline solution is sodium hydroxide solution;

[0159] In step S2, machine learning includes:

[0160] By combining historical data with real-time data, prediction models in the recycling process are established, and these models help to identify the key factors affecting metal recycling efficiency and predict the recycling effects under different operating conditions;

[0161] Through regression analysis and neural network technology, multiple parameters such as temperature, pH value, and current density are modeled to obtain the most suitable recovery conditions;

[0162] The multi-dimensional data analysis specifically includes:

[0163] By analyzing and combining sensor data from different sources, joint analysis of each parameter is carried out to determine its influence degree on the metal recovery rate;

[0164] Using time series data analysis, the change trends of different parameters in the solution are mined, possible deviations in the recovery process are predicted, and operating conditions are provided for subsequent adjustment;

[0165] In step S3, the leaching temperature of the acidic solution is controlled at 50°C to 80°C, and the pH value is controlled at 1 to 3; the leaching temperature of the alkaline solution is controlled at 60°C to 90°C, and the pH value is controlled at 9 to 11;

[0166] In step S4, the electrolytic deposition process includes:

[0167] By adjusting the current density, voltage, and temperature of the electrolytic cell, zinc metal is first precipitated, and its precipitation voltage is -1.0V to -0.7V;

[0168] Then copper metal is precipitated, and the precipitation voltage is -0.4V to -0.2V;

[0169] Finally, lead and silver are precipitated, and the precipitation voltages are -0.2V to +0.1V and +0.7V to +0.9V respectively;

[0170] The current density is between 50A / m 2 ~150A / m 2 when zinc is precipitated; between 100A / m 2 ~200A / m 2 when copper is precipitated; and between 30A / m 2 ~80A / m 2 when lead and silver are precipitated;

[0171] In step S5, the waste residue is treated by high-temperature roasting. The roasting temperature is 800°C to 1000°C, and the roasting time is 2h to 4h to recover copper and lead in it. The remaining waste residue is treated by physical and chemical methods and used as building materials or road fillers;

[0172] In step S5, the chemical reduction roasting includes:

[0173] The roasting process: The waste residue is sent into a high-temperature furnace, and the temperature is controlled within the range of 600°C to 1200°C; the high temperature causes the metal oxides in the waste residue to undergo a reduction reaction and transform into a metal form;

[0174] Reducing atmosphere: During the roasting process, a reducing atmosphere is provided to reduce the oxidation state of metal oxides in the waste residue and convert them into metals;

[0175] The reducing atmosphere is selected according to the remaining metals, specifically including:

[0176] Carbon monoxide, which is usually used to reduce zinc, copper, and lead;

[0177] Hydrogen, which is usually used to reduce lead, copper, and silver;

[0178] Methane, which is used to reduce iron;

[0179] A mixed gas of carbon monoxide and hydrogen, which is usually used to reduce iron, copper, zinc, and lead;

[0180] Ammonia, which is usually used to reduce aluminum, titanium, magnesium, tantalum, and tungsten;

[0181] The remaining metals include:

[0182] Zinc: Zinc in the waste residue usually exists in the form of oxides and can be reduced to metallic zinc through high-temperature roasting;

[0183] Copper: Copper in the waste residue also exists in the form of oxides and can be reduced to metallic copper through a reduction reaction;

[0184] Lead: Lead in the waste residue exists in the form of lead oxides and can be reduced to metallic lead through a reduction roasting process;

[0185] Silver: A small amount of silver and silver oxides in the waste residue can also be reduced to metallic silver under a reducing atmosphere;

[0186] In step S5, the industrial raw materials are processed specifically as follows:

[0187] Preliminary screening and classification of the waste residue: The waste residue is screened through a sieve and divided into particles of different particle sizes. The large-particle waste residue is crushed, and the small-particle waste residue is used for subsequent processing;

[0188] Crushing and pulverizing: The larger-particle waste residue is crushed into small particles by a crusher, and then further pulverized into a powder form by a pulverizing device to increase the surface area;

[0189] High-temperature roasting treatment: The waste residue is heated to 600°C - 1200°C in a high-temperature roasting furnace for metal reduction and removal of harmful components;

[0190] Chemical treatment and modification: The waste residue is treated by acid washing or alkali washing to remove impurities and heavy metals, and stabilizers are added if necessary to improve the performance;

[0191] Physical processing and mixing of the waste residue: The waste residue is mixed with cement, sand, or lime;

[0192] Molding and solidification of waste residue: The mixed waste residue is molded into bricks, plates and concrete, and solidification treatment is carried out to enhance the strength;

[0193] Quality inspection and standardization: The molded waste residue products are subjected to quality inspection to ensure that they meet the relevant standards, mainly including compressive strength and particle size;

[0194] In step S6, the waste liquid is chemically precipitated by adding sodium hydroxide. After precipitation, zinc, copper and lead metal ions in the waste liquid are recovered by the ion exchange method, and the recovery rate reaches more than 90%. The treated waste liquid meets the environmental protection discharge standards.

[0195] Although the embodiments of the present invention have been shown and described, those of ordinary skill in the art can understand that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principle and spirit of the present invention. The scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A comprehensive recovery and treatment method for zinc anode mud, characterized in that: The following steps are involved: S1. Material pretreatment: Screening and flotation treatment of zinc anode mud to remove non-metallic impurities and obtain metal mineral materials suitable for further recovery; S2. Optimal control: Based on the optimal control theory, the metal mineral material is put into an acidic solution or an alkaline solution, and the optimization objective function of the recovery process is constructed. By using machine learning and multi-dimensional data analysis, the optimal operating temperature, pH value and current density are solved; S3, metal dissolution and leaching: adjusting the acidic solution and the alkaline solution according to the calculated optimal operating temperature, pH value and current density, dissolving metal zinc, copper, lead and silver through leaching reaction to form metal ions; S4, electrolytic deposition: the separated metal solution is subjected to an electrolytic deposition process to sequentially precipitate metal zinc, copper, lead, and silver, the precipitated metals are collected respectively, and the waste residue and waste liquid remaining after the precipitation is completed are stored separately; S5. Waste slag treatment and metal recovery: chemically reduce the waste slag and calcine it at high temperature to further recover the residual metals therein, and treat the remaining waste slag as industrial raw materials; S6. Waste liquid treatment and recovery: The waste liquid is treated by chemical precipitation to recover the metal ions in it, so that the waste liquid meets the environmental emission standards for discharge.

2. A comprehensive recovery and treatment method for zinc anode mud according to claim 1, characterized in that: In the step S1, the non-metallic impurities include: Silicate minerals: including quartz and feldspar, these minerals do not contain metals of recycling value and usually have no direct impact on the metal recovery process, but they will affect the recovery efficiency; Oxides: including iron oxide and aluminum oxide. These oxides are non-metallic components and do not participate in the dissolution and deposition process of metals; Chlorides and sulfates: These include sodium chloride, calcium chloride salt compounds and calcium sulfate minerals. These salts are often not dissolved during the recovery process and need to be removed in the pretreatment stage; Organic matter: including residual grease, resin and coal slag, these organic impurities have no positive effect on metal recovery; Heavy metal impurities: including cadmium and mercury. Although these elements are metals, they need to be screened or flotated before being removed during the recycling process; The screening is carried out by using different apertures of the sieve and the sieve bed, and the operation method is as follows: After the zinc anode mud is crushed, it is sent to the screening equipment; The mesh size is selected according to the size of the impurity particles; Large impurities and larger mineral particles will be retained in the screen, while smaller particles will pass through the screen and enter the next processing step; The screening particle size of the sieve and the sieve bed is 0.1 mm to 10 mm.

3. The comprehensive recovery and treatment method of zinc anode mud according to claim 1, characterized in that: In the step S2, the optimization objective function of the recovery process adjusts the temperature, pH value and current density of the solution based on real-time data feedback, and automatically adjusts the temperature, pH value and current density through sensors and control systems; The sensors include a temperature sensor, a pH sensor, a current density sensor, an ion concentration sensor and an oxidation-reduction potential sensor; In the step S2, the acidic solution is a sulfuric acid solution, and the alkaline solution is a sodium hydroxide solution.

4. The comprehensive recovery and treatment method of zinc anode mud according to claim 1 is characterized in that: In the step S2, the machine learning includes: By combining historical data with real-time data, predictive models are established in the recycling process. These models help identify the key factors that affect metal recycling efficiency and predict the recycling effect under different operating conditions; Through regression analysis and neural network technology, multiple parameters such as temperature, pH value and current density are modeled to obtain the most suitable recovery conditions; The multi-dimensional data analysis specifically includes: By analyzing and combining sensor data from different sources, each parameter is jointly analyzed to determine its impact on metal recovery rate; By using time series data analysis, we can find out the changing trends of different parameters in the solution, predict possible deviations in the recovery process, and provide operating conditions for subsequent adjustments.

5. The comprehensive recovery and treatment method of zinc anode mud according to claim 1 is characterized in that: In the step S3, the leaching temperature of the acidic solution is controlled at 50°C to 80°C, and the pH value is controlled at 1 to 3; the leaching temperature of the alkaline solution is controlled at 60°C to 90°C, and the pH value is controlled at 9 to 11.

6. The comprehensive recovery and treatment method of zinc anode mud according to claim 1 is characterized in that: In the step S4, the electrolytic deposition process includes: By adjusting the current density, voltage and temperature of the electrolytic cell, zinc metal is first precipitated, and its precipitation voltage is -1.0V to -0.7V; Then copper metal is precipitated, and the precipitation voltage is -0.4V to -0.2V; Finally, lead and silver are precipitated at voltages of -0.2V to +0.1V and +0.7V to +0.9V respectively; The current density is 50A / m 2 ~150A / m 2 Between; when copper is precipitated at 100A / m 2 ~200A / m 2 Between; when precipitating lead and silver, 30A / m 2 ~80A / m 2 between.

7. The comprehensive recovery and treatment method of zinc anode mud according to claim 1 is characterized in that: In the step S5, the waste residue is treated by high-temperature roasting at a temperature of 800°C to 1000°C for a time of 2h to 4h to recover copper and lead therein, and the remaining waste residue is treated by physical and chemical methods as a building material or road filler.

8. The method for comprehensive recovery and treatment of zinc anode mud according to claim 1, characterized in that: In the step S5, the chemical reduction roasting comprises: Calcination process: the waste slag is sent into a high temperature furnace, and the temperature is controlled within the range of 600℃~1200℃; the high temperature causes the metal oxides in the waste slag to undergo a reduction reaction and transform into metal form; Reducing atmosphere: During the roasting process, a reducing atmosphere is provided to reduce the oxidation state of the metal oxides in the waste slag and convert them into metals; The reducing atmosphere is selected according to the remaining metal, and specifically includes: Carbon monoxide, commonly used to reduce zinc, copper, and lead; Hydrogen, commonly used to reduce lead, copper, and silver; methane, by being used to reduce iron; A mixture of carbon monoxide and hydrogen, usually used to reduce iron, copper, zinc, and lead; Ammonia, commonly used to reduce aluminum, titanium, magnesium, tantalum, and tungsten; The residual metals include: Zinc: Zinc in waste slag usually exists in the form of oxides, which can be reduced to metallic zinc by high-temperature roasting; Copper: Copper in waste slag also exists in the form of oxides and can be reduced to metallic copper through reduction reactions; Lead: Lead in waste residue exists in the form of lead oxide, which can be reduced to metallic lead through reduction roasting process; Silver: There will be a small amount of silver and silver oxide in the waste slag, which can also be reduced to metallic silver under a reducing atmosphere.

9. The comprehensive recovery and treatment method of zinc anode mud according to claim 1, characterized in that: In the step S5, the industrial raw materials are processed specifically including: Preliminary screening and classification of waste residue: the waste residue is screened through a screen and divided into particles of different sizes. Large particles of waste residue are crushed, and small particles of waste residue are used for subsequent treatment; Crushing and pulverizing: The larger particles of waste slag are crushed into small particles by a crusher, and then the waste slag is further crushed into powder by a pulverizing device to increase the surface area; High temperature roasting treatment: the waste slag is heated to 600℃~1200℃ in a high temperature roasting furnace to reduce metals and remove harmful components; Chemical treatment and modification: acid or alkali washing of waste residue to remove impurities and heavy metals, and adding stabilizers to improve performance if necessary; Physical processing and mixing of waste residues: mixing waste residues with cement, sand or lime; Molding and solidification of waste residue: Molding the mixed waste residue into bricks, panels and concrete, and solidifying it to enhance its strength; Quality inspection and standardization: Carry out quality inspection on the waste residue products after molding to ensure that they meet the relevant standards, mainly testing the compressive strength and particle size; Final Application: The treated waste residue can be used as building material or road fill.

10. The method for comprehensive recovery and treatment of zinc anode mud according to claim 1, characterized in that: In the step S6, the waste liquid is chemically precipitated by adding sodium hydroxide, and the zinc, copper and lead metal ions in the waste liquid are recovered by ion exchange after precipitation, with a recovery rate of more than 90%. The treated waste liquid meets environmental emission standards.

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