阅读说明：本技术 一种废铅蓄电池中铅膏的资源化回收处理方法 (Resource recovery processing method for lead plaster in waste lead storage battery ) 是由 谢锋 张壮 王伟 路殿坤 畅永锋 于 2021-09-26 设计创作，主要内容包括：一种废铅蓄电池中铅膏的资源化回收处理方法,属于废铅蓄电池资源化回收处理领域,本发明使用硫酸溶液对铅膏除杂,除杂处理后的铅膏中的非硫含铅组分通过无氟氯高效选择性浸出工艺处理成为可溶的有机酸铅,以有机酸铅溶液为电解液进行电沉积,阳极使用IrO-(2)·Ta-(2)O-(5)涂层钛电极,阴极制备高纯度的精铅。电沉积后电解液循环用于废铅膏中非硫含铅组分的浸出,实现废铅膏高效选择性浸出-电沉积制备精铅循环技术。本发明工艺缩短了回收处理废铅膏制备精铅的流程,减少了工艺流程中浸出剂的使用,一定程度上解决了在湿法回收废铅膏工艺中的试剂消耗量大,耗能高且设备条件要求高等问题,在减少污染的同时降低了成本,具有相当的市场前景。(The invention discloses a resource recovery processing method of lead plaster in waste lead storage batteries, belonging to the field of resource recovery processing of waste lead storage batteries 2 ·Ta 2 O 5 Coating a titanium electrode, and preparing high-purity refined lead by using a cathode. The electrolyte after electrodeposition is circularly used for leaching the non-sulfur lead-containing component in the waste lead paste, so that the high efficiency of the waste lead paste is realizedA selective leaching-electrodeposition refined lead preparation circulating technology. The process shortens the process of preparing refined lead by recycling the waste lead plaster, reduces the use of a leaching agent in the process flow, solves the problems of high reagent consumption, high energy consumption, high equipment condition requirement and the like in the process of recycling the waste lead plaster by a wet method to a certain extent, reduces the pollution and the cost, and has a considerable market prospect.)

1. A resource recycling treatment method for lead plaster in waste lead storage batteries is characterized by comprising the following steps:

(1) crushing and sorting the waste lead-acid storage batteries to obtain waste lead plaster;

(2) fully reacting the obtained waste lead plaster with sulfuric acid, and carrying out solid-liquid separation to obtain a solid phase and a liquid phase, wherein the solid phase is the lead plaster subjected to impurity removal, the liquid phase is a sulfuric acid solution containing impurity ions, and the solution is recycled as the leaching agent in the step (2);

(3) mixing the obtained lead plaster subjected to impurity removal and washing with a leaching agent, and performing pre-size mixing to obtain a solid-liquid mixture; adding hydrogen peroxide into the obtained solid-liquid mixture, reacting, and carrying out solid-liquid separation to obtain a solid phase and a liquid phase; the solid phase contains lead sulfate and is used as a lead sulfate product after washing and drying operations, and the liquid phase is a leaching pregnant solution which contains organic acid lead, free acid and hydrogen peroxide;

(4) adding an additive 1 serving as an anode lead dioxide inhibitor into the liquid phase obtained in the step (3), adding an additive 2 to regulate the appearance of the surface of cathode lead, and performing electrodeposition by using the mixed solution as electrolyte, wherein the anode uses a titanium anode, and the cathode obtains elemental lead;

(5) and (4) recycling the electrolyte after electrodeposition as a leaching agent in the step (3).

2. The resource recycling method for the lead plaster in the waste lead-acid storage battery as claimed in claim 1, wherein in the step (2), the concentration of the sulfuric acid is 1.5-6 mol/L, wherein the molar ratio of the sulfuric acid to lead elements of the non-sulfur lead-containing components in the waste lead-acid storage battery is (1-20): 1, and the reaction temperature is 50-80 ℃; the non-sulfur lead-containing component comprises PbO and PbO₂And Pb.

3. The resource recovery processing method of the lead plaster in the waste lead storage battery according to the claim 1, characterized in that in the step (3), the leaching agent is methanesulfonic acid or ethanesulfonic acid; the concentration of the methanesulfonic acid or the ethylsulfonic acid is 1-3.5 mol/L, the molar ratio of the methanesulfonic acid or the ethylsulfonic acid to the lead element of the lead-free component in the waste lead-acid storage battery is (2-8): 1, and the reaction temperature is 20-60 ℃.

4. The resource recycling method for lead plaster in waste lead-acid storage batteries according to claim 1, wherein in the step (3), the concentration of hydrogen peroxide solution is 1-10 mol/L, wherein the hydrogen peroxide and PbO in the waste lead-acid storage batteries₂The molar ratio of (1-1.2) to (1), and the reaction temperature is 20-60 ℃.

5. The resource recovery processing method of the lead plaster in the waste lead storage battery according to the claim 1, characterized in that in the step (4), the additive 1 for inhibiting the generation of anode lead dioxide is phosphoric acid, and the effective concentration of the phosphoric acid in the liquid phase is 1-3 g/L; the additive 2 for regulating and controlling the surface morphology of the cathode lead is any one of calcium lignosulphonate, sodium lignosulphonate and amino trimethylene phosphonic acid, and the effective concentration of the additive in a liquid phase is 0.1-10 g/L.

6. The method for recycling lead plaster of waste lead storage batteries according to claim 1, wherein in the step (4), the anode is IrO₂·Ta₂O₅Coating a titanium electrode; the current density is 150 to 300A/m²The electrodeposition temperature is 20-60 ℃, and the electrode spacing is 30-50 mm; the concentration of free organic acid in the electrolyte is 0.5-3.5 mol/L, the concentration of lead ions is 10-400 g/L, and the electrodeposition time is 3-6 h.

7. The method for recycling and treating the lead plaster in the waste lead-acid battery as claimed in claim 1, wherein the cathode current efficiency of the method for recycling and treating the lead plaster in the waste lead-acid battery is 94-99%, and the energy consumption in the electrodeposition process is 550-700 kWh/t.

Technical Field

The invention belongs to the field of resource recovery and treatment of waste lead storage batteries, and particularly relates to a resource recovery and treatment method for preparing refined lead by selective leaching and electrodeposition of a non-sulfur lead-containing component in a lead storage battery.

Background

China is the world's largest lead producing and consuming country. Statistically, the worldwide lead production trend is continuously increasing from 2007 to 2018, and the lead concentrate production in 2018 in China is up to 483 ten thousand tons, which is 4 times that in the second United states (116 ten thousand tons). About 86% of the refined lead produced annually worldwide is used in the production of lead-acid batteries. The lead-acid storage battery has the advantages of high safety, no memory effect, mature production process, low production cost and the like, and is widely applied.

The lead resource is mainly derived from primary lead resource and secondary lead resource. The raw lead resource is mainly a lead resource existing in a mineral form, such as galena (PbS) and white lead ore (PbCO)₃) And lead sulphate ore (PbSO)₄) And the like, and the secondary lead resource mainly originates from the waste lead-acid storage battery. Lead production has increased year by year over the last two decades, with the secondary lead resource being a more significant part of the year. With the annual increase of the waste lead-acid storage batteries, the waste lead-acid storage batteries become a main lead resource.

The waste lead-acid storage battery is usually recovered by a factory and can be used for producing and manufacturing a new lead-acid storage battery after being recovered. The waste lead-acid storage batteries can be divided into four components such as grid, plastics, waste sulfuric acid, waste lead plaster and the like after being crushed and sorted, wherein the waste lead plaster is the most difficult part to recycle in the waste lead-acid storage batteries. Four main components exist in the waste lead plaster, namely PbSO₄，PbO₂PbO and Pb.

At present, the lead in the waste lead plaster is mainly recovered by adopting a pyrometallurgical process in the industry. Compared with the wet smelting process for recovering lead, the pyrometallurgical process has high energy consumption and is easy to produce a large amount of pollution gases (lead dust, sulfur dioxide and the like). In order to reduce the pollution to the environment, the wet lead smelting process gradually receives more attention.

The leaching-electrodeposition is a common technical route in the wet lead smelting process, and a similar technical route also comprises a pre-desulfurization-leaching-electrodeposition process. A representative example of a pre-desulfurization-leaching-electrodeposition process is US 4769116A. The process adopts Na₂CO₃As a desulfurizing agent, adding a reducing agent to convert PbO₂Fluoboric acid is used as the leaching agent. And taking the acid soluble lead salt solution obtained after leaching as electrolyte for electrolytic deposition to obtain refined lead. In addition to using fluoroboric acid, there are processes that utilize fluorosilicic acid leaching. The purity of the lead obtained by the process is 99.98%, and the energy consumption of each ton of lead is 800 kWh. The fluoboric acid and the fluosilicic acid are strong in corrosivity and easy to volatilize, so that the operating personnel and equipment are greatly damaged. Andrews et al teach recovery of waste lead plaster by the PLACID process, which uses the HCl-NaCl system to directly leach the waste lead plaster, and uses lime to neutralize the remaining acid, the byproduct being gypsum. The lead salt in the leached solution is PbCl₂And obtaining refined lead after electrodeposition. The purity of the refined lead prepared by the process is 99.995%, and the energy consumption is up to 1300 kWh/t. In addition, hydrochloric acid is highly corrosive and has high requirements on equipment. Pan et al propose to use perchloric acid as leaching agent to leach waste lead plaster, directly dissolve the desulfurized lead plaster in excessive perchloric acid solution, and use HClO₄-Pb(ClO₄)₂The solution is used as electrolyte for electrodeposition, and refined lead is obtained at the cathode. The cathode current efficiency of the process is 98.5%, the energy consumption per ton of lead is 500kWh, and the purity of the lead is 99.9991%. But perchloric acid is highly corrosive to equipment and is environmentally hazardous. Most of the existing wet processes are difficult to implement industrially on a large scale, and the main reasons include large reagent consumption, strong reagent corrosivity, high requirements on operating conditions and the like.

In the technical route of leaching-electrodeposition wet lead smelting, in addition to the selection of a leaching agent needing to be considered seriously, the impurity removal of lead paste is also extremely important, but the existing technical route is rarely related. The concentration of impurity ions in the electrolyte affecting the electrodeposition of refined leadAnd (4) purity. Because the regenerated lead produced by the lead paste leaching-electrodeposition technical route is mostly used for manufacturing lead storage batteries, strict requirements are imposed on the purity of the regenerated lead. Research shows that impurities such as Fe, Cu, Ca and the like can influence the capacity and the service life of the lead storage battery, wherein the influence of the Fe impurity component is most obvious. The Fe impurity can not only cause the self-discharge of the battery, but also cause the positive plate to become hard and brittle when the content is more than 0.01 percent, and obviously influence the capacity of the battery, so the impurity removal step is very important in the production process of the secondary lead. CN105197987A discloses PbO, PbSO₄、PbO₂The separation method of the mixture adopts the technologies of acid leaching dissolution, separation refining and solid-liquid separation coupling to realize the separation of the mixture, and the technical route mainly removes soluble impurities in the lead plaster by washing and adsorption methods, but has no good effect on impurity elements such as Fe, Cu and the like in the lead plaster. Patent CN101514395 discloses a method for recovering lead oxide from waste lead-acid storage batteries, which comprises the steps of reducing the waste lead-acid storage batteries with oxalic acid, leaching with nitric acid, desulfurizing with ammonium carbonate, leaching with nitric acid after desulfurization, precipitating with ammonia water, and roasting lead hydroxide to obtain lead oxide with the purity of 98.9%. Therefore, for the secondary lead product, the impurity removal effect will affect the quality of the final product, so the impurity removal is very necessary.

Disclosure of Invention

The invention provides a resource recovery processing method of lead plaster in waste lead storage batteries, which aims at the defects of the prior art, and comprises the steps of crushing and sorting the waste lead-acid storage batteries to obtain the waste lead plaster, removing impurities from the waste lead plaster by utilizing sulfuric acid, recycling sulfuric acid solution after the impurities are removed, carrying out solid-liquid separation, carrying out wet treatment on the lead plaster after the impurities are removed to convert the lead plaster into lead methanesulfonate or lead ethylsulfonate solution, carrying out solid-liquid separation, carrying out electrodeposition on the solution, and obtaining high-purity refined lead by a cathode. The electrolyte after electrodeposition is reused for leaching the waste lead plaster. The invention solves the technical problems of high production cost, long and complicated flow, high requirement on operating conditions and the like of the existing wet process through the circulating technology of efficient selective leaching-electrodeposition preparation of refined lead from waste lead paste.

In order to realize the aim, the invention provides a resource recovery processing method of lead plaster in waste lead storage batteries, which comprises the following steps:

(1) crushing and sorting the waste lead-acid storage batteries to obtain waste lead plaster;

(2) fully reacting the obtained waste lead plaster with sulfuric acid, and carrying out solid-liquid separation to obtain a solid phase and a liquid phase, wherein the solid phase is the lead plaster subjected to impurity removal, the liquid phase is a sulfuric acid solution containing impurity ions, and the solution is recycled as the leaching agent in the step (2);

(3) fully mixing the obtained lead plaster subjected to impurity removal and washing with a leaching agent, and performing pre-size mixing to obtain a solid-liquid mixture; adding hydrogen peroxide into the obtained solid-liquid mixture, fully reacting, and carrying out solid-liquid separation to obtain a solid phase and a liquid phase; the solid phase contains lead sulfate and is used as a lead sulfate product after washing and drying operations, and the liquid phase is a leaching pregnant solution which contains organic acid lead, free acid and a small amount of hydrogen peroxide;

(4) adding an additive 1 serving as an anode lead dioxide inhibitor into the liquid phase obtained in the step (3), adding an additive 2 to regulate the appearance of the surface of cathode lead, taking the mixed solution as electrolyte for electrodeposition, wherein the anode uses a size-stable titanium anode, and the cathode obtains elemental lead;

(5) and (4) recycling the electrolyte after electrodeposition as a leaching agent in the step (3).

In the preparation process:

in the step (2), the concentration of the sulfuric acid is 1.5-6 mol/L, wherein the molar ratio of the sulfuric acid to lead elements of the non-sulfur lead-containing component in the waste lead-acid storage battery is (1-20): 1, and the reaction temperature is 50-80 ℃; the non-sulfur lead-containing component comprises PbO and PbO₂And Pb.

In the step (3), the leaching agent is methanesulfonic acid or ethanesulfonic acid; the concentration of the methanesulfonic acid or the ethylsulfonic acid is 1-3.5 mol/L, the molar ratio of the methanesulfonic acid or the ethylsulfonic acid to the lead element of the lead-free component in the waste lead-acid storage battery is (2-8): 1, and the reaction temperature is 20-60 ℃;

the concentration of the hydrogen peroxide solution is 1-10 mol/L, wherein the hydrogen peroxide and PbO in the waste lead-acid storage battery₂The molar ratio of (1-1.2): 1, the reaction temperatureIs 20 to 60 ℃.

In the step (4), the additive 1 for inhibiting the generation of the anode lead dioxide is phosphoric acid, and the effective concentration of the additive in a liquid phase is 1-3 g/L; the additive 2 for regulating and controlling the surface morphology of the cathode lead is any one of calcium lignosulphonate, sodium lignosulphonate and amino trimethylene phosphonic acid, and the effective concentration of the additive in a liquid phase is 0.1-10 g/L;

the anode is IrO₂·Ta₂O₅Coating a titanium electrode; the current density is 150 to 300A/m²The electrodeposition temperature is 20-60 ℃, and the electrode spacing is 30-50 mm; the concentration of free organic acid in the electrolyte is 0.5-3.5 mol/L, the concentration of lead ions is 10-400 g/L (determined by the initial lead ion concentration in the electrolyte and the final leaching rate in the step (3)), and the electrodeposition time is 3-6 h.

One of the invention is to provide the method which adopts sulfuric acid as an impurity removal solvent, removes impurities through sulfuric acid leaching pretreatment, and removes impurity components under the condition of little influence on the components of the original lead plaster. The lead-containing component in the lead paste is usually PbO, PbO₂Pb and PbSO₄. In the process of removing impurities by sulfuric acid, only a small amount of Pb can be obtained, and PbO can be converted into PbSO₄，PbO₂Hardly generates conversion, and impurity elements such as Fe, Cu, Ca, Na and the like react with sulfuric acid under certain conditions, and can be removed by filtration after being dissolved in sulfuric acid solution. In addition, the sulfuric acid solution after impurity removal can be recycled, and the industrial cost is reduced.

The second invention proposes that methanesulfonic acid or ethylsulfonic acid is used as a leaching agent, lead in the lead plaster and lead dioxide are subjected to a centering reaction through a pre-pulping process, so that the use of a reducing agent is reduced, hydrogen peroxide is used as the reducing agent, and finally, a non-sulfur lead-containing component in the lead plaster is converted into a corresponding soluble lead salt in a methanesulfonic acid solution. In the specific implementation process, 1-3.5 mol/L of methanesulfonic acid solution or ethanesulfonic acid solution and 1-10 mol/L of hydrogen peroxide solution are prepared. The stirring and target temperature conditions are maintained, and the reaction speed is accelerated. After mixing the waste lead plaster and the methanesulfonic acid for pre-sizing for a period of time, adding hydrogen peroxide. Generally, the reaction temperature in the leaching process is controlled to be 20-60 ℃, the stirring speed is 400-700 r/min, and the reaction time is 10-600 minutes. The reaction scheme of the reaction process can be represented as follows:

Pb+PbO₂+4CH₄O₃S→2Pb(CH₃O₃S)₂+2H₂O (1-1)

PbO₂+H₂O₂+2CH₄O₃S→Pb(CH₃O₃S)₂+2H₂O+O₂ (1-2)

Pb+PbO₂+4C₂H₆O₃S→2Pb(C₂H₅O₃S)₂+2H₂O (1-3)

PbO₂+H₂O₂+2C₂H₆O₃S→Pb(C₂H₅O₃S)₂+2H₂O+O₂ (1-4)

wherein the formulas (1-1) and (1-3) are respectively the reactions in the pre-slurry-mixing process in the methanesulfonic acid system and the ethanesulfonic acid system, and the formulas (1-2) and (1-4) are respectively the reactions in which lead dioxide is reduced by hydrogen peroxide in the methanesulfonic acid system and the ethanesulfonic acid system.

And (3) with the progress of the reaction, the lead ion concentration in the solution is higher and higher, when the lead ion concentration in the solution is stable, the heating and the stirring are stopped, the reaction solution is taken out for solid-liquid separation, and the leaching residue containing the free acid and the soluble lead salt solution and the lead sulfate which is kept stable before and after the reaction are obtained.

The third invention is that the electrolyte containing lead organic acid and free acid is electrodeposited to obtain refined lead at the cathode, and the organic acid is regenerated. In the implementation process of the invention, the concentration of free organic acid in the electrolyte is controlled to be 0.5-3.5 mol/L, the concentration of lead ions is controlled to be 10-400 g/L, the temperature of electrodeposition is controlled to be 20-60 ℃, and the current density is controlled to be 150-300A/m²And adding 1-3 g/L phosphoric acid into the electrolyte to inhibit the generation of anode lead dioxide. At the moment, the cathode current efficiency of the lead ions is 94-99%, and the morphology of the electrodeposited lead is loose dendritic lead. On the basis of the third invention point, in the electrolyteAn additive can be added to regulate the surface appearance of the electro-deposition refined lead, wherein the additive is one of calcium lignosulphonate, sodium lignosulphonate and amino trimethylene phosphonic acid, and the concentration of the additive is 0.1-10 g/L.

The fourth invention is that the method of circulating and converting the electrolyte and the leachate is adopted to combine the high-efficiency selective leaching process with the process of preparing the refined lead by the electro-deposition. As the electrodeposition is carried out, the concentration of lead ions in the electrolyte is reduced, and finally the prepared electrodeposited lead and the regenerated electrolyte containing the organic acid are obtained.

The invention has the advantages that:

the method uses sulfuric acid to remove impurities from lead plaster, uses methanesulfonic acid-hydrogen peroxide or ethanesulfonic acid-hydrogen peroxide as a leaching system, uses different additives to respectively inhibit the generation of lead dioxide at an anode and regulate and control the appearance of a cathode, combines a leaching process and an electrodeposition process in a circulating mode of a leaching solution and electrolyte, avoids the loss of lead to the greatest extent, obviously reduces the loss of chemical agents, and reduces the influence on the environment due to the natural degradation characteristic of the methanesulfonic acid and the ethanesulfonic acid. Through calculation, the cathode current efficiency is 94-99%, the energy consumption in the electrodeposition process is 588-611 kWh/t, and the purity of lead obtained through electrodeposition is high. The invention provides a new way for wet recovery and treatment of waste lead plaster.

The method combines a fluorine-free chlorine-free clean high-efficiency selective leaching process with an electrodeposition process for preparing the refined lead, shortens the process of preparing the refined lead by recovering and treating the waste lead paste, reduces the use of a leaching agent in the process flow, solves the problems of high reagent consumption, high energy consumption, high equipment condition requirement and the like in the wet process for recovering the waste lead paste to a certain extent, reduces the pollution and the cost, and has a considerable market prospect. Meanwhile, the organic acid regenerated in the electrolyte after electrodeposition can be recycled for leaching the non-sulfur lead-containing component in the waste lead paste, so that the circulation technology for preparing refined lead by high-efficiency selective leaching-electrodeposition of the waste lead paste is realized.

Drawings

FIG. 1 is a flow chart of one embodiment of the method of the present invention.

Detailed Description

The present invention is further characterized by the flow chart of fig. 1. The waste lead-acid storage battery is crushed and sorted to obtain waste lead paste, the waste lead paste is subjected to impurity removal by using a sulfuric acid solution, the sulfuric acid solution after impurity removal is recycled, and after solid-liquid separation, the waste lead paste after impurity removal and an organic acid solution are fully mixed for pre-size mixing to obtain a solid-liquid mixture. Adding hydrogen peroxide into the solid-liquid mixture, and fully reacting to obtain a soluble lead salt solution. And carrying out vacuum filtration on the solution and unreacted lead sulfate to obtain a soluble lead salt solution and insoluble filter residue mainly containing lead sulfate.

The lead salt solution mainly contains organic acid lead and free organic acid, the solution is electrolyzed to obtain electro-deposited lead at a cathode, and the electrolyte after electro-deposition can be returned to the leaching process for recycling.

The following are examples:

example 1

A resource recovery processing method of lead plaster in waste lead storage batteries comprises the following steps:

(1) and crushing and sorting the waste lead-acid storage batteries to obtain 50g of lead plaster.

(2) 500mL of a 3mol/L sulfuric acid solution was added thereto, the reaction temperature was 55 ℃, the stirring speed was controlled at 400 rpm, and the reaction time was 90 minutes. And after the reaction is finished, stopping stirring, and carrying out vacuum filtration to obtain the lead plaster after impurity removal and the sulfuric acid solution containing impurity ions.

(3) And adding 500mL of 1mol/L methanesulfonic acid into the lead plaster after impurity removal and washing, controlling the reaction temperature at 25 ℃, controlling the stirring speed at 400 rpm, and reacting for 2 hours. When the reaction proceeded for 10 minutes, 10mL of 9.27mol/L hydrogen peroxide was added. In the process, lead dioxide, simple substance lead and lead oxide in the lead plaster are gradually converted into lead methylsulfonate in a methanesulfonic acid-hydrogen peroxide system. After the reaction is carried out for 2 hours, the heat preservation and the stirring are stopped, and the filter residue and the lead-containing salt leaching solution are obtained by vacuum filtration.

(4) And adding the leachate serving as electrolyte into an electrolytic bath for electrolysis, adding 1g of phosphoric acid into the electrolyte to inhibit the generation of anode lead dioxide, and adding 1g of sodium lignosulphonate to regulate the appearance of the cathode.

The anode adopts IrO with the thickness of 2.5mm and the length and the width of 40mm and 70mm respectively₂·Ta₂O₅The cathode of the titanium electrode is made of 316L stainless steel with the thickness of 2.5mm and the length and width of 40mm and 70mm respectively, and the effective area of the titanium electrode is 600mm². The power supply of the electrolytic cell is in a constant-current electrolysis mode, and the current density is controlled to be 210A/m²The temperature during the electrolysis is controlled at 25 ℃. The electrolysis was stopped after 3 hours of electrodeposition.

(5) The contents of Si, Cu, Fe, Ca and Na in the lead plaster after impurity removal are respectively 1.103%, 0.001%, 0.002%, 0.021% and 0.029%, and the impurity removal rates are respectively 0.63%, 98.57%, 93.33%, 89.50% and 89.64%. The cathode current efficiency is 99.35 percent, the unit energy consumption is 586kWh/t, and the purity of the cathode lead is 99.990 percent. The regenerated methanesulfonic acid in the electrodeposition process is reused in the leaching step for recycling.

TABLE 1 lead pastes containing lead-containing component and impurities

Example 2

A resource recovery processing method of lead plaster in waste lead storage batteries comprises the following steps:

(1) and crushing and sorting the waste lead-acid storage batteries to obtain 50g of lead plaster.

(2) 500mL of a 3mol/L sulfuric acid solution was added thereto, the reaction temperature was 65 ℃, the stirring speed was controlled at 400 rpm, and the reaction time was 90 minutes. And after the reaction is finished, stopping stirring, and carrying out vacuum filtration to obtain the lead plaster after impurity removal and the sulfuric acid solution containing impurity ions.

(3) And adding 500mL of 1mol/L methanesulfonic acid into the lead plaster after impurity removal and washing, controlling the reaction temperature at 25 ℃, controlling the stirring speed at 400 rpm, and reacting for 2 hours. When the reaction proceeded for 10 minutes, 10mL of 9.27mol/L hydrogen peroxide was added. In the process, lead dioxide, simple substance lead and lead oxide in the lead plaster are gradually converted into lead methylsulfonate in a methanesulfonic acid-hydrogen peroxide system. After the reaction is carried out for 2 hours, the heat preservation and the stirring are stopped, and the filter residue and the lead-containing salt leaching solution are obtained by vacuum filtration.

(4) And adding the leachate serving as electrolyte into an electrolytic cell for electrolysis, adding 1g of phosphoric acid into the electrolyte to inhibit the generation of anode lead dioxide, and adding 2g of aminotrimethylene phosphonic acid to regulate the appearance of the cathode.

The anode adopts IrO with the thickness of 2.5mm and the length and the width of 40mm and 70mm respectively₂·Ta₂O₅The cathode of the titanium electrode is made of 316L stainless steel with the thickness of 2.5mm and the length and width of 40mm and 70mm respectively, and the effective area of the titanium electrode is 600mm². The power supply of the electrolytic cell is in a constant-current electrolysis mode, and the current density is controlled to be 210A/m²The temperature during the electrolysis is controlled at 25 ℃. The electrolysis was stopped after 3 hours of electrodeposition.

(5) The contents of Si, Cu, Fe, Ca and Na in the lead plaster after impurity removal are respectively 1.093%, 0.004%, 0.003%, 0.015% and 0.032%, and the impurity removal rates are respectively 1.53%, 94.29%, 90.00%, 92.50% and 88.57%. The cathode current efficiency is 99.35 percent, the unit energy consumption is 583kWh/t, and the purity of the cathode lead is 99.993 percent. The regenerated methanesulfonic acid in the electrodeposition process is reused in the leaching step for recycling.

TABLE 2 lead pastes containing lead-containing component and impurities

Example 3

A resource recovery processing method of lead plaster in waste lead storage batteries comprises the following steps:

(1) and crushing and sorting the waste lead-acid storage batteries to obtain 50g of lead plaster.

(2) 250mL of a 2.5mol/L sulfuric acid solution was added thereto, the reaction temperature was 70 ℃, the stirring speed was controlled at 400 rpm, and the reaction time was 90 minutes. And after the reaction is finished, stopping stirring, and carrying out vacuum filtration to obtain the lead plaster after impurity removal and the sulfuric acid solution containing impurity ions.

(3) And adding 500mL of 1mol/L ethyl sulfonic acid into the lead plaster after impurity removal and washing, controlling the reaction temperature at 45 ℃, controlling the stirring speed at 400 r/m, and reacting for 2 hours. When the reaction proceeded for 10 minutes, 10mL of 9.27mol/L hydrogen peroxide was added. In the process, lead dioxide, simple substance lead and lead oxide in the lead plaster are gradually converted into lead ethylsulfonate in an ethylsulfonic acid-hydrogen peroxide system. After the reaction is carried out for 2 hours, the heat preservation and the stirring are stopped, and the filter residue and the lead-containing salt leaching solution are obtained by vacuum filtration.

(4) And adding the leachate serving as electrolyte into an electrolytic cell for electrolysis, adding 1g of phosphoric acid into the electrolyte to inhibit the generation of anode lead dioxide, and adding 1g of calcium lignosulphonate to regulate the appearance of the cathode.

The anode adopts IrO with the thickness of 2.5mm and the length and the width of 40mm and 70mm respectively₂·Ta₂O₅The cathode of the titanium electrode is made of 316L stainless steel with the thickness of 2.5mm and the length and width of 40mm and 70mm respectively, and the effective area of the titanium electrode is 600mm². The power supply of the electrolytic cell is in a constant-current electrolysis mode, and the current density is controlled to be 210A/m²The temperature during the electrolysis was controlled at 45 ℃. The electrolysis was stopped after 3 hours of electrodeposition.

(5) The calculated contents of Si, Cu, Fe, Ca and Na in the lead plaster after impurity removal are respectively 1.109%, 0.001%, 0.002%, 0.018% and 0.030%, and the impurity removal rates are respectively 0.09%, 98.57%, 93.33%, 91.00% and 89.29%. The cathode current efficiency is 98.80 percent, the unit energy consumption is 579kWh/t, and the purity of the cathode lead is 99.992 percent. The ethyl sulfonic acid regenerated in the electrodeposition process is reused in the leaching step for recycling.

TABLE 3 lead paste content of lead-containing component and impurities

Example 4

A resource recovery processing method of lead plaster in waste lead storage batteries comprises the following steps:

(1) 5000g of lead paste was prepared.

(2) 25L of a 5mol/L sulfuric acid solution was added thereto, with a stirring speed of 600 rpm, a reaction temperature of 50 ℃ and a reaction time of 90 minutes. And stopping stirring after the reaction is carried out for the target time, and filtering to obtain the lead plaster after impurity removal and the sulfuric acid solution containing impurity ions.

(3) Preparing 25L of 2mol/L methanesulfonic acid, adding the lead plaster after impurity removal and washing, and reacting for 2 hours at the reaction temperature of 25 ℃ and the stirring speed of 600 rpm. After the reaction proceeded for 10 minutes, 1L of hydrogen peroxide was added in portions at a concentration of 9.27 mol/L. During this process, the lead, lead dioxide and lead oxide in the waste lead paste are converted to soluble lead methanesulfonate, while the lead sulfate remains in the form of a precipitate. After the reaction is carried out for 2 hours, the heat preservation and the stirring are stopped, and the leaching solution of the filter residue and the lead-containing salt is obtained by vacuum filtration.

(4) Adding leachate as electrolyte into an electrolytic tank for electrolysis, adding 50g of phosphoric acid to inhibit the generation of anode lead dioxide, adding 50g of calcium lignosulfonate to regulate the appearance of a cathode, wherein the anode of the electrolytic tank adopts IrO with the thickness of 2.5mm and the length and width of 180mm and 110mm respectively₂·Ta₂O₅The cathode of the coated titanium electrode is made of 316L stainless steel with the thickness of 2.5mm and the length and the width of 180mm and 110mm respectively. The power supply of the electrolytic cell is in a constant-current electrolysis mode, and the current density is controlled to be 230A/m²The temperature during the electrolysis is controlled at 25 ℃. The electrolysis was stopped after 3 hours of electrodeposition.

(5) The calculated contents of Si, Cu, Fe, Ca and Na in the lead plaster after impurity removal are respectively 1.104%, 0.001%, 0.002%, 0.016% and 0.024%, and the impurity removal rates are respectively 0.54%, 98.57%, 93.33%, 92.00% and 91.43%. The cathode current efficiency is 98.67%, the unit energy consumption is 602kWh/t, and the purity of the cathode lead is 99.989%. The regenerated methanesulfonic acid in the electrodeposition process is reused in the leaching step for recycling.

TABLE 4 lead pastes containing lead-containing component and impurities