CN106676270B - A method of Whote-wet method extracts lead from lead plaster and concentrate of lead sulfide ore - Google Patents

Abstract

The invention discloses a method for extracting lead from lead paste and lead sulfide concentrate by a full-wet method. The method is to carry out desulfurization conversion reaction between waste lead-acid storage battery lead paste and carbonate solution, and separate solid and liquid to obtain sulfate solution and desulfurization conversion material, the desulfurization conversion material is neutrally leached with a solution containing methanesulfonic acid, and the liquid and solid are separated to obtain a neutral leaching solution and a neutral leaching residue; the neutral leaching solution is mixed with waste electrowinning solution to prepare electrowinning solution for electrowinning lead, to obtain lead plates and waste lead electrolysis; using neutral leaching slag as an oxidant, the lead sulfide concentrate is acid leached with waste electrolysis, liquid and solid are separated to obtain acid leaching solution and acid leaching slag, and the acid leaching solution is returned to the lower One time neutral leaching use. The method not only realizes the efficient extraction of lead, but also realizes the recycling of the leaching solution and the electrolytic solution, and no waste solution is generated, which meets the requirements of green environmental protection.

Description

A method for extracting lead from lead plaster and lead sulfide concentrate by wet method

technical field

The present invention relates to a method for extracting lead from lead paste and lead sulfide concentrate, in particular to a green and clean method for recovering lead from lead paste and lead sulfide concentrate through a full wet method, which belongs to non-ferrous metallurgy and The field of resource regeneration.

Background technique

Methanesulfonic acid has many uses. It is a raw material for medicine and pesticides. It can be used as a dehydrating agent, a paint curing accelerator, and a fiber treatment agent. In recent years, it has been widely used as a solvent for electroplating solutions. Metal methanesulfonate is widely used in the field of electrochemical deposition, and the applications related to the surface finishing industry include: replacing fluoroboric acid and fluoroborate in tin, lead and tin-lead alloy electroplating; metal wire and steel bar plating Tin; metal finishing of silver, copper, nickel and palladium; removal of nickel, tin, lead, tin-lead and cadmium plating from copper and its alloys, zinc and its alloys by dipping and spraying.

With the development of transportation and other industries, the demand for lead continues to increase, and the lead consumption of lead-acid batteries accounts for about 85% of the total lead consumption, and the waste lead batteries amount to more than one million tons every year, and the stockpile continues to increase. Therefore, recycled lead Technology has become particularly important. At the same time, the secondary lead industry is an important part of the circular economy industry.

At present, the methods of recovering lead from the lead paste obtained after the dismantling of waste lead-acid batteries are divided into pyroprocessing and wet processing. The disadvantages of low yield, heavy pollution, and high energy consumption restrict its further development. In contrast, hydrometallurgy has many advantages, but the mature system still has disadvantages such as high corrosion to equipment and poor operating environment. At present, the full wet lead smelting method mostly uses HBF ₄ and H ₂ SiF ₆ to leach the desulfurized lead paste, and then obtains lead through electrodeposition, but there are many processes, and HBF ₄ with high toxicity and corrosion is used. and H ₂ SiF ₆ , resulting in high requirements for subsequent electrolysis equipment and control technology, high power consumption, high equipment corrosion, and expensive reagents; the PLACID process uses HCl-NaCl system to leach lead paste, which is cheap in raw materials and simple in operation, but High energy consumption, a large amount of chlorine gas is produced in the electrolysis process, which is very corrosive to the environment and equipment; NaOH can be used as a desulfurization agent in alkaline leaching to generate lead oxide or lead hydroxide, and sulfuric acid and ferrous sulfate can be combined to reduce lead dioxide. - KNaC ₄ H ₄ O ₆ solution dissolves lead oxide and then electrolyzes to obtain high-purity lead powder; Ca(OH) ₂ can also be used to treat desulfurized lead paste, and then electrodeposit to obtain pure lead. The above hydrometallurgical secondary lead processes all adopt desulfurization-leaching-electrodeposition process. In recent years, the direct leaching method has also realized the regeneration of lead sulfate paste. Lead citrate precursor can be obtained by direct leaching with citric acid (adding ammonia water), and then lead powder can be prepared by low-temperature roasting, and fine particles can be obtained by adding ethylene glycol as a dispersant; in addition, lead sulfate paste can be leached by mixing urea and acetic acid In the research, iron is added as reducing agent after leaching to obtain lead element, but the whole process needs nitrogen protection, and is greatly affected by the pH value and the specific surface area of iron, so it cannot be industrialized. At present, the wet-fire combined method is commonly used, that is, the "wet pre-desulfurization-reduction smelting" process, but there are still problems in the pyro-method lead smelting, such as low direct recovery rate, heavy pollution, and high energy consumption.

Chinese patent (application number CN 201410019612) mixes sodium sulfate filtrate, anhydrous sodium sulfate and sodium hydroxide and then cools at low temperature to obtain sodium sulfate crystals, which solves the problem of recovering sodium sulfate in the liquid after desulfurization. The Chinese patent (Application No. CN201510733622) uses lead paste as raw material to obtain PbSO ₄ , PbO ₂ and PbO respectively through processes such as leaching and solid-liquid separation. Realized the recovery and reuse of lead. Chinese patent (application number CN 201210071501.X) redox reaction between lead in lead paste and lead dioxide in an acid liquid reaction kettle containing a catalyst, the acid adopts one or both of perchloric acid or methanesulfonic acid The catalyst is chloroacetic acid or ammonium acetate. After the reaction, soluble lead salt and lead sulfate filter residue are obtained. The lead sulfate filter residue is re-selected to obtain lead sulfate. The soluble lead salt is electro-deposited to obtain lead plate, oxygen and waste electrolyte. The electrolyte returns The leaching process realizes the recovery of lead in lead sulfate paste.

At present, more than 80% of domestic lead is produced by pyrolysis from lead sulfide concentrate. The traditional pyrometallurgy of lead adopts the sintering and burning-blast furnace reduction process, which has high energy consumption and low-concentration SO ₂ emission pollutes the environment, and has been banned by the state. At present, the bottom-blown oxidation smelting-high-lead slag blast furnace reduction smelting is mostly used in our country. The problem of SO ₂ acid production needs to be solved, but the high-temperature reduction of high-lead slag and coke after cooling consumes a lot of energy. As well as the currently more advanced Kiefset method, QSL method, Osmelt method, and the domestically developed bottom-blown oxidation smelting-liquid slag reduction method, these pyrometallurgical smelting methods are all above 1100 ° C, the reduction temperature is high, and the lead vapor volatilizes ,polluted environment.

At present, domestic and foreign research methods for extracting lead from lead sulfide concentrate by wet method include: ①FeCl ₃ oxidation method: PbS+2FeCl ₃ =PbCl ₂ +2FeCl ₂ +S°, various soluble lead-chlorine complexes are formed at higher temperatures , by adding alkali metal chlorides to increase the total concentration of Cl ^- , the lead in the solution can mainly exist in the form of PbCl ₄ ^2- , then cool and crystallize PbCl ₂ , then dry, and finally electrolyze metallic lead in a low-temperature molten salt system With chlorine, chlorine returns to leaching, but it has problems: hydrochloric acid is volatile, corrodes equipment, high-temperature chlorine is not easy to collect, and lead chloride in molten salt electrolytic lead contacts with air to produce lead oxide, which hinders the progress of electrolysis. There is also research on combined oxidation extraction of ozone-hydrogen peroxide-ferric chloride, and the reaction equation is as follows:

PbS+H ₂ O ₂ +O ₃ +2NaCl=PbCl ₂ +Na ₂ SO ₄ +H ₂ O

PbS+2NaCl+8FeCl ₃ +4H ₂ O＝PbCl ₂ +Na ₂ SO ₄ +8FeCl ₂ +8HCl

8FeCl ₂ +H ₂ O ₂ +3H ₂ O+O ₃ +8HCl＝8FeCl ₃ +8H ₂ O

PbCl ₂ +2Cl ^- ＝[PbCl ₄ ] ^2-

②Galena-pyrolulusite two-mine method leaching: Utilize the oxidation of manganese dioxide in pyrolusite to oxidize negative divalent sulfur ions in galena, thereby leaching lead and manganese at the same time. The reaction equation is as follows:

PbS+MnO ₂ +4HCl=PbCl ₂ +MnCl ₂ +S+2H ₂ O

PbCl ₂ +2Cl ^- ＝[PbCl ₄ ] ^2-

③ Oxidative leaching in fluorosilicic acid medium: the oxidants used include oxygen, H ₂ O ₂ , Fe ₂ (SiF ₆ ) ₃ , and their reactions are:

2PbS+O ₂ +2H ₂ SiF ₆ ＝2PbSiF ₆ +2S°+2H ₂ O

PbS+H ₂ O ₂ +H ₂ SiF ₆ ＝PbSiF ₆ +S°+2H ₂ O

PbS+Fe ₂ (SiF ₆ ) ₃ ＝PbSiF ₆ +S°+2FeSiF ₆

Oxygen and H ₂ O ₂ are used to leach lead, and lead can be electro-deposited after purification; Fe ₂ (SiF ₆ ) ₃ is an oxidant, which requires conjunctival electro-deposition to obtain lead at the cathode and regenerate Fe ₂ (SiF ₆ ) ₃ at the anode. However, the fluoride leaching agent is unstable and easy to decompose to produce hydrogen fluoride gas, which is harmful to the human body and leads to poor operating environment.

Contents of the invention

Aiming at the problems such as environmental pollution in the existing waste lead-acid battery lead paste and lead sulphide concentrate smelting process, the purpose of the present invention is to propose a green and efficient method for using the waste lead-acid battery lead paste and lead sulphide concentrate A method for extracting lead from lead sulfide concentrate.

In order to realize the above-mentioned technical purpose, the present invention provides a kind of method that extracts lead from waste lead-acid storage battery lead plaster and lead sulfide concentrate, and the method comprises the following steps:

1) Carrying out the desulfurization conversion reaction of the lead plaster and the carbonate solution, and separating the solid and liquid to obtain the sulfate solution and the desulfurization conversion material containing lead carbonate and lead dioxide; the sulfate solution reclaims sulfate through evaporative crystallization;

2) Neutrally leaching the desulfurized converted material with a solution containing methanesulfonic acid, and separating the liquid and solid to obtain a neutral leaching solution and a neutral leaching residue; the neutral leaching uses the desulfurized converted material as a neutralizing agent ;

3) The neutral leaching solution is mixed with the waste lead electrolytic solution to prepare the lead electrolytic solution to carry out the electrolytic lead deposition to obtain a lead plate and the waste lead electrolytic solution;

4) The neutral leaching slag is used as an oxidant together with the lead sulfide concentrate to carry out acidic leaching with the waste electrolytic solution, and the liquid and solid are separated to obtain an acidic leaching solution and an acidic leaching slag, and the acidic leaching solution contains methanesulfonic acid Solution, return to neutral leaching for use.

In a preferred solution, the lead paste is the lead paste recovered from waste lead storage batteries, and the lead paste is obtained from waste lead storage batteries through steps such as crushing and screening.

More preferably, the conditions of the desulfurization conversion reaction are as follows: the reaction temperature is 25-85° C., the stirring speed is 100-800 rpm, the reaction time is 30-300 minutes, and the pH value at the end of the reaction is above 10.

In a more preferred solution, the amount of carbonate solution used in the desulfurization conversion reaction process is measured by carbonate, which is 1 to 1.7 times the molar amount of lead sulfate in the lead sulfate material.

In a preferred scheme, the conditions for the neutral leaching are: the concentration of free methanesulfonic acid contained in the solution containing methanesulfonic acid is 0.3-1.5 mol/L, and the liquid-solid ratio to the desulfurization conversion material is 4mL/g- 20mL/g, the leaching temperature is 40-100°C, the stirring speed is 200-1000 rpm, the leaching time is 30-300 minutes, and the pH of the leaching solution at the leaching end point is above 4.5.

In a preferred solution, the lead ion concentration in the lead electrolysis solution prepared by mixing the neutral leaching solution with the waste lead electrolysis solution is 30-120 g/L.

In a preferred scheme, the conditions for the electrodeposition of lead are as follows: the current density is 80-400A/m ² , and the temperature of the lead electrodeposition solution is 30-65°C.

Preferably, in the process of electrowinning lead, graphite plate, titanium-based lead dioxide mesh or titanium-based platinum mesh are used as anode plate, and lead starter sheet, titanium plate or stainless steel plate are used as cathode plate; the peripheral ratio of the cathode plate is The anode plate is 1-3 cm long.

In a preferred scheme, the conditions for acidic leaching are: the liquid-solid ratio of waste lead electrowinning solution to lead sulfide concentrate is 5mL/g-20mL/g, the leaching temperature is 40-100°C, and the stirring speed is 200-1000 rpm /min, the leaching time is 30-300 minutes.

In the preferred solution, during the acid leaching process, the amount of neutral leaching slag is measured by the lead dioxide it contains, which is 1 to 1.5 times the theoretical molar amount required to oxidize the negative divalent sulfur ions in the lead sulfide concentrate to elemental sulfur .

Preferably, the carbonate is at least one of sodium carbonate, potassium carbonate and ammonium carbonate.

Below in conjunction with Fig. 1, the method for the full wet extraction of lead from lead sulfide concentrate of the present invention is described in detail:

1) The waste lead-acid storage battery lead paste is subjected to desulfurization conversion reaction with carbonate solution, and solid-liquid separation is carried out to obtain sulfate solution and desulfurization conversion materials containing lead carbonate and lead dioxide; the sulfate solution recovers sulfate through evaporative crystallization . The used lead-acid battery lead paste used is mainly materials containing lead dioxide and lead sulfate. After reacting with carbonate (such as sodium carbonate), lead sulfate is converted into lead carbonate;

PbSO ₄ +Na ₂ CO ₃ ＝PbCO ₃ +Na ₂ SO ₄

After filtration and separation, both lead carbonate and lead dioxide remain in the slag phase, that is, the desulfurization conversion material;

2) In the neutral leaching process, the desulfurization conversion material is used as a neutralizing agent, and the lead carbonate contained in the desulfurization conversion material is mainly used to react with the solution containing methanesulfonic acid:

PbCO ₃ +2CH ₃ SO ₃ H=Pb(CH ₃ SO ₃ ) ₂ +CO ₂ +H ₂ O

The neutral leaching conditions are as follows: liquid-solid ratio is 4mL/g-20mL/g, temperature is 40-100°C, stirring speed is 200-1000 rpm, leaching reaction time is 30-300 minutes, and the leaching end point is determined by the pH of the leachate at Above 4.5; lead carbonate is leached from the neutral leaching slag, which mainly contains lead dioxide;

3) Under the action of the neutral leaching slag containing lead dioxide, the lead sulfide concentrate reacts with the solution containing methanesulfonic acid:

4CH ₃ SO ₃ H+PbS+PbO ₂ =2Pb(CH ₃ SO ₃ ) ₂ +S°+2H ₂ O

Neutral leaching slag is used as an oxidant for acidic leaching. The amount of neutral leaching slag is measured by the lead dioxide contained in it, which is to oxidize the negative divalent sulfur in lead sulfide to 1 to 1.5 times the theoretical molar amount of elemental sulfur. The acidic leaching solution Using waste lead electrowinning solution, the acidic leaching conditions are: liquid-solid ratio of 5mL/g-20mL/g, temperature of 40-100°C, stirring speed of 200-1000 rpm, leaching reaction time of 30-300 minutes; acidic leaching solution It also contains free methanesulfonic acid with a concentration of 0.3-1.5mol/L, which is returned to neutral leaching for use, and elemental sulfur can be recovered from acidic leaching residue, and the rest is waste residue.

Through neutral leaching and acid leaching, the lead in lead sulfide, lead dioxide and lead carbonate is all leached.

4) The neutral leaching solution and part of the waste electrolyte are configured to form a certain concentration of lead electrolysis solution, and then the lead is electrolytically deposited to obtain a lead plate and waste electrolyte. The lead ion concentration in the prepared lead electrolysis solution is 30-100g/L. The electrodeposition anode plate adopts one of graphite plate, titanium-based lead dioxide mesh, and titanium-based platinum mesh, and the electrodeposition cathode plate adopts one of lead initial plate, titanium plate, and stainless steel plate, and the periphery of the cathode plate is larger than that of the anode The size of the plate is 1-3 cm; the current density is 80-400A/m ² , and the temperature is 35-65°C.

Compared with the prior art, the beneficial technical effect brought by the technical solution of the present invention:

1) After the technical scheme of the present invention desulfurizes the lead paste in the lead-acid storage battery, skillfully utilize the lead carbonate material and the lead dioxide in the desulfurization material as the neutralizing agent of neutral leaching and the oxidant of acid leaching respectively, obtain leaching, In addition, the lead in the lead sulfide concentrate is leached during the acid leaching process. Combining the two-stage countercurrent leaching and electrowinning process, the full-wet method has realized the efficient and comprehensive recovery of lead in the lead sulfide concentrate and the lead paste of the waste lead-acid battery. High-purity lead plate, this method solves the problems of high energy consumption and heavy metal pollution caused by the existing pyrometallurgy.

2) According to the technical solution of the present invention, the leaching solution and the electrowinning solution in the whole leaching process and the electrowinning process are circulated, no waste liquid and waste gas are generated, and the full circulation of the waste liquid is realized, and the sulfate solution produced in the desulfurization conversion process is obtained. Recycling meets the requirements of green industrial production.

3) The technical scheme of the present invention adopts methanesulfonic acid as leaching agent, on the one hand, methanesulfonic acid is as organic strong acid, is nontoxic liquid, and stability is good, and can be decomposed into sulfate radical and carbon dioxide by bacterial action in nature , will not cause environmental pollution; on the other hand, lead methanesulfonic acid is leached and converted into lead methanesulfonate, and then regenerated through the electrolytic lead process, and methanesulfonic acid can be recycled, and there are no compounds that are not conducive to the environment during the cycle release, which greatly reduces the cost of leaching agents, and is beneficial to environmental protection; at the same time, the methanesulfonic acid of the present invention, as the main component of the electrolyte, replaces the traditional fluoride-containing formula, and the fluorine-containing compounds are easy to decompose and release harmful gases , such as fluoboric acid and fluosilicic acid, are not conducive to environmental protection.

4) The technical solution of the present invention uses waste lead-acid battery lead paste as the neutralizing agent for neutral leaching and the oxidizing agent for acidic leaching of lead sulfide concentrate, avoiding the consumption of neutralizing agent and simultaneously avoiding the use of existing conventional _O2 , H ₂ O ₂ and other oxidizing agents have the disadvantages of high price and large consumption, and solve the problems of difficult lead recovery in lead sulfate materials such as lead plaster, so that lead sulfate materials such as lead plaster can be combined with lead sulfide concentrate to achieve comprehensive recovery .

Description of drawings

[Fig. 1] is a process flow diagram of the present invention;

[Fig. 2] is the physical map of the electrodeposited lead plate;

[Figure 3] The XRD spectrum of the electrodeposited lead plate.

Detailed ways

Further illustrate the substantive content of the present invention with example below, but protection scope of the present invention is not limited thereto.

Example 1

The phases of the lead sulfate material used in the test are shown in Table 1, and the chemical composition of the lead sulfide concentrate is shown in Table 2.

Table 1 lead sulfate material lead phase analysis/%

Phase Pb/ _PbSO4 Pb/PbO Pb/ _PbO2 Pb T _Pb content/% 30.40 12.90 25.63 <1 72.90

Table 2 Chemical composition of lead sulfide concentrate

element Pb S Fe Ag Element/% 48.71 17.32 7.76 0.0057

Get lead sulfate material 200g (its lead material phase is as table 1), and the carbonate consumption in the carbonate solution of preparation is 1.3 times of theoretical amount, press material and carbonate solution in beaker by liquid-solid ratio 4:1mL/g Mix and mix in medium, stir at 200r/min, convert at a temperature of 85°C for 1.0h; filter and wash until no sulfate exists in the washing liquid. Take the material after desulfurization and conversion, add the material to the acidic leachate (containing 1mol/L of free methanesulfonic acid and 50g/L of lead methanesulfonate) according to the liquid-solid ratio of 4:1mL/g, and stir at a stirring speed of 500r/min. The temperature was leached at 65°C for 1 hour, and the filter residue and neutral leachate were obtained after separation. Neutral leaching slag and lead sulfide concentrate are carried out acidic leaching, according to liquid-solid ratio 5:1mL/g, join in the waste electrolyte, the consumption of neutral leaching slag is measured by the lead dioxide contained in it, and lead sulfide concentrate Negative divalent sulfide ions are oxidized to 1.1 times the theoretical molar amount required for elemental sulfur, and stirred for 1 hour at a stirring speed of 300 r/min and a temperature of 90°C. The filtered solution is returned to the next neutral leaching; the slag recovers elemental sulfur and valuable metals. The neutral leaching solution is diluted with waste electrolyte to a lead concentration of 75g/L. The titanium-based lead dioxide grid is used as the anode, the lead sheet is used as the cathode, the pole distance is 4cm, the electrodeposition temperature is 40°C, and the current density is 250A/m ² for 4 hours, and the current efficiency reaches 99.8%. The electrodeposited lead plate is shown in Figure 2, and the XRD spectrum is shown in Figure 3.

Example 2

The phases of the lead sulfate material used in the test are shown in Table 1, and the chemical composition of the lead sulfide concentrate is shown in Table 2.

Get lead sulfate material 400g (its lead material phase is as table 1), and the carbonate consumption in the carbonate solution of preparation is 1.5 times of theoretical amount, press material and carbonate solution in beaker by liquid-solid ratio 6:1mL/g and put it into a water bath with a stirring speed of 200r/min, transform at a temperature of 25°C for 2.5h; filter and wash until no sulfate exists in the lotion. Take the desulfurized conversion material, add the material to the acidic leachate (containing 1.3mol/L of free methanesulfonic acid and 30g/L of lead methanesulfonate) according to the liquid-solid ratio of 5:1mL/g, and stir at a stirring speed of 400r/min. Leach at a temperature of 75°C for 2.5 hours, and obtain filter residue and neutral leachate after separation; lead sulfide concentrate is subjected to acid leaching, take 400g of lead sulfide concentrate, and add the material to the waste electrolyte at a liquid-solid ratio of 6:1mL/g , at a stirring speed of 350r/min and a temperature of 95°C, slowly add the above-mentioned neutral leaching slag, the amount of neutral leaching slag is measured by the lead dioxide contained in it, and the negative divalent sulfur ions in the lead sulfide concentrate are oxidized into elemental sulfur 1.2 times the required theoretical molar amount, and then stirred for 1.0h. The filtered solution is returned to the next neutral leaching; the slag recovers elemental sulfur and valuable metals. The neutral leaching solution is diluted with waste electrolyte to a lead concentration of 60g/L. The graphite plate is used as the anode, the stainless steel is used as the cathode, the pole distance is 3.5cm, the electrodeposition temperature is 50°C, and the current density is 150A/m ² for 8 hours, and the current efficiency reaches 99.6%.

Claims (7)

1. a method for extracting lead by full wet method from lead plaster and lead sulfide concentrate, is characterized in that: comprise the following steps: 1) Carrying out the desulfurization conversion reaction of the lead plaster and the carbonate solution, and separating the solid and liquid to obtain the sulfate solution and the desulfurization conversion material containing lead carbonate and lead dioxide; the sulfate solution reclaims sulfate through evaporative crystallization; 2) Neutrally leaching the desulfurized converted material with a solution containing methanesulfonic acid, and separating the liquid from the solid to obtain a neutral leachate and a neutral leach residue; 3) The neutral leaching solution is mixed with the waste lead electrolytic solution to prepare the lead electrolytic solution to carry out the electrolytic lead deposition to obtain a lead plate and the waste lead electrolytic solution; 4) The neutral leaching slag is used as an oxidizing agent together with the lead sulfide concentrate to carry out acidic leaching with waste lead electrolysis solution, and the liquid and solid are separated to obtain an acidic leaching solution and an acidic leaching slag, and the acidic leaching solution is a solution containing methanesulfonic acid , returns neutral leach use. 2. The method for fully wet extraction of lead from lead plaster and lead sulfide concentrate according to claim 1, characterized in that: the conditions of the desulfurization conversion reaction are: the reaction temperature is 25 to 85°C, and the stirring speed is 100-800 rpm, the reaction time is 30-300 minutes, and the pH value at the end of the reaction is above 10. 3. the method for fully wet extraction of lead from lead paste and lead sulfide concentrate according to claim 1, characterized in that: the condition of the neutral leaching is: the solution containing methanesulfonic acid contains free formazan The concentration of sulfonic acid is 0.3-1.5mol/L, the liquid-solid ratio to the desulfurization converted material is 4mL/g-20mL/g, the leaching temperature is 40-100℃, the stirring speed is 200-1000 rpm, the leaching time After 30 to 300 minutes, the pH of the leaching liquid at the end of leaching is above 4.5. 4. the method for extracting lead by full wet method from lead plaster and lead sulfide concentrate according to claim 1, is characterized in that: the lead in the lead electrolysis solution that described neutral leachate and waste lead electrolysis solution are mixed prepares The ion concentration is 30-120g/L; the conditions for lead electrodeposition are: the current density is 80-400A/m ² , and the temperature of the lead electrodeposition solution is 30-65°C. 5. the method for extracting lead by full wet method from lead plaster and lead sulfide concentrate according to claim 4, is characterized in that: in the process of electrowinning lead, with graphite plate, titanium-based lead dioxide net or titanium-based platinum The mesh is an anode plate, and a lead starting plate, a titanium plate or a stainless steel plate is used as a cathode plate; the periphery of the cathode plate is 1-3 cm longer than the anode plate. 6. The method for fully wet extraction of lead from lead plaster and lead sulfide concentrate according to claim 1, characterized in that: the condition of the acidic leaching is: the solution of waste lead electrolysis and lead sulfide concentrate The solid ratio is 5mL/g-20mL/g, the leaching temperature is 40-100°C, the stirring speed is 200-1000 rpm, and the leaching time is 30-300 minutes. 7. the method for extracting lead by full wet method from lead plaster and lead sulfide concentrate according to claim 6, is characterized in that: in the acidic leaching process, the consumption of neutral leaching slag is measured with the lead dioxide that it comprises, It is 1 to 1.5 times the theoretical molar amount required to oxidize negative divalent sulfur ions in lead sulfide concentrate to elemental sulfur.