CN105197987B

CN105197987B - PbO, PbSO4, PbO2the separation method of mixture

Info

Publication number: CN105197987B
Application number: CN201510731341.0A
Authority: CN
Inventors: 许文林; 聂文; 王雅琼; 张涛; 吕佳乐; 张小兴
Original assignee: Yangzhou University
Current assignee: Yangzhou University
Priority date: 2015-11-02
Filing date: 2015-11-02
Publication date: 2016-08-24
Anticipated expiration: 2035-11-02
Also published as: CN105197987A

Abstract

The present invention relates to a kind of PbO, PbSO₄、PbO₂The technique of the separation method of mixture, the particularly comprehensive utilization of resources of waste lead accumulator lead-containing material and technology, belong to the comprehensive utilization of the waste lead accumulator three wastes or the separation and purification technical field of inorganic compound.With the lead-containing material of waste lead accumulator through physical separation method process obtain containing PbO, PbSO₄、PbO₂The lead plaster of mixture is raw material, uses acidleach to dissolve, leaches dissolving, separation and purification, solid-liquid separation coupling technique, it is achieved PbO, PbSO₄、PbO₂The separation of mixture.Present invention process is reasonable, and preparation method is simple, and product purity and yield are high, drastically reduce the area the by-product of process, reduce the comprehensive utilization cost of lead plaster resource, and process safety is reliable, beneficially heavy industrialization.

Description

PbO、PbSO4、PbO2The separation method of mixture

Technical field

The present invention relates to the process that a kind of waste lead accumulator lead recycles, specifically with the lead-containing material of waste lead accumulator through physical separation method process obtain containing PbO, PbSO₄、PbO₂The lead plaster of mixture is raw material, uses acidleach to dissolve, leaches dissolving, separation and purification, solid-liquid separation coupling technique, it is achieved PbO, PbSO₄、PbO₂The separation of mixture.

Belong to three-protection design and application technology as the second resource field, especially Comprehensive Utilization of Waste Lead Accumulator technical field；Fall within technical field of chemical separation；Fall within the preparing technical field of inorganic material.

Background technology

1. the lead resourceization of waste lead accumulator recycles

1.1 lead battery

The critical piece of lead battery is positive plate, negative plate, electrolyte, barrier film or dividing plate, battery case, additionally, also have some parts such as terminal, connection strap, blow-cook etc..Lead battery has in the advantages, always electrochmical power source such as simple in construction, easy to use, dependable performance, price are low that yield is big, the product of applied range.Along with new material and the research and development of new technique and application, the properties of lead battery has had and has increased substantially, lead battery more manifests in the advantage of some special application fields, and as Moped Scooter, extraordinary electric motor car, new automobile power supply, the nearly stage is still main flow power supply.

1.2 waste lead accumulator

In use, through long-term charge and discharge process, capacity drops to the lowest or time grid corrosion is seriously difficult to repair, lead battery will be unable to be normally carried out charge/discharge operation, thus produces waste lead accumulator for lead battery.Owing to lead battery improper use causes damaging, waste lead accumulator also can be produced.

What lead battery was common scraps reason active substance softening and shedding etc. on the sulfation of pole plate, grid corrosion, pole plate.Wherein the sulfation of pole plate is to generate the hard lead sulfate crystal speckle of white on pole plate, is very difficult to again be converted into active substance, does not reaches the purpose charged normal during charging, and the sulfation of lead battery is modal to scrap reason.

The importance that 1.3 waste lead accumulator lead resourceizations recycle

The structure of waste lead accumulator is essentially identical with lead battery with composition.As the main composition material lead of composition lead battery, being one of conventional metal, its yield, after ferrum, copper, aluminum, zinc metal, occupies the 5th.At present, the lead of about 70% is used for preparing lead battery, and the painting cream that lead plaster is actually in accumulator is through being melted into and PbO, PbSO of formation after use₄、PbO₂In the mixture of composition, its composition and content depend on cycle-index and the life-span length of waste lead accumulator.

Therefore, recycling lead from waste lead accumulator is extremely important lead source.Sufficiently and reasonably utilize the lead resource of waste lead accumulator, be possible not only to alleviate the situation that lead resource falls sharply day by day, preparation cost can also be reduced simultaneously, reduce environmental pollution.So, it is achieved the recycling of the lead of waste lead accumulator, not only there is the strategic importance of sustainable development, and there is important economy and social value.

The technique of the most existing lead resourceization recycling and technology

The lead plaster that waste lead accumulator obtains after sorting and pretreatment is most important lead-containing compounds, and in lead plaster, main component is substantially: 45%-65%PbSO₄, 10%-30%PbO, 10%-20%PbO₂With the mixture of 2%-3% metallic lead, wherein PbSO in lead plaster₄Content reaches more than 50%.

It is mainly process and the Utilizing question of lead plaster, the i.e. processing method of lead-containing compounds in lead plaster from the technique of waste lead battery lead recovery and technology, currently mainly has: pyrogenic process, wet method, pyrogenic process-wet method coupled processing method etc..The technique that existing lead resourceization recycles is not discussed below with technical point:

2.1 pyrometallurgical smelting lead recovery technologies

2.1.1 direct pyrometallurgical smelting lead recovery technology

Directly pyrogenic process lead smelting recovery technology dominating process route is: PbO, the PbSO directly obtained after sorting and pretreatment with waste lead accumulator₄、PbO₂Mixture is raw material, through being thermally treated resulting in metallic lead and lead oxides.Because PbSO₄Fusing point is high, and the temperature reaching to decompose completely will be more than 1000 DEG C, and generally with combustion gas, fuel oil, bituminous coal etc. as fuel, in high temperature melting furnace, at a temperature of the furnace of 1260 DEG C-1316 DEG C, melting obtains metallic lead.

Directly the advantage of pyrogenic process lead smelting recovery process is that operating unit is few.Shortcoming is because smelting temperature is high, reaches about 1300 DEG C from kiln gas temperature, and process energy consumption is big；Substantial amounts of lead volatility is caused to lose and formed the lead dust of contaminative under high temperature；The SO produced in fusion process₂Concentration is high, seriously polluted；SO₂Tail gas pollution environment.Metal recovery rate typically only has 80%-85% simultaneously, and the lead tolerance of slag reaches more than 10%.Unreasonable disposal in waste lead accumulator regenerative process also can produce the secondary pollution to environment, and causes the low inferior wasting of resources phenomenon of level of comprehensive utilization.

2.1.2 the pyrogenic process lead recovery technology improved

In order to overcome the shortcomings such as the pyrogenic process regeneration high energy consumption of melting, metallic lead volatilization loss amount are big, seriously polluted, have developed lead plaster desulfurization conversion technique, the pyrogenic process lead recovery process i.e. improved.First lead sulfate is converted into and is easier to other compound of pyrogenic attack and (typically lead sulfate is converted into ceruse by this technique, because the fusing point of ceruse is more much lower than lead sulfate, owing to ceruse just can be decomposed into lead monoxide at 340 DEG C, therefore pyrometallurgical smelting can be carried out at a lower temperature, sulfate radical in lead sulfate is converted into water-soluble sulfate, i.e. " desulfurization conversion " method simultaneously.Conventional desulfurizing agent is (NH₄)₂CO₃、NH₄HCO₃、Na₂CO₃、NaHCO₃, NaOH etc., by the PbSO in lead plaster₄It is converted into solvable Na₂SO₄And insoluble Pb₂CO₃Or Pb (OH)₂Precipitation.Na in filtrate₂SO₄、(NH₄)₂SO₄Na is obtained after cooling₂SO₄·10H₂O or (NH₄)₂SO₄Crystal, for the by-product of process.

The pyrogenic process of improvement reclaims splicer's skill due to PbCO₃For primary raw material, therefore, smelting temperature can be greatly lowered, decrease SO₂Pollute, improve operating environment.Its major defect is to there is desulfurization conversion during desulfurization conversion to be difficult to problem thoroughly, typically has the PbSO of about 5%₄In residual lead plaster in post-conversion, melting still can produce SO₂Discharge.Employing carbonate is desulfurizing agent, during produce a large amount of sulfate by-products, certainly exist the recycling problem of sulfate, and during yet suffer from that lead recovery utilization rate is low and the problem such as energy expenditure is big.

2.2 wet method lead recovery technologies

In order to solve the problem in pyrogenic process lead recovery technology, from the 1950's, have developed wet method lead recovery technology.The core of wet method lead recovery technology is to utilize the Pb dissolved in the solution²⁺Generate metal Pb in negative electrode generation reduction reaction, thus realize the recovery of lead, be a kind of environmentally friendly lead recovery technology.According to the feature of technical process, hydrometallurgic recovery smelting technique is divided into Direct Electrochemistry sedimentation and indirect electrochemical sedimentation.

2.2.1 Direct Electrochemistry sedimentation

Direct Electrochemistry sedimentation will be placed directly within electrochemical reactor by lead plaster, reclaims through electrochemical deposition and obtains lead.Typical Direct Electrochemistry sedimentation is the technology that the lead monoxide in a kind of NaOH of the employing aqueous dissolution lead plaster researched and developed by Chinese Academy Of Sciences Process Engineering Research Institute's (former chemical industry metallurgical institute) prepares leaded aqueous solution.This technique, using 10%-15%NaOH aqueous solution as electrolyte electrolyte, carries out electrochemical deposition under conditions of tank voltage is 1.8-2.6V, and negative electrode generation reduction reaction obtains metallic lead, and lead recovery is more than 95%, and current efficiency is up to 85%.

The subject matter that this technique exists is that power consumption is high, because only that the reduction reaction that negative electrode occurs is effecting reaction, energy expenditure is 350kWh/tPb, and alkaline consumption is 100kgNaOH/tPb.

2.2.2 indirect electrochemical sedimentation

Due to PbSO in lead plaster₄、PbO₂Existence, most of electrochemical deposition method techniques cannot Direct Electrochemistry deposition processes lead plaster, need to through further converting, leaching carry out electrochemical deposition method process again after processing.

In indirect electrochemical sedimentation processes lead plaster technique, typically there are RSR technique, USBM technique, CX-EW technique, NaOH-KNaC₄H₄O₆Technique etc..Being common that first by PbSO of these techniques₄And PbO₂Convert, then lead plaster is carried out leaching process, finally use electrochemical deposition method to obtain highly purified lead.Main technique has:

(1) RSR indirect electrochemical depositing operation

The core technology of RSR technique is: (NH₄)₂CO₃Desulfurization-Na₂SO₃Conversion-H₂SiF₄Dissolving-electrochemical cathode reduces.Use (NH₄)₂CO₃The PbSO in lead plaster is made for desulfurizing agent₄Desulfurization conversion is PbCO₃Precipitation, with SO₂Gas or sulphite are reducing agent and the PbO in lead plaster solution₂Reduction reaction is occurred to generate PbO precipitation, with the HBF of about 20%₄Or H₂SiF₆Solution is the PbCO that leaching liquid will obtain₃With PbO precipitation leaching in solution, make electrolyte, then by obtain containing Pb²⁺The further remove impurity of leaching liquid carries out electrochemical deposition after processing.In electrochemical deposition process, general employing graphite or coating PbO₂Titanium plate etc. as insoluble anode, the metal such as lead or corrosion resistant plate is negative electrode.During electrolysis, precipitating metal lead on negative electrode, owing to hydrogen overvoltage is higher, therefore there is H⁺The side reaction of electrochemical reduction is fewer；Anode mainly separates out O₂But, have part Pb²⁺On anode, electrochemical oxidation generates PbO₂.In order to reduce precipitation PbO on anode₂, it is necessary to manage to reduce oxygen deposition potential, or add some valence variation element (such as P, As, Co) in the electrolytic solution to reduce PbO₂Growing amount.The tank voltage of electrochemical deposition operation is about 2.2V, operation electric current density is 200A/m²-300A/m², purity can be obtained at negative electrode and be more than 99.99% metallic lead, general cathode efficiency is up to more than 90%.

(2) USBM indirect electrochemical depositing operation

The core technology of USBM technique is: (NH₄)₂CO₃Desulfurization-metal Pb conversion-H₂SiF₄Dissolving-electrochemical cathode reduces.USBM technique is essentially identical with RSR technique, is that desulfurizing agent makes the lead sulfate desulfurization conversion in lead plaster be ceruse precipitation also with ammonium sulfate.It is a difference in that with Hydrocerussitum (Ceruse) for reducing agent and the PbO in lead plaster solution₂Reduction reaction is occurred to generate PbO precipitation, PbO and PbCO of generation₃Use H₂SiF₆Electrolyte is made in dissolving, then carries out electrochemical deposition operation, the Pb in solution²⁺Separate out at negative electrode and obtain metallic lead.

(3) CX-EW indirect electrochemical depositing operation

The core technology of CX-EW technique is: Na₂CO₃Desulfurization-H₂O₂Conversion-H₂BF₄/H₂SiF₄Dissolving-electrochemical cathode reduces.CX-EW technique is essentially identical with RSR technique, utilizes Na₂CO₃As desulfurizing agent, next uses H₂O₂PbO in reduction lead plaster₂, use HBF the most equally₄Or H₂SiF₆Solution leaches PbO and PbCO₃The electrolyte prepared, electrochemical deposition method generates the cathode lead that purity is higher.

(4)NaOH-FeSO₄-KNaC₄H₄O₆Indirect electrochemical depositing operation

Hunan University have developed the lead plaster hydrometallurgical processes similar to RSR technology path.The core technology of this technique is: FeSO₄Convert-NaOH desulfurization-KNaC₄H₄O₆Dissolving-electrochemical cathode reduces.Use H₂SO₄FeSO in solution₄For reducing agent by PbO₂Reduction generates PbSO₄Carry out reduction to convert, use NaOH as desulfurizing agent by PbSO afterwards₄It is converted into PbO, finally utilizes NaOH-KNaC₄H₄O₆Dissolve PbO and prepare electrolyte, obtain lead by electrochemical deposition method.

2.2.3 the subject matter that electrochemical deposition process exists

Electrochemical deposition method recovery process, solves the SO in lead plaster pyrometallurgical smelting process₂The volatilization problems of metallic lead under discharge and high temperature.But existing hydrometallurgic recovery processes technique exists problem highlighted below:

(1) PbO on anode₂Precipitation problem: although each technique is all reducing PbO on anode₂Precipitation aspect done corresponding research, but be also difficult to thoroughly suppress PbO on anode at present₂Generation, the response rate causing lead is low.

(2) consume a large amount of chemical reagent and produce by-product problem: it is many that each technique relates to flow process, time-consuming length also introduces substantial amounts of chemical reagent, and during desulfurization conversion, produce a large amount of sulfate by-products, not only add the preparation cost of Pb, also have impact on economic benefit.

(3) energy expenditure is high, investment is big: because in electrochemical deposition process, only at negative electrode generation effecting reaction, and therefore electrochemical deposition reclaims the energy consumption height of metallic lead, the energy expenditure about 12kWh of 1 kilogram of lead of preparation, even taller than the energy consumption of tradition fire metallurgy process.It addition, employing electrochemical deposition technique, it is necessary to using special equipment, plant investment is big, is suitable only for large-scale recovery plant and uses.

For problem present in above-mentioned technological process, the most constantly have developed following several new technique, economic benefit and environmental benefit have had further improvement.

2.3 wet method lead plaster conversion-pyrogenic processes are prepared lead oxide coupling and are recycled splicer's technology

In order to give full play to wet method and the advantage of pyrogenic process recycling Technology, simultaneously taking account of and reclaim the feature that lead uses mainly as lead battery lead plaster, using wet method lead plaster conversion-pyrogenic process prepare lead oxide coupling to recycle splicer's technology is comparatively ideal Technology.

2.3.1PbO the importance in prepared by lead-acid battery electrode material

Traditional technique preparing lead-acid battery electrode plate active substance for raw material with metallic lead mainly obtains green plate through operation such as molten lead, Hydrocerussitum (Ceruse) manufacture and cream, coated plate etc., by the green plate obtained through pickling and the active substance that regains after chemical conversion on pole plate after using the operations such as electrochemistry chemical conversion.

By this production technology it can be seen that the Hydrocerussitum (Ceruse) based on PbO produced by metal lead pig, Hydrocerussitum (Ceruse) again through with the multiple working procedures such as cream, coated plate, green plate, pole plate chemical conversion after the active substance that regains after chemical conversion on pole plate.Wherein prepared Hydrocerussitum (Ceruse) by lead pig, again through high energy consumption techniques such as melted-oxidations.The manufacturing technology of Hydrocerussitum (Ceruse) is to be used ball-milling method (Shimadzu method) or vapour phase oxidation process (Ba Dunfa) by lead pig, makes the Hydrocerussitum (Ceruse) with PbO as main component through special equipment lead-power machine by oxidation screening.Due to shot or lead phase mutual friction and clash into and produce substantial amounts of heat in lead-power machine in ball-milling method, a body temperature is increased, inputting in the air draught of uniform temperature and humidity under the effect of oxygen in lead-power machine, shot or lead surface occur oxidation to generate PbO.Vapour phase oxidation process refers to that the lead liquid melted reacts the process making Hydrocerussitum (Ceruse) after gaseous oxidation indoor are stirred mist formation drop-wise with the oxygen in air.In general control Hydrocerussitum (Ceruse), PbO mass fraction is about 75% (the also referred to as oxidizability of Hydrocerussitum (Ceruse)).

Hydrocerussitum (Ceruse) forms the fertile material of battery lead plate active substance, the character of Hydrocerussitum (Ceruse) and quality control as lead battery and has a major impact for the performance of lead battery.Lead battery prepared by ultra-fine PbO granule has the advantage such as high power capacity and long discharge and recharge life-span, and its shortcoming is that to prepare ultra-fine lead oxide cost the highest.In sum, the metal Pb that waste lead accumulator lead plaster reclaims is applied in storage battery production, needs consumed energy again, just can be prepared as the Hydrocerussitum (Ceruse) with PbO as main component by ball-milling method or vapour phase oxidation process.

2.3.2 the Technology of PbO is directly prepared in research and development

Tradition scrap lead cream is through the pyrometallurgy of high energy consumption or electrodeposition hydrometallurgical recovery metal Pb, if metal Pb to be re-used for producing lead battery as raw material prepares the active substance of pole plate, it is necessary to through the complicated production technological process of multiple working procedure.If using suitable wet method lead plaster conversion-pyrogenic process to prepare lead oxide coupling technique, by the direct application and preparation of waste lead accumulator lead plaster in the ultra-fine PbO powder body of battery production, energy consumption will be reduced, and due to characteristics such as superfine powder large specific surface area, high power capacity, long-life high-performance accumulator can be prepared.Typical Technology has:

(1) the Placid technique improved

Pyrogenic process-wet method combined lead recovery technology that the Placid technique of improvement is come by Placid technological development, is the process integration of a kind of pyrogenic process-wet method.Leaching identical with Placid technique with purification process, unique except for the difference that employing lime precipitation replaces electrochemical deposition method.This technique primary raw material is lead plaster and inexpensive common lime, and residue is mainly Gypsum Fibrosum, its lead content 5%, the Pb (OH) of generation₂The most originally obtained pure lead with hard coal after decomposing in subsequent reactions still.The leaching efficiency of this technique is identical with Placid technique with product purity.In addition, sodium carbonate can also be utilized to carry out pyrogenic process lead recovery again after lead plaster is carried out wet desulphurization conversion, the decomposition temperature making lead plaster is reduced to 358 DEG C after conversion by 800 DEG C before converting, thus reduce the energy consumption during recycling waste lead batteries processes, avoid the discharge of sulfur dioxide simultaneously, decrease the pollution to environment.

(2) citric acid hydrometallurgic recovery and directly prepare ultra-fine PbO powder body technique

Utilize the structure of the stable chelant complex of lead citrate, citric acid is used for the wet recycling process of lead plaster, under the inspiration of this thinking, univ cambridge uk (Cambridge University) material science and Department of Metallurgy have developed a kind of new technology using citric acid wet treatment waste lead accumulator lead plaster.

The core technology of this technique is: citric acid desulfurization-H₂O₂Conversion-lead citrate thermal decomposition process.Lead plaster is mainly composed of PbO, PbSO₄And PbO₂, possibly together with metals such as a small amount of metal Pb and Sb.Utilizing citric acid that above-mentioned 3 kinds of leaded materials are changed into organo-lead compound, concrete reaction equation is as follows:

PbO+C₆H₈O₇·H₂O→Pb(C₆H₆O₇)·H₂O+H₂O

PbO₂+C₆H₈O₇·H₂O+H₂O₂→Pb(C₆H₆O₇)·H₂O+O₂+2H₂O

3PbSO4+2[Na₃C₆H₅O₇·2H₂O]→[3Pb·2(C₆H₅O₇)]·3H₂O+3Na₂SO₄+H₂O

PbO、PbSO₄And PbO₂3 kinds of starting materials and blending ingredients composition lead plaster react with citric acid solution, all can obtain the white crystal being similar to lead citrate.Can be with direct reaction synthesizing citric acid lead under PbO yellow powder and aqueous citric acid solution room temperature；PbO₂During black powder reacts with aqueous citric acid solution, it is simultaneously introduced H₂O₂For reducing agent, Pb (IV) is reduced to Pb (II), generation lead citrate can also be reacted under room temperature, release oxygen simultaneously；PbSO₄White powder and aqueous citric acid solution, add trisodium citrate as desulfurizing agent, it is also possible to reaction generates lead citrate crystal, synchronously completes desulfurization conversion, simultaneously by-product Na₂SO₄, Na in filtrate₂SO₄General employing crystallisation by cooling is as side-product (Na₂SO₄·10H₂O) reclaim.Filtrate returns original wet processing process, it is achieved the closed circulation of whole filtrate, it is to avoid cause the secondary pollution of discharging of waste liquid.Above-mentioned 3 reactions are carried out for 3 kinds of main matter in lead plaster, and operation is easy, the time is short, and lead recovery is above 99%.The lead citrate precipitated product obtained, after further remove impurity, washing and filtering, through low-temperature bake (300～500 DEG C), can be prepared by the powder body material with PbO and Pb as main component, can be directly as the raw material preparing lead battery active substance.

Lead citrate is the Metal-organic complex with macromolecular structure that the atoms such as lead and oxygen, carbon, hydrogen are formed.Because lead and organic ligand combine is likely to be formed different configurations and different ligancies, thus the Nomenclature Composition and Structure of Complexes of the lead citrate generated probably due to the change of reaction condition and there are differences.

The organic compound calcination at relatively low temperature of above-mentioned gained lead can be directly obtained lead oxide, and whole during without the generation of the pollutant such as lead steam, lead dust and sulfur dioxide, also produce without slag.

Citric acid wet treatment lead plaster technique has the advantage that compared with tradition pyrometallurgical smelting flow process

1. eliminating the preparation process of metallic lead, only the organo-lead compound obtained need to be carried out low temperature calcination, energy consumption is relatively low, considerably reduces energy consumption.

2. carry out low temperature calcination with organo-lead compound for raw material, directly prepare PbO powder body, can use directly as the Hydrocerussitum (Ceruse) producing lead battery, eliminate and prepare PbO powder process with lead.

3. being that raw material carries out low temperature calcination and can prepare ultra-fine PbO powder body by organo-lead compound, ultra-fine PbO powder body, as the active substance of pole plate, provides condition for preparing the active substance of high performance lead-acid battery electrode.

4. simplify technological process, decrease unit operation, operate relatively easy, security reliability is high.

5. high melt discharge SO is eliminated₂With the atmosphere pollution of volatility lead dust, improve the response rate of lead.

6. technical process directly obtains lead monoxide, decrease in the production engineering of lead battery lead to the production link of lead monoxide.The lead that can utilize existing waste lead accumulator reclaims existing equipment, reduces the equipment investment of technical process.

Although this technique is now also in the conceptual phase of laboratory, but considers from above several respects, this technique has preferably application and DEVELOPMENT PROSPECT, and the recycling technology of waste lead accumulator is had great reference.

This process technique there is also problem highlighted below:

1. a large amount of chemical reagent is consumed: at citric acid desulfurization-H₂O₂In conversion process, consume citric acid, sodium citrate and H₂O₂, the technical-economic index of influence process, the use of a large amount of chemical reagent, increase considerably preparation cost, the economic benefit of influence process.

2. a large amount of sulfate by-products is produced: during desulfurization conversion, produce a large amount of sulfate by-products, not only add the preparation cost of Pb, affect economic benefit, and open up the application of these by-products and find suitable market product and become the major control factors of this technology.

3. the price height of citric acid, sodium citrate, and the atom utilization of this technique is the most on the low side.

Therefore, researching and developing Technology economic and environment-friendly, that atom utilization is high, the problem tool solving to exist is of great significance.

Summary of the invention

The present invention provide a kind of with waste lead accumulator through pretreatment obtain containing PbO, PbSO₄、PbO₂Lead plaster be raw material, through PbO, PbSO that separation and purification obtains₄、PbO₂, and directly as preparing the raw material of lead-acid battery electrode active substance, it is achieved directly utilizing of waste lead accumulator lead plaster.

Realizing above-mentioned purpose technical scheme is:

A kind of PbO, PbSO₄、PbO₂The separation method of mixture, the lead plaster particularly obtained with the lead-containing material of waste lead accumulator through physical separation method process obtain containing PbO, PbSO₄、PbO₂Mixture is raw material, uses acidleach to dissolve, leaches dissolving, separation and purification, solid-liquid separation coupling technique, it is achieved PbO, PbSO₄、PbO₂The separation of mixture.Step is as follows:

(1) washing impurity-removing: in washing impurity-removing equipment, by PbO, PbSO₄、PbO₂Mixture carries out washing impurity-removing removing soluble impurity, and the material of scrubbed remove impurity enters next step；

(2) solid-liquid separation: in solid-liquid separation equipment, carries out solid-liquid separation by material obtained in the previous step, and the liquid phase material obtained enters the first step after further remove impurity processes and recycles as cleaning mixture, and the solid-phase material of isolated enters next step；

(3) acidleach is dissolved: in leaching dissolution equipment, add Acid leaching agent, with PbO, PbSO₄、PbO₂Mixture mixes, and PbO therein reacts with acid, makes the PbO in material generate water-soluble Pb²⁺Ion enters solution, and the material dissolved through acidleach enters next step；

(4) solid-liquid separation: in solid-liquid separation equipment, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained obtains water-soluble lead salt through further separation and purification or processes further and obtain PbO, and the solid-phase material obtained enters next step；

(5) leaching is dissolved: in leaching dissolution equipment, add leaching agent and PbSO obtained in the previous step₄And PbO₂Mixture, PbSO therein₄Entering leaching liquid, the material dissolved through leaching enters next step；

(6) in solid-liquid separation equipment, material obtained in the previous step being carried out solid-liquid separation, the liquid phase material obtained enters the tenth further separation and purification of step, and solid-phase material enters the 13rd further separation and purification of step；

(7) remove impurity decolouring: in remove impurity decolorizing and refining equipment, add adsorption-edulcoration agent, the liquid phase material that the 4th step obtains is carried out remove impurity decolouring, through adsorption-edulcoration decolouring containing Pb²⁺Solution enters next step；

(8) solid-liquid separation: in solid-liquid separation equipment, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the 9th further separation and purification of step, and solid-phase material enters previous step after treatment and realizes recycling as adsorption-edulcoration agent；

(9) crystallisation by cooling: in cooling crystallizing equipment, by obtained in the previous step containing Pb²⁺Refined soln cools down, Pb²⁺Salt-pepper noise separates out, and obtains Pb through solid-liquid separation²⁺Product salt, the separation mother solution obtained enters the 3rd step after further separation, impurity removal and uses as preparation nitrate leaching agent；

(10) remove impurity decolouring: in remove impurity decolorizing and refining equipment, adds adsorption-edulcoration agent, the liquid phase material that the 6th step obtains is carried out remove impurity decolouring, through the PbSO of adsorption-edulcoration₄Solution enters next step；

(11) solid-liquid separation: in solid-liquid separation equipment, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the 12nd further separation and purification of step, and solid-phase material enters previous step after treatment and realizes recycling as adsorption-edulcoration agent；

(12) evaporative crystallization: in evaporation crystallization equipment, carry out material obtained in the previous step heating, decompression operation, the solvent evaporating removing in solution enters gas phase, enters vapor phase solvent and enters the 5th step and realize recycling as leaching liquid, while evaporative crystallization, PbSO₄Crystallization, through solid-liquid separation, the liquid phase material obtained enters the 5th step and realizes recycling as leaching liquid, and solid-phase material is PbSO₄Product；

(13) washing impurity-removing: in washing impurity-removing equipment, adds cleaning mixture, and the solid-phase material that the 6th step obtains carries out washing impurity-removing separation (wash, extract, dissolve the removal of impurity)；

(14) solid-liquid separation: in solid-liquid separation equipment, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the 13rd step after further separation and purification and realizes recycling as cleaning mixture, and the solid-phase material obtained enters next step；

(15) drying and roasting: be dried by solid-phase material obtained in the previous step, roasting removes impurity, and the solid-phase material obtained is PbO₂Product.

Further, the acid described in the 3rd step acidleach course of dissolution is any one in nitric acid, acetic acid, citric acid, hexafluorosilicic acid, trifluoromethane sulfonic acid.

Further, the 5th step leaching liquid NH₃·H₂O-(NH₄)₂SO₄Or C₆H₈O₇·H₂O-Na₃C₆H₅O₇·2H₂O or (NH₄)₂SiF₆-H₂SiF₆Any one.

Further, the remove impurity decolorising agent described in the 7th step remove impurity decolouring and the tenth step remove impurity decolorization is activated carbon, kieselguhr and adsorbent of molecular sieve, it is also possible to being wherein two components or the mixture of three components, consumption is the 1.0%-5.0% of solution quality.

Further, the 9th step crystallisation by cooling temperature is 0 DEG C-20 DEG C, and operation pressure is for being generally pressed onto 10.0MPa.

Further, the absolute pressure of the 12nd step evaporation deamination decompression operation is 0.01MPa-0.08Ma, and operation temperature is at 20 DEG C-80 DEG C.

Further, PbO, PbSO during second step washing separates₄、PbO₂Mixture is 1:1-1:10 with the mass ratio of water.

Further, the washing impurity-removing liquid described in the tenth three steps of washing dedoping step is water, methanol, ethanol, it is also possible to be that wherein two components or the mixture of three components, total addition of described washing impurity-removing liquid and the mass ratio of Lead oxide brown are 1:1-1:10.

Further, during the 15th step drying and roasting, baking temperature is 20 DEG C-200 DEG C, and sintering temperature is 200 DEG C-600 DEG C.

Further, described during first step washing impurity-removing washing impurity-removing liquid is water, methanol, ethanol, it is also possible to be the mixture of wherein arbitrarily component, and total addition of described washing impurity-removing liquid is solid-phase material and the mass ratio of washing impurity-removing liquid is 1:1-1:10.

The technical thought of the inventive method is as follows:

(1) first, utilizing PbO easily and acid reaction, the product of generation is easily soluble in the characteristic of water, and with acid as leaching agent, PbO and acid react and generates water-soluble Pb²⁺Salt, by lead plaster mixture (PbO, PbSO₄、PbO₂PbO in) leaches in acid solution, reclaims the Pb being dissolved in water²⁺Salt, as the raw material preparing other lead compounds.

(2) secondly, NH is used₃·H₂O-(NH₄)₂SO₄Or C₆H₈O₇·H₂O-Na₃C₆H₅O₇·2H₂O or (NH₄)₂SiF₆-H₂SiF₆For leaching agent, utilize PbSO₄The feature that dissolubility in leaching agent increases with concentration and the rising of temperature, in leaching process, uses the leaching agent of high concentration to make PbSO₄Transfer to liquid phase from solid phase, the PbSO obtained₄Solution can process further in remove impurity, is met the electrolyte that electrochemical method processes, through the PbSO of separation and purification₄Solution can use the de-NH of evaporation₃Method, reduce NH in leaching agent₃Concentration, make PbSO₄Crystallization, obtains the PbSO refined₄Product, prepares PbO as electrochemical process₂Raw material with Pb.

(3) the 3rd, take into full account PbO₂Difficulty reacts and there is the characteristic of suitable solvent, exists with solid, to reduce the processing procedure of material in separation process.Through separating leaching PbO and PbSO₄Process, further remove impurity, obtain the PbO refined₂Material.

The main technical principle that the present invention uses:

(1) make use of the particularity of waste lead accumulator lead plaster: the product that waste lead accumulator lead plaster converts after being mainly the long-term discharge and recharge of active substance on battery lead plate.Lead plaster is mainly composed of PbO, PbSO₄And PbO₂, possibly together with the metals such as a small amount of metal Pb and Sb, wherein PbSO₄Up to more than 50%.Suitable separation and refining method is used to carry out separating available lead-containing compounds (PbO, PbSO₄And PbO₂), these lead-containing compounds, directly as preparing the raw material of lead-acid battery electrode, are waste lead accumulator lead plaster Application way most economical, effective, particularly improve the most efficient method of atom economy utilization rate.

(2) make use of the particularity of the operation principle of lead battery: after lead battery electric discharge, two electrode active materials are converted to the lead sulfate of indissoluble.In charging process, it is changed into PbO at anode lead sulfate₂, it is changed into Pb at negative electrode lead sulfate.Therefore, PbSO₄、PbO₂It is mainly comprising and existence form of lead-acid battery electrode active substance with Pb.

(3) make use of lead-acid battery electrode active substance particularity in preparation process: traditional technique preparing lead-acid battery electrode plate active substance for raw material with metallic lead is mainly operated obtained green plate by molten lead, Hydrocerussitum (Ceruse) manufacture and the unit such as cream, coated plate, the green plate obtained after using the operations such as electrochemistry chemical conversion, regain the active substance on pole plate after chemical conversion.Important intermediate during wherein PbO is electrode active material preparation process.

(4) PbSO is utilized₄It is soluble in the characteristic of compound electrolyte solution: PbSO₄Dissolve in following three kind solvents:

①NH₃·H₂O-(NH₄)₂SO₄

②C₆H₈O₇·H₂O-Na₃C₆H₅O₇·2H₂O

③PbSiF₆-H₂SiF₆

Therefore, select suitable solvent system, can be by PbSO₄Transferring to liquid phase from solid phase, convert thoroughly, efficiency is high.

(5) PbO is considered₂Difficulty reacts and there is the characteristic of suitable solvent: taken into full account PbO₂Difficulty reacts and there is the characteristic of suitable solvent, still exists with solid, to reduce material processing procedure in separation process.Lead sulfate is insoluble in water, and its dissolubility is 0.0041g/100g water (20 DEG C).Lead sulfate is practically insoluble in dilute strong acid solution, but can be dissolved in denseer sulfuric acid solution, ammonium acetate solution and strong base solution, generates readily soluble material.Take into full account PbO₂Difficulty reacts and there is the characteristic of suitable solvent, still exists with solid, to reduce material processing procedure in separation process.Through separating leaching PbO and PbSO₄Process, further remove impurity processes, obtains at refined PbO₂Material, can be directly as PbO₂Product material uses.

Beneficial effects of the present invention is embodied in: the present invention with waste lead accumulator through pretreatment obtain containing PbO, PbSO₄、PbO₂Lead plaster be raw material, through PbO, PbSO that separation and purification obtains₄、PbO₂Product.PbO, the PbSO prepared₄、PbO₂Product, directly as preparing the raw material of lead-acid battery electrode active substance, is melted into by electrochemistry in sulfuric acid solution, obtains PbO at anode and negative electrode respectively₂With Pb active substance, it is achieved directly utilizing of waste lead accumulator lead plaster, it it is the process of the waste lead accumulator lead resourceization recycling that a kind of technique is simple, production cost is low, by-product is few, atom utilization is high.

Accompanying drawing explanation

Fig. 1 is the process chart of the present invention.

Detailed description of the invention

Major process unit is: washing impurity-removing equipment, leaching dissolution equipment, solid-liquid separation equipment etc..

The present invention is further detailed explanation with embodiment below in conjunction with the accompanying drawings.

Embodiment one

As it is shown in figure 1, a kind of PbO, PbSO₄、PbO₂The separation method of mixture, particularly processes, with the lead-containing material of waste lead accumulator, PbO, the PbSO obtained through physical separation method₄、PbO₂The lead plaster of mixture is raw material, uses acidleach to dissolve, leaches dissolving, separation and purification, solid-liquid separation coupling technique, it is achieved PbO, PbSO₄、PbO₂The separation of mixture.It is characterized in that described method step is as follows:

(1) washing impurity-removing: in autoclave agitator treating impurity removing equipment, by PbO, PbSO₄、PbO₂Mixture carries out washing impurity-removing removing soluble impurity, and the washing impurity-removing liquid used in the process of washing impurity-removing is water, and the addition of water is solid-phase material and the mass ratio of washing impurity-removing liquid is 1:1, and the material of scrubbed remove impurity enters next step；

(2) solid-liquid separation: in decanter type solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the first step after further remove impurity processes and recycles as cleaning mixture, and the solid-phase material of isolated enters next step；

(3) acidleach is dissolved: in autoclave leaching dissolution equipment, adding Acid leaching agent nitric acid, concentration of nitric acid is 1.0mol/L, nitric acid dosage and PbO, PbSO₄And PbO₂In mixture, the mol ratio with PbO is 1.0:1.2, and operation temperature is 20 DEG C, and the PbO in material reacts with acid, makes the PbO in material generate water-soluble Pb²⁺Ion enters solution, and the material dissolved through acidleach enters next step；

(4) solid-liquid separation: in decanter type solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained obtains water-soluble lead salt through further separation and purification or processes further and prepare PbO, and the solid-phase material obtained enters next step；

(5) leaching is dissolved: in tubular type leaching dissolution equipment, addition leaching agent is NH₃·H₂O-(NH₄)₂SO₄, leaching liquid NH₃·H₂O-(NH₄)₂SO₄Middle free ammonia molar concentration is 36.0mol/L, and in solution, ammonium sulfate molar concentration concentration is 6.0mol/L, and operation temperature is 20 DEG C, and the material dissolved through leaching enters next step；

(6) in centrifugal solid-liquid separation equipment, material obtained in the previous step being carried out solid-liquid separation, the liquid phase material obtained enters the tenth further separation and purification of step, and solid-phase material enters the 13rd further separation and purification of step；

(7) remove impurity decolouring: autoclave stirring remove impurity decolorizing and refining equipment in, add activated carbon, the consumption of activated carbon is the 1.0% of solution quality, and the liquid phase material that the 4th step obtains is carried out remove impurity decolorization operations, through adsorption-edulcoration decolouring containing Pb²⁺Solution enters next step；

(8) solid-liquid separation: in any one solid-liquid separation equipment in decanter type solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the 9th further separation and purification of step, and solid-phase material enters previous step after treatment and realizes recycling as adsorption-edulcoration agent；

(9) crystallisation by cooling: in autoclave agitated crystallizer equipment, by obtained in the previous step containing Pb²⁺Refined soln is cooled to 0 DEG C, Pb²⁺Salt-pepper noise separates out, and obtains Pb through solid-liquid separation²⁺Product salt, the separation mother solution obtained enters the 3rd step after further separation, impurity removal and uses as the liquid configuring acid solution leaching；

(10) remove impurity decolouring: in remove impurity decolorizing and refining equipment, adds adsorption-edulcoration agent activated carbon, and activated carbon content is the 5.0% of solution quality, the liquid phase material that the 6th step obtains is carried out remove impurity decolorization operations, through the PbSO of adsorption-edulcoration₄Solution enters next step；

(11) solid-liquid separation: in decanter type solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the 12nd further separation and purification of step, and solid-phase material enters previous step after treatment and realizes recycling as adsorption-edulcoration agent；

(12) evaporative crystallization: in autoclave stirring evaporation crystallization equipment, carry out material obtained in the previous step heating, decompression operation, the absolute pressure of evaporation deamination decompression operation is 0.01MPa, the solvent evaporating removing in solution enters gas phase, enter vapor phase solvent and enter the 5th step as leaching liquid realization recycling, while evaporative crystallization, PbSO₄Crystallization, through solid-liquid separation, the liquid phase material obtained enters the 5th step and realizes recycling as leaching liquid, and solid-phase material is PbSO₄Product；

(13) washing impurity-removing: in washing impurity-removing equipment, adds cleaning mixture water, and the consumption of water is solid-phase material Lead oxide brown quality and the mass ratio of washing impurity-removing liquid is 1:10；

(14) solid-liquid separation: in centrifugal solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the 13rd step after further separation and purification and realizes recycling as cleaning mixture, and solid-phase material enters next step；

(15) drying and roasting: be dried by solid-phase material obtained in the previous step, baking temperature is 200 DEG C, and sintering temperature is 600 DEG C.Roasting removes impurity, and the solid-phase material obtained is PbO₂Product.

Embodiment two

(1) washing impurity-removing: in tubular type scrubber washing impurity-removing equipment, by PbO, PbSO₄、PbO₂Mixture carries out washing impurity-removing removing soluble impurity, and the washing impurity-removing liquid used in the process of washing impurity-removing is methanol, and total addition of described washing impurity-removing liquid is solid-phase material and the mass ratio of washing impurity-removing liquid is 1:1, and the material of scrubbed remove impurity enters next step；

(2) solid-liquid separation: in vane type solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the first step after further remove impurity processes and recycles as cleaning mixture, and the solid-phase material of isolated enters next step；

(3) acidleach is dissolved: in tubular type leaching dissolution equipment, adding Acid leaching agent acetic acid, acetic acid concentration is 8.0mol/L, acid consumption and PbO, PbSO₄And PbO₂In mixture, the mol ratio with PbO is 1.0:2.0, and operation temperature is 40 DEG C, and the PbO in material reacts with acid, makes the PbO in material generate water-soluble Pb²⁺Ion enters solution, and the material dissolved through acidleach enters next step；

(4) solid-liquid separation: in filter-press type solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained obtains water-soluble lead salt through further separation and purification or processes further and prepare PbO, and solid-phase material enters next step；

(5) leaching is dissolved: leach in dissolution equipment in static mixer, and adding leaching agent leaching liquid is C₆H₈O₇·H₂O-Na₃C₆H₅O₇·2H₂O, leaching liquid NH₃·C₆H₈O₇·H₂The concentration of O is 6.0mol/L, Na in solution₃C₆H₅O₇Molar concentration concentration is 4.0mol/L, and the material dissolved through leaching enters next step；

(6) in centrifugal solid-liquid separation device, material obtained in the previous step being carried out solid-liquid separation, the liquid phase material obtained enters the tenth further separation and purification of step, and solid-phase material enters the 13rd further separation and purification of step；

(7) remove impurity decolouring: in static mixing remove impurity decolorizing and refining equipment, add adsorption-edulcoration agent kieselguhr and adsorbent of molecular sieve, consumption is the 3.0% of solution quality, and the liquid phase material that the 4th step obtains is carried out remove impurity decolorization operations, through adsorption-edulcoration decolouring containing Pb²⁺Solution enters next step；

(8) solid-liquid separation: in filter-press type-liquid separating apparatus, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the 9th further separation and purification of step, and solid-phase material enters previous step after treatment and realizes recycling as adsorption-edulcoration agent；

(9) crystallisation by cooling: in static mixing cooling crystallizing equipment, by obtained in the previous step containing Pb²⁺Refined soln is cooled to 20 DEG C, Pb²⁺Salt-pepper noise separates out, and obtains Pb through solid-liquid separation²⁺Product salt, the separation mother solution obtained enters the 3rd step after further separation, impurity removal and uses as the liquid configuring acid solution leaching；

(10) remove impurity decolouring: in remove impurity decolorizing and refining equipment, adds adsorption-edulcoration agent molecule sieve adsorbant, and molecular sieve consumption is the 1.0% of solution quality, the liquid phase material that the 6th step obtains is carried out remove impurity decolorization operations, through the PbSO of adsorption-edulcoration₄Solution enters next step；

(11) solid-liquid separation: in vane type solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the 12nd further separation and purification of step, and solid-phase material enters previous step after treatment and realizes recycling as adsorption-edulcoration agent；

(12) evaporative crystallization: in static mixer in evaporation crystallization equipment, carry out material obtained in the previous step heating, decompression operation, the absolute pressure of evaporation deamination decompression operation is 0.08Ma, the solvent evaporating removing in solution enters gas phase, enter vapor phase solvent and enter the 5th step as leaching liquid realization recycling, while evaporative crystallization, PbSO₄Crystallization, through solid-liquid separation, the liquid phase material obtained enters the 5th step and realizes recycling as leaching liquid, and solid-phase material is PbSO₄Product；

(13) washing impurity-removing: in washing impurity-removing equipment, adds cleaning mixture methanol, and methanol addition is 1:1 with the mass ratio of Lead oxide brown；

(14) solid-liquid separation: in decanter type solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the 13rd step after further separation and purification and realizes recycling as cleaning mixture, and solid-phase material enters next step；

(15) drying and roasting: be dried by solid-phase material obtained in the previous step, baking temperature is 80 DEG C, and sintering temperature is 200 DEG C.Roasting removes impurity, and the solid-phase material obtained is PbO₂Product.

Embodiment three

(1) washing impurity-removing: in static mixing washing impurity-removing equipment, by PbO, PbSO₄、PbO₂Mixture carries out washing impurity-removing removing soluble impurity, and the washing impurity-removing liquid used in the process of washing impurity-removing is ethanol, and total addition of described washing impurity-removing liquid is solid-phase material and the mass ratio of washing impurity-removing liquid is 1:10, and the material of scrubbed remove impurity enters next step；

(2) solid-liquid separation: in filter-press type solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the first step after further remove impurity processes and recycles as cleaning mixture, separates solid-phase material and enters next step；

(3) acidleach is dissolved: in autoclave stirring leaching dissolution equipment, adding Acid leaching agent citric acid, acid concentration is 4.0mol/L, acid consumption and PbO, PbSO₄And PbO₂In mixture, the mol ratio with PbO is 1.0:2.0, and operation temperature is 60 DEG C, and the PbO in material reacts with acid, makes the PbO in material generate water-soluble Pb²⁺Ion enters solution, and the material dissolved through acidleach enters next step；

(4) solid-liquid separation: in centrifugal solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained obtains water-soluble lead salt through further separation and purification or processes further and prepare PbO, and solid-phase material enters next step；

(5) leaching is dissolved: in tubular type leaching dissolution equipment, adding leaching agent leaching liquid is C₆H₈O₇·H₂O-Na₃C₆H₅O₇·2H₂O, leaching liquid C₆H₈O₇Molar concentration be 6.0mol/L, Na in solution₃C₆H₅O₇Molar concentration concentration be 6.0mol/L, operation temperature be 60 DEG C, through leaching dissolve material enter next step；

(6) in decanter type solid-liquid separation device, material obtained in the previous step being carried out solid-liquid separation, the liquid phase material obtained enters the tenth further separation and purification of step, and solid-phase material enters the 13rd further separation and purification of step；

(7) remove impurity decolouring: in autoclave stirring remove impurity decolorizing and refining equipment, add adsorption-edulcoration agent activated carbon, kieselguhr and molecular sieve, its consumption is the 3.0% of solution quality, and the liquid phase material that the 4th step obtains is carried out remove impurity decolorization operations, through adsorption-edulcoration decolouring containing Pb²⁺Solution enters next step；

(8) solid-liquid separation: in vane type solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the 9th further separation and purification of step, and solid-phase material enters previous step after treatment and realizes recycling as adsorption-edulcoration agent；

(10) remove impurity decolouring: in remove impurity decolorizing and refining equipment, adding adsorption-edulcoration agent is activated carbon, kieselguhr and adsorbent of molecular sieve, its consumption is the 2.0% of solution quality, and the liquid phase material that the 6th step obtains is carried out remove impurity decolorization operations, through the PbSO of adsorption-edulcoration₄Solution enters next step；

(12) evaporative crystallization: in autoclave stirring evaporation crystallization equipment, carry out material obtained in the previous step heating, decompression operation, the absolute pressure of evaporation deamination decompression operation is 0.04Ma, the solvent evaporating removing in solution enters gas phase, enter vapor phase solvent and enter the 5th step as leaching liquid realization recycling, while evaporative crystallization, PbSO₄Crystallization, through solid-liquid separation, the liquid phase material obtained enters the 5th step and realizes recycling as leaching liquid, and solid-phase material is PbSO₄Product；

(13) washing impurity-removing: in washing impurity-removing equipment, addition cleaning mixture is water, methanol and ethanol, and total addition of washing impurity-removing liquid and the mass ratio of Lead oxide brown are 1:5；

(14) solid-liquid separation: in vane type solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the 13rd step after further separation and purification and realizes recycling as cleaning mixture, and solid-phase material enters next step；

(15) drying and roasting: be dried by solid-phase material obtained in the previous step, baking temperature is 120 DEG C, and sintering temperature is 300 DEG C.Roasting removes impurity, and the solid-phase material obtained is PbO₂Product.

Embodiment four

(1) washing impurity-removing: in static mixing scrubber in washing impurity-removing equipment, by PbO, PbSO₄、PbO₂Mixture carries out washing impurity-removing removing soluble impurity, washing impurity-removing liquid used in the process of washing impurity-removing is water, methanol and ethanol, total addition of washing impurity-removing liquid is solid-phase material and the mass ratio of washing impurity-removing liquid is 1:4, and the material of scrubbed remove impurity enters next step；

(3) acidleach is dissolved: in autoclave agitated crystallizer leaching dissolution equipment, adding Acid leaching agent hexafluorosilicic acid, acid concentration is 8.0mol/L, acid consumption and PbO, PbSO₄And PbO₂In mixture, the mol ratio with PbO is 1.0:1.2, and operation temperature is 60 DEG C, and the PbO in material reacts with acid, makes the PbO in material generate water-soluble Pb²⁺Ion enters solution, and the material dissolved through acidleach enters next step；

(4) solid-liquid separation: in decanter type solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained obtains water-soluble lead salt through further separation and purification or processes further and prepare PbO, and solid-phase material enters next step；

(5) leaching is dissolved: in tubular type leaching dissolution equipment, add leaching agent leaching liquid (NH₄)₂SiF₆-H₂SiF₆, the material dissolved through leaching enters next step；

(7) remove impurity decolouring: autoclave stirring remove impurity decolorizing and refining equipment in, add adsorption-edulcoration agent activated carbon, activated carbon content is the 2.0% of solution quality, and the liquid phase material that the 4th step obtains is carried out remove impurity decolorization operations, through adsorption-edulcoration decolouring containing Pb²⁺Solution enters next step；

(8) solid-liquid separation: in filter-press type solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the 9th further separation and purification of step, and solid-phase material enters previous step after treatment and realizes recycling as adsorption-edulcoration agent；

(9) crystallisation by cooling: in autoclave stirring cooling crystallizing equipment, by obtained in the previous step containing Pb²⁺Refined soln is cooled to 20 DEG C, Pb²⁺Salt-pepper noise separates out, and obtains Pb through solid-liquid separation²⁺Product salt, the separation mother solution obtained enters the 3rd step after further separation, impurity removal and uses as the liquid configuring acid solution leaching；

(10) remove impurity decolouring: in remove impurity decolorizing and refining equipment, add adsorption-edulcoration agent kieselguhr and adsorbent of molecular sieve, kieselguhr and adsorbent of molecular sieve consumption are the 2.0% of solution quality, and the liquid phase material that the 6th step obtains is carried out remove impurity decolorization operations, through the PbSO of adsorption-edulcoration₄Solution enters next step；

(13) washing impurity-removing: in washing impurity-removing equipment, adding cleaning mixture washing impurity-removing liquid is water, methanol, ethanol, and total addition of washing impurity-removing liquid and the mass ratio of Lead oxide brown are 1:4；

(14) solid-liquid separation: in filter-press type solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the 13rd step after further separation and purification and realizes recycling as cleaning mixture, and the solid-phase material obtained enters next step；

(15) drying and roasting: be dried by solid-phase material obtained in the previous step, baking temperature is 80 DEG C, and sintering temperature is 320 DEG C.Roasting removes impurity, and the solid-phase material obtained is PbO₂Product.

Embodiment five

(1) washing impurity-removing: in autoclave agitator treating device washing impurity-removing equipment, by PbO, PbSO₄、PbO₂Mixture carries out washing impurity-removing removing soluble impurity, and the washing impurity-removing liquid used in the process of washing impurity-removing is water, and water addition is solid-phase material and the mass ratio of washing impurity-removing liquid is 1:8, and the material of scrubbed remove impurity enters next step；

(3) acidleach is dissolved: in autoclave stirring leaching dissolution equipment, adding Acid leaching agent trifluoromethane sulfonic acid, acid concentration is 8.0mol/L, acid consumption and PbO, PbSO₄And PbO₂In mixture, the mol ratio with PbO is 1.0:1.6, and operation temperature is 20 DEG C DEG C, and the PbO in material reacts with acid, makes the PbO in material generate water-soluble Pb²⁺Ion enters solution, and the material dissolved through acidleach enters next step；

(4) solid-liquid separation: in vane type solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained obtains water-soluble lead salt through further separation and purification or processes further and prepare PbO, and solid-phase material enters next step；

(5) leaching is dissolved: in autoclave stirring leaching dissolution equipment, add leaching agent leaching liquid (NH₄)₂SiF₆-H₂SiF₆, the material dissolved through leaching enters next step；

(6) in filter-press type solid-liquid separation device, material obtained in the previous step being carried out solid-liquid separation, the liquid phase material obtained enters the tenth further separation and purification of step, and solid-phase material enters the 13rd further separation and purification of step；

(7) remove impurity decolouring: in autoclave stirring remove impurity decolorizing and refining equipment, add adsorption-edulcoration agent molecule sieve adsorbant, molecular sieve consumption is the 1.0% of solution quality, and the liquid phase material that the 4th step obtains is carried out remove impurity decolorization operations, through adsorption-edulcoration decolouring containing Pb²⁺Solution enters next step；

(10) remove impurity decolouring: in remove impurity decolorizing and refining equipment, adds adsorption-edulcoration agent adsorbent, and molecular sieve consumption is the 1.0%% of solution quality, the liquid phase material that the 6th step obtains is carried out remove impurity decolorization operations, through the PbSO of adsorption-edulcoration₄Solution enters next step；

(12) evaporative crystallization: in autoclave stirring evaporation crystallization equipment, carry out material obtained in the previous step heating, decompression operation, the absolute pressure of operation is 0.01MPa, the solvent evaporating removing in solution enters gas phase, enter vapor phase solvent and enter the 5th step as leaching liquid realization recycling, while evaporative crystallization, PbSO₄Crystallization, through solid-liquid separation, the liquid phase material obtained enters the 5th step and realizes recycling as leaching liquid, and solid-phase material is PbSO₄Product；

(13) washing impurity-removing: in washing impurity-removing equipment, adds cleaning mixture, the solid-phase material that the 6th step obtains is carried out washing impurity-removing separation, and washing impurity-removing liquid described during washing impurity-removing is water, and water addition is 1:1-1:10 with the mass ratio of Lead oxide brown；

(14) solid-liquid separation: in any one solid-liquid separation equipment in centrifugal solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the 13rd step after further separation and purification and realizes recycling as cleaning mixture, and solid-phase material enters next step；

Embodiment six

(1) washing impurity-removing: in autoclave agitator treating impurity removing equipment, by PbO, PbSO₄、PbO₂Mixture carries out washing impurity-removing removing soluble impurity, and the washing impurity-removing liquid used in the process of washing impurity-removing is water, and water addition is solid-phase material and the mass ratio of washing impurity-removing liquid is 1:1-1:10, and the material of scrubbed remove impurity enters next step；

(3) acidleach is dissolved: in autoclave leaching dissolution equipment, adding Acid leaching agent trifluoromethane sulfonic acid, acid concentration is 8.0mol/L, acid consumption and PbO, PbSO₄And PbO₂In mixture, the mol ratio with PbO is 1.0:2.0, and 60 DEG C, the PbO in material reacts with acid, makes the PbO in material generate water-soluble Pb²⁺Ion enters solution, and the material dissolved through acidleach enters next step；

(5) leaching is dissolved: in autoclave stirring leaching dissolution equipment, adding leaching agent leaching liquid is NH₃·H₂O-(NH₄)₂SO₄, the material dissolved through leaching enters next step；

(6) in solid-liquid separation device, material obtained in the previous step being carried out solid-liquid separation, the liquid phase material obtained enters the tenth further separation and purification of step, and solid-phase material enters the 13rd further separation and purification of step；

(7) remove impurity decolouring: in remove impurity decolorizing and refining equipment, add adsorption-edulcoration agent molecule sieve adsorbant, consumption is the 1.0% of solution quality, and the liquid phase material that the 4th step obtains is carried out remove impurity decolorization operations, through adsorption-edulcoration decolouring containing Pb²⁺Solution enters next step；

(8) solid-liquid separation: in any one solid-liquid separation equipment in solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the 9th further separation and purification of step, and solid-phase material enters previous step after treatment and realizes recycling as adsorption-edulcoration agent；

(9) crystallisation by cooling: in cooling crystallizing equipment, by obtained in the previous step containing Pb²⁺Refined soln is cooled to 0 DEG C, Pb²⁺Salt-pepper noise separates out, and obtains Pb through solid-liquid separation²⁺Product salt, the separation mother solution obtained enters the 3rd step after further separation, impurity removal and uses as the liquid configuring acid solution leaching；

(10) remove impurity decolouring: in remove impurity decolorizing and refining equipment, adds adsorption-edulcoration agent kieselguhr, consumption is the 1.0% of solution quality, and the liquid phase material that the 6th step obtains is carried out remove impurity decolorization operations, through the PbSO of adsorption-edulcoration₄Solution enters next step；

(11) solid-liquid separation: in solid-liquid separation device, material obtained in the previous step is carried out solid-liquid separation, the liquid phase material obtained enters the 12nd further separation and purification of step, and solid-phase material enters previous step after treatment and realizes recycling as adsorption-edulcoration agent；

(12) evaporative crystallization: in autoclave stirring evaporation crystallization equipment, carry out material obtained in the previous step heating, decompression operation, the absolute pressure of evaporation deamination decompression operation is 0.08Ma, the solvent evaporating removing in solution enters gas phase, enter vapor phase solvent and enter the 5th step as leaching liquid realization recycling, while evaporative crystallization, PbSO₄Crystallization, through solid-liquid separation, the liquid phase material obtained enters the 5th step and realizes recycling as leaching liquid, and solid-phase material is PbSO₄Product；

(13) washing impurity-removing: in washing impurity-removing equipment, adds cleaning mixture water, and water addition is 1:4 with the mass ratio of Lead oxide brown；

(14) solid-liquid separation: in solid-liquid separation device, carries out solid-liquid separation by material obtained in the previous step, and the liquid phase material obtained enters the 13rd step after further separation and purification and realizes recycling as cleaning mixture, and solid-phase material enters next step；

The invention is not restricted to above-described embodiment, the technical scheme of all employing equivalents or equivalence replacement formation belongs to the scope of protection of present invention.Except the various embodiments described above, embodiment of the present invention also have a lot, and all technical schemes using equivalent or equivalence to replace, all within protection scope of the present invention.

Claims

1. a PbO, PbSO₄、PbO₂The separation method of mixture, it is characterised in that be that the lead-containing material with waste lead accumulator is through physics Separation method process obtain containing PbO, PbSO₄、PbO₂The lead plaster of mixture is raw material, use acidleach dissolve, leaching dissolving, separation and purification, Solid-liquid separation coupling process, it is achieved PbO, PbSO₄、PbO₂The separation of mixture；Step is as follows:

(1) washing impurity-removing: in washing impurity-removing equipment, by PbO, PbSO₄、PbO₂Mixture carries out washing impurity-removing, removes soluble impurity, through washing Wash away miscellaneous material and enter next step；

(2) solid-liquid separation: in solid-liquid separation equipment, carries out solid-liquid separation by material obtained in the previous step, and the liquid phase material obtained is through further remove impurity Entering (1st) step after process to recycle as cleaning mixture, the solid-phase material of isolated enters next step；

(3) acidleach is dissolved: in leaching dissolution equipment, add Acid leaching agent, with PbO, PbSO₄、PbO₂Mixture mixes, therein PbO reacts with acid, makes the PbO in material generate water-soluble Pb²⁺Ion enters solution, and the material dissolved through acidleach enters next step； Described acid is any one in nitric acid, acetic acid, citric acid, hexafluorosilicic acid, trifluoromethane sulfonic acid；

(4) solid-liquid separation: in solid-liquid separation equipment, carries out solid-liquid separation by material obtained in the previous step, and the liquid phase material obtained is through further Separation and purification obtains water-soluble lead salt or further process obtains PbO, and the solid-phase material obtained enters next step；

(5) leaching is dissolved: in leaching dissolution equipment, adding leaching agent and solid-phase material obtained in the previous step, the material dissolved through leaching enters Enter next step；Described leaching agent is NH₃·H₂O-(NH₄)₂SO₄Or C₆H₈O₇·H₂O-Na₃C₆H₅O₇·2H₂O or (NH₄)₂SiF₆-H₂SiF₆'s Any one；

(6) in solid-liquid separation equipment, material obtained in the previous step being carried out solid-liquid separation, the liquid phase material obtained enters (10th) step and divides further From refined, solid-phase material enters (13rd) the further separation and purification of step；

(7) remove impurity decolouring: in remove impurity decolorizing and refining equipment, adds adsorption-edulcoration agent, the liquid phase material that (4th) step obtains is carried out remove impurity decolouring, Through adsorption-edulcoration decolouring containing Pb²⁺Solution enters next step；

(8) solid-liquid separation: in solid-liquid separation equipment, carries out solid-liquid separation by material obtained in the previous step, and the liquid phase material obtained enters (9th) Walking further separation and purification, solid-phase material reclaims adsorption-edulcoration agent after treatment and enters previous step realization recycling；

(9) crystallisation by cooling: in cooling crystallizing equipment, cools down liquid phase material obtained in the previous step, Pb²⁺Salt-pepper noise separates out, and divides through solid-liquid From obtaining Pb²⁺Product salt, the separation mother solution obtained enters (3rd) step after further separation, impurity removal and uses as preparating acid leaching agent；

(10) remove impurity decolouring: in remove impurity decolorizing and refining equipment, adds adsorption-edulcoration agent, the liquid phase material that (6th) step obtains is carried out remove impurity decolouring, PbSO through adsorption-edulcoration₄Solution enters next step；

(11) solid-liquid separation: in solid-liquid separation equipment, carries out solid-liquid separation by material obtained in the previous step, and the liquid phase material obtained enters (12nd) Walking further separation and purification and enter next step, solid-phase material reclaims adsorption-edulcoration agent after treatment and enters previous step realization recycling；

(12) evaporative crystallization: in evaporation crystallization equipment, carries out material obtained in the previous step heating, decompression operation, in solution evaporation removing molten Agent enters gas phase, and this vapor phase solvent enters (5th) step and realizes recycling as leaching liquid；While evaporative crystallization, PbSO₄Crystallization, Through solid-liquid separation, the liquid phase material obtained enters (5th) step and realizes recycling as leaching liquid, and solid-phase material is PbSO₄Product；

(13) washing impurity-removing: in washing impurity-removing equipment, adds cleaning mixture, the solid-phase material that (6th) step obtains is carried out washing impurity-removing separation；

(14) solid-liquid separation: in solid-liquid separation equipment, carries out solid-liquid separation by material obtained in the previous step, and the liquid phase material obtained is through further Entering (13rd) step after separation and purification to realize recycling as cleaning mixture, solid-phase material enters next step；

(15) drying and roasting: be dried by solid-phase material obtained in the previous step, at 200 DEG C-600 DEG C, roasting removes impurity, and the solid-phase material obtained is PbO₂Product.

PbO, PbSO the most according to claim 1₄、PbO₂The separation method of mixture, it is characterised in that: (7th) step remove impurity decolouring It is the one in activated carbon, kieselguhr and adsorbent of molecular sieve with the remove impurity adsorbent described in (10th) step remove impurity decolorization, or they In any two components or the mixture of three components, the consumption of remove impurity adsorbent is the 1.0%-5.0% of solution quality.

PbO, PbSO the most according to claim 1₄、PbO₂The separation method of mixture, it is characterised in that: (9th) step crystallisation by cooling Temperature is 0 DEG C-20 DEG C.

PbO, PbSO the most according to claim 1₄、PbO₂The separation method of mixture, it is characterised in that: (12nd) step evaporation is de- The absolute pressure of ammonia decompression operation is 0.01MPa-0.08MPa.

Separation method the most according to claim 1, it is characterised in that: PbO, PbSO in (2nd) step washing separation₄、PbO₂Mixture It is 1:1-1:10 with the mass ratio of water.

PbO, PbSO the most according to claim 1₄、PbO₂The separation method of mixture, it is characterised in that: (13rd) step washing removes Cleaning mixture described during miscellaneous is water, methanol, ethanol, or any two components or the mixture of three components in them, described washing impurity-removing liquid The mass ratio of total addition and Lead oxide brown be 1:1-1:10.

PbO, PbSO the most according to claim 1₄、PbO₂The separation method of mixture, it is characterised in that: (15th) step is dried roasting During burning, baking temperature is 20 DEG C-200 DEG C.

Separation method the most according to claim 1, it is characterised in that: the washing impurity-removing liquid used in (1st) step washing impurity-removing process is Water, methanol, ethanol, or the mixture of any component in them, total addition of described washing impurity-removing liquid is solid-phase material and washing impurity-removing The mass ratio of liquid is 1:1-1:10.