CN104789776B - A method of from recycling lead oxide in the scrap lead containing oxidation - Google Patents
A method of from recycling lead oxide in the scrap lead containing oxidation Download PDFInfo
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- CN104789776B CN104789776B CN201410019975.9A CN201410019975A CN104789776B CN 104789776 B CN104789776 B CN 104789776B CN 201410019975 A CN201410019975 A CN 201410019975A CN 104789776 B CN104789776 B CN 104789776B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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Abstract
The present invention provides a kind of methods recycling lead oxide from the scrap lead containing oxidation, and this approach includes the following steps：（1）Oxidation scrap lead will be contained to contact with enveloping agent solution, and the mixture after contact will be separated by solid-liquid separation, obtain leaded filtrate and filter residue；（2）Above-mentioned leaded filtrate is reacted with precipitating reagent, and obtained reaction product is separated by solid-liquid separation, obtains lead salt precipitation and regenerated complexing agent filtrate, and by the complexing agent filtrate return to step（1）Course of dissolution；（3）Above-mentioned lead salt is precipitated and carries out desalination decomposition to obtain PbO.This method can efficiently in selective recovery scrap lead containing oxidation PbO, and effectively remove impurity therein, the PbO of obtained high-purity.
Description
Technical field
The present invention relates to a kind of methods recycling lead oxide from the scrap lead containing oxidation.
Background technology
Since 1859 by French engineer Pulan spy invention lead-acid battery, lead-acid battery with its cheap price with can
The stability leaned on is in secondary cell market, especially automobile batteries and electric bicycle market in occupation of important position.According to electricity
Pond statistics shows that Chinese lead bullion total quantity consumed in 2012 is more than 464.6 ten thousand tons, and wherein lead-acid battery consumption figure is 3,300,000 tons, about
Account for the 71% of lead total quantity consumed.Due to the fast development of China's automobile consumption, it is anticipated that a very long time still suffers from from now on
Lead consumption sustainable growth and lead resource problem increasingly in short supply.The major way of current lead large-scale production is pyrometallurgical smelting.
Show to be mingled in the flue gas generally generated during pyrometallurgical smelting according to the statistical data of Yu Guangdeng enterprises a small amount of leaded
Dust, these leaded dust particles typically constitute the 7-12% of lead yield after electric field or cloth bag absorption dedusting.Therefore right
Yu Yijia is produced per year for 400,000 tons of Lian Qian enterprises, is intended to handle nearly 40,000 tons of leaded flue dust every year.Similarly,
In existing lead-acid battery manufacturing enterprise, the Shimadzu ball milling process of lead powder, the brush earrings section of polar plate plaster coating process, battery pole ear
The a large amount of scrap lead containing oxidation can be all generated with the welding sequence of pole plate, therefore, one kind is found and efficiently, economical and environmentally friendlyly returns
The method for receiving the scrap lead containing oxidation of smeltery and the generation of lead-acid battery production link has become resource high-efficiency profit urgently to be resolved hurrily
Use problem.
In a large amount of leaded flue dust that the pyrometallurgical smelting process of existing lead bullion generates, the oxidation of 30-70% is typically contained
Lead contains the metallic compounds such as a small amount of silica, aluminium oxide and micro iron, copper, tin simultaneously.Existing leaded flue dust
Processing mode be divided into two kinds of pyrogenic process and wet method.Wherein, pyrogenic process is exactly used leaded flue dust as refining leady raw materials.Tool
Body, the substances such as a small amount of waterglass or milk of lime are generally added in leaded flue dust, pre-bonding is carried out to leaded flue dust
Knot, to reduce the airborne dust generated in smelting process, improves the organic efficiency of lead.Although hydrometallurgic recovery lead oxide is considered as ratio
The more clean recycling lead oxide mode of pyrogenic process, but show that the hydrometallurgic recovery reported at present aoxidizes according to available data analysis situation
Lead substantially belongs to expendable recycling, that is, is not based on atomic economy reaction in removal process and sets out, structure atom warp
Ji reaction realizes zero consumption of raw materials of extraction process with Cycling And Utilizing Patterns.Since existing most recycling lead oxide needs
A large amount of chemical raw materials realize the recycling of lead oxide, therefore the cost recovery of great number is not only brought in removal process, but also
Also secondary lead contamination is brought to environment.
Hydrometallurgic recovery typical method is the lead oxide dissolved first using fluosilicic acid in leaded flue dust, obtains fluorine silicon
Then quantitative sulfuric acid is added in lead plumbate filtrate and filter residue in lead fluorosilicate filtrate, make it that lead sulfate precipitation be precipitated, finally by sulphur
Ceruse is obtained by the reaction in lead plumbate and sodium carbonate, is sold after filtering obtain lead oxide with high-temperature roasting again.However, this method
Major defect it is as follows：
（1）During dissolving leaded flue dust using the fluosilicic acid of highly acid, contained in the leaded flue dust
The metallic compounds such as a large amount of aluminium, iron, copper and tin can be also dissolved in fluosilicic acid, so as to cause impurity in lead fluorosilicate filtrate
Content is constantly accumulated；
（2）Also with fluosilicic acid side reaction can occur for silica contained in leaded flue dust, to exacerbate fluosilicic acid
Consumption；
（3）The sulfuric acid and sodium carbonate used in reaction process cannot recycle, and often produce the lead oxide of 1mol, theoretically
It is minimum to need to consume 1mol sulfuric acid and 1mol sodium carbonate, while discharging 1mol sodium sulphate and 1mol carbon dioxide.
In order to overcome the problem, some scholars attempt to substitute fluosilicic acid using salpeter solution to dissolve flue dust, but
There are problems that a large amount of nitric acid, ammonium carbonate and carbonic acid sodium waste and nitric acid are constantly tired to equipment heavy corrosion and foreign metal
Long-pending problem.For example, the technical study for preparing lead monoxide using leaded flue dust of the reports such as seven gold medal of Zhu（Environmental project,
2000,18 (5):44-46）The technique mentioned is as follows：（1）Washing flue dust obtains lead sulfate；（2）Become using ammonium carbonate precipitation
Ceruse；（3）Nitric acid dissolving ceruse is converted into plumbi nitras；（4）Basic lead carbonate is obtained using sodium carbonate precipitation plumbi nitras；
（5）Roasting basic lead carbonate obtains lead oxide.Guo Cuixiang etc. is in " China's lead bearing waste present situation and lead recovery technology progress "
（Nonferrous metallurgy design and research, 2007,28 (2-3), 46-54）In contrast to other leaded hydrometallurgic recoveries Jie of system
It continues.
In addition, the Yang Jiakuan seminars of the Central China University of Science and Technology recently trial citric acid and hydrogen peroxide to contain scrap lead into
The main problem of row recycling, this method is that citric acid consumes the high cost brought in the roasting of removal process high temperature and pollution is asked
Topic.Dissolving and the recrystallization of the scrap lead containing oxidation are realized in Beijing University of Chemical Technology's Pan Jun blueness seminar trial with sodium hydroxide solution
Process, experimental study show that this method directly converts the obtained scrap lead containing oxidation for the lead-acid battery of single variety and has
Very superior recycling effect, but the complicated components such as waste lead acid battery lead plaster and flue dust for multi items mixing, especially
The scrap lead containing oxidation containing 10-30% sial composite oxides, aluminium oxide and silica, stannic oxide in removal process
Deng the phenomenon that there are more significant dissolving and consumption in alkali sodium hydroxide solution.The presence of these problems forces researcher urgently
A kind of technique for recycling the lead oxide in the scrap lead containing oxidation such as flue dust preferably need to be found.
Invention content
When carrying out hydrometallurgic recovery PbO to containing oxidation scrap lead using existing method the purpose of the invention is to overcome,
In the presence of needing to consume a large amount of chemical raw materials, and the cost recovery caused by recovery process length is high, low yield and purity are lower
Defect, and provide a kind of simple for process and can realize the new method for recycling high-purity PbO from high efficiency in the scrap lead containing oxidation.
The present invention provides a kind of methods recycling lead oxide from the scrap lead containing oxidation, and this approach includes the following steps：
（1）Oxidation scrap lead will be contained to contact with enveloping agent solution, and the mixture after contact will be separated by solid-liquid separation, obtained leaded
Filtrate and filter residue；
（2）Above-mentioned leaded filtrate is reacted with precipitating reagent, and obtained reaction product is separated by solid-liquid separation, obtains lead salt
Precipitation and regenerated complexing agent filtrate, and by the complexing agent filtrate return to step（1）Course of dissolution；
（3）Above-mentioned lead salt is precipitated and carries out desalination decomposition to obtain PbO.
In the present invention, ingenious combined use is decomposed into complexing dissolving, precipitation reaction and desalination, it can be efficiently selective
Recycling effectively removes impurity therein containing the PbO in scrap lead, obtains the PbO products of high-purity.Specifically, oxidation will be contained
Scrap lead is contacted with complexing agent, and the PbO in the scrap lead containing oxidation can be made to be complexed dissolving, and other non-lead impurity are then still
It deposits in solid form in the reaction product, the insoluble impurities in the scrap lead containing oxidation can be removed after separation of solid and liquid；
Then the leaded filtrate is reacted with precipitating reagent, so that the lead ion of complexing is precipitated in the form of indissoluble lead salt precipitates, by these
Lead salt sedimentation desalination can be obtained PbO after decomposing.In addition, with the existing technique for recycling lead oxide from the scrap lead containing oxidation
It compares, method provided by the invention farthest shortens technological process, and the complexing agent and precipitating reagent that removal process uses can
To be repeatedly circulated, and whole process can not have waste liquid to generate, and meet atomic economy reaction feature, to greatly disappear
In addition to the secondary pollution that is generated in recycling lead-containing material of regeneration plumbing, be a kind of energy conservation and environmental protection, clean and effective recycling oxygen
Change the new process of lead.
A preferred embodiment of the invention, when the precipitating reagent is selected from carbon dioxide, sulfur dioxide and three oxygen
It is one or more in change sulphur, and it further includes by step to recycle the method for lead oxide from the scrap lead containing oxidation（3）The lead
Salt precipitation carries out the gas circulation that desalination is decomposed and is used as step（2）When the described precipitating reagent, high yield and high-purity is being obtained
On the basis of the PbO of degree, the atomic economy reaction of lead oxide removal process is also achieved, to realize zero consumption, zero-emission, section
About production cost, more prospects for commercial application.
According to another preferred method of implementation of the present invention, when the precipitating reagent is selected from ammonium sulfate, ammonium oxalate and ammonium carbonate
In it is one or more, and from containing oxidation scrap lead in recycling lead oxide method further include by step（2）React the ammonia generated
The ammonia spirit that gas is formed is used for step（3）Desalination decomposable process, and the product that desalination is decomposed is separated by solid-liquid separation,
One or more in the ammonium sulfate, ammonium oxalate solution and the sal volatile that are obtained after desalination is decomposed again are re-used for walking
Suddenly（2）Precipitation process when, also can realize that atomic economy reaction is wanted on the basis of obtaining the PbO of high yield and high-purity
It asks, to realize zero consumption, zero-emission.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Attached drawing is to be used to provide further understanding of the present invention, an and part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is when using carbon dioxide as precipitating reagent, provided by the invention from recycling lead oxide in the scrap lead containing oxidation
The flow chart of specific implementation mode.
Fig. 2 is the electromicroscopic photograph of the lead oxide recycled from the scrap lead containing oxidation according to the method for embodiment 3.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
Method provided by the invention from recycling lead oxide in the scrap lead containing oxidation includes the following steps：
（1）Oxidation scrap lead will be contained to contact with enveloping agent solution, and the mixture after contact will be separated by solid-liquid separation, obtained leaded
Filtrate and filter residue；
（2）Above-mentioned leaded filtrate is reacted with precipitating reagent, and obtained reaction product is separated by solid-liquid separation, obtains lead salt
Precipitation and regenerated complexing agent filtrate, and by the complexing agent filtrate return to step（1）Course of dissolution；
（3）Above-mentioned lead salt is precipitated and carries out desalination decomposition to obtain PbO.
In order to more preferably state the principle of the present invention, the complexing agent is indicated with general formula P/S, then it is provided by the invention from containing
The step of method of recycling lead oxide, can be divided into oxidation scrap lead：
（1）Oxidation scrap lead will be contained to contact with enveloping agent solution, the PbO components in the scrap lead containing oxidation will be complexed
It is dissolved in the complexing agent, and product of contact is separated by solid-liquid separation, obtains leaded filtrate and filter residue, the reaction equation of dissolving is complexed
It is expressed as：
PbO+P/S+H2O=Pb(P/S)2++2OH- (1)
（2）Lead salt precipitation is obtained by the reaction in the leaded filtrate and precipitating reagent, while complexing agent realizes regeneration, with CO2Make
For precipitating reagent, reaction equation is expressed as：
CO2+2OH-=CO3 2-+H2O (2)
Pb(P/S)2++CO3 2-=PbCO3+P/S (3)
（3）The lead salt sedimentation desalination is decomposed to obtain PbO, while precipitating reagent regenerates：
PbCO3=PbO+CO2 (4)
The complexing by P/S complexing agents is can be seen that from the above reaction principle, the scrap lead containing oxidation can be made
In PbO components dissolved, while generating OH-（See reaction equation（1））, it is separated by solid-liquid separation at this time to remove insoluble filter residue, is obtained
To the leaded filtrate of alkalinity.Then by being passed through carbon dioxide into the leaded filtrate, alkaline leaded filtrate can make its turn
Turn to CO3 2-Ion.Due to PbCO3Solubility very little, Ksp constants generally only 7.4 × 10-14, lead complex ion at this time
It is easy to and CO3 2-In conjunction with the PbCO for forming more indissoluble3Precipitation, while releasing complexing agent.Precipitate obtained PbCO3Pass through heat point
The desalination decomposable process of solution form obtains PbO and CO2, therefore, while recycling PbO, it is also possible that CO2Precipitating reagent obtains
Regeneration.The present invention needs complexing agent and precipitating reagent during the reaction, but the reaction process of entire recycling PbO can not be complexed
The consumption of agent and precipitating reagent meets the requirement of atomic economy reaction.
According to the present invention, the complexing agent is that can react to generate dissoluble lead with the PbO in the scrap lead containing oxidation
Salt but the substance not reacted with the insoluble impurities in the scrap lead containing oxidation.The present inventor is by a large amount of experiment
It was found that effectively with PbO complex reaction can occur for following preferred complexing agent, and generate soluble lead salt.The preferred network
Mixture is selected from ethylenediamine diacetic acid, trimethylen-edinitrilo-tetraacetic acid, nitrilotriacetic acid, aspartic acid, alanine, valine, glutamic acid, dried meat ammonia
Acid, sarcosine, phenylalanine, leucine, histidine, asparagine, glycine, threonine, serine, glutamine, melon ammonia
Sodium salt, sylvite corresponding to acid, lysine, arginine, cysteine, methionine, ornithine, acetic acid and above-mentioned substance and ammonium
Salt and one kind or more in quaternary ammonium salt, imidazoles, ethanol amine, phenylacetic acid, methylamine, ethamine, ethylenediamine, propane diamine and triethanolamine
Kind.
In the present invention, the dosage of the complexing agent can contain according to what is contacted with the complexing agent in oxidation scrap lead
The content of PbO is selected, for example, relative to the PbO in the scrap lead containing oxidation of 1mol contacted with complexing agent, the complexing
The dosage of agent can be 0.3-5.5mol, preferably 0.4-4.5mol.It should be noted that if the scrap lead containing oxidation contains
There are other non-PbO or Pb (OH)2When the lead compound of form, before being contacted with complexing agent, it usually needs first contain by described in
Oxidation scrap lead is pre-processed, by non-PbO or Pb (OH)2The lead compound of form is converted into PbO and/or Pb (OH)2,
At this point, the above-mentioned scrap lead containing oxidation contacted with complexing agent refers to the preprocessed material obtained later.
The present invention is not particularly limited the type of the precipitating reagent, as long as carbon can be generated with the soluble lead salt
At least one of lead plumbate, sulfurous acid lead plumbate, lead sulfate and its corresponding alkali formula lead salt deposit, for example, described
Precipitating reagent can be selected from aqueous solution and alkali metal acid corresponding to carbon dioxide, sulfur dioxide, sulfur trioxide and above-mentioned substance
It is one or more in salt and ammonium sulfate, ammonium oxalate and ammonium carbonate.Wherein, the specific example of the alkali metal acid salt includes
But it is not limited to：It is one or more in sodium carbonate, potassium carbonate, sodium sulphate and potassium sulfate.
In the present invention, the dosage of the precipitating reagent can be carried out according to the content of soluble lead salt in the leaded filtrate
Selection, for example, relative to the soluble lead salt in the leaded filtrate of 1mol, the dosage of the precipitating reagent can be 0.35-
1.55mol, preferably 0.4-1.2mol.
A preferred embodiment of the invention, the precipitating reagent are selected from carbon dioxide, sulfur dioxide and three oxidations
One or more in sulphur, the method from recycling lead oxide in the scrap lead containing oxidation preferably further includes by step（3）It is described
Lead salt precipitation carry out the gas circulation decomposed of desalination and be used as step（2）The precipitating reagent, may be implemented atom in this way
Economic response requirement, to realize zero consumption and zero-emission, more prospects for commercial application.
According to another preferred method of implementation of the present invention, the precipitating reagent is in ammonium sulfate, ammonium oxalate and ammonium carbonate
It is one or more, it is described from containing oxidation scrap lead in recycling lead oxide method preferably further include by step（2）Reaction generates
Ammonia formed ammonia spirit be used for step（3）Desalination decomposable process, and the product that desalination is decomposed carries out solid-liquid
In separation, then the ammonium sulfate, ammonium oxalate solution and the sal volatile that are obtained after desalination is decomposed it is one or more again
For step（2）Precipitation process, can also realize atomic economy reaction requirement in this way, to realize zero consumption and zero-emission,
More prospects for commercial application.
When precipitating reagent selects ammonium sulfate, ammonium oxalate or ammonium carbonate, the reaction principle of precipitation process is made with carbon dioxide
For precipitating reagent difference.Below by taking ammonium sulfate as an example, illustrate the difference between both precipitating reagent principles：
（1）Oxidation scrap lead will be contained to contact with enveloping agent solution, the PbO components in the scrap lead containing oxidation will be complexed
It is dissolved in the complexing agent, and product of contact is separated by solid-liquid separation, obtains leaded filtrate and filter residue, the reaction equation of dissolving is complexed
It is expressed as：
PbO+P/S+H2O=Pb(P/S)2++2OH- (1)
（2）Lead salt precipitation is obtained by the reaction in the leaded filtrate and precipitating reagent, while complexing agent realizes regeneration, the ammonia of generation
Gas volatilizees to obtain ammonium hydroxide, using ammonium sulfate as precipitating reagent for, reaction equation is expressed as：
Pb(P/S)2++SO4 2-=PbSO4+P/S (5)
2NH4 ++2OH-=2NH3+2H2O (6)
（3）The lead salt sedimentation desalination is decomposed to obtain PbO, while precipitating reagent regenerates：
PbSO4+2NH3+2H2O=PbO+H2O+(NH4)2SO4 (7)
Ammonium sulfate is added in reaction process, the alkalinity generated in course of dissolution is complexed using PbO, makes NH3Volatilization, and make Pb
(P/S)2+And SO4 2-Precipitation reaction occurs and obtains PbSO4, while complexing agent P/S is regenerated.The ammonium hydroxide that volatilization generates can be taken advantage of
Hot and isolated PbSO4Desalination reaction is carried out, PbO solids and ammonium sulfate are obtained, the ammonium sulfate regenerated can be with
It is re-used for step as precipitating reagent（2）Precipitation process.In addition, in this process, carrying out desalination using ammonium hydroxide and decomposing to obtain
PbO carries a small amount of Pb (OH) secretly sometimes2, these carry a small amount of Pb (OH) secretly2The desalination decomposition product containing PbO can be in 60-300
Lead hydroxide is set thoroughly to be decomposed into PbO and H after dry 10-60min at DEG C2O, to obtain pure PbO.
The present invention is to step（1）The middle condition for contacting the scrap lead containing oxidation with complexing agent is not particularly limited,
But in order to be more advantageous to the dissolving of the complexing to the PbO, there is the leaded network of higher concentration in the leaded filtrate to make
Close ion concentration, it is preferable that include by the condition that the scrap lead containing oxidation is contacted with enveloping agent solution：Temperature is 5-102 DEG C,
Further preferably 25-95 DEG C, more preferably 45-80 DEG C；Time is 1-150min, further preferably 3-120min, more excellent
It is selected as 20-60min.
The present invention is to step（2）The middle condition for reacting the leaded filtrate with precipitating reagent is not particularly limited, as long as
The soluble lead salt can be made at least one in ceruse, sulfurous acid lead plumbate, lead sulfate and its corresponding alkali formula lead salt
The form of kind deposit is precipitated, for example, including by the condition that the leaded filtrate is reacted with precipitating reagent：Temperature can be with
For -2 DEG C to 80 DEG C, preferably 5-80 DEG C, more preferably 50-80 DEG C；Time can be 1-300min, preferably 2-80min, more
Preferably 10-60min.
In order to ensure that desalination decomposes to obtain the purity of PbO, when the precipitating reagent is selected from carbon dioxide, sulfur dioxide and three oxygen
Change sulphur in it is one or more when, by the lead salt precipitate carry out desalination decomposition mode be by the lead salt precipitate carry out heat point
Solution, the thermal decomposition include two stages carried out successively；The condition of first stage includes：Temperature is 60-290 DEG C, and the time is
1-30min；The condition of second stage includes：Temperature is 300-1350 DEG C, time 2-90min.When the precipitating reagent is selected from sulphur
When one or more in sour ammonium, ammonium oxalate and ammonium carbonate, the lead salt is precipitated and carries out the condition of desalination decomposition and includes：Temperature
It is 45-100 DEG C, time 1-150min, a concentration of 0.1-5.5mol/L of ammonia spirit.
In order to ensure that best solute effect, the concentration of the enveloping agent solution are preferably controlled in 0.1-4.5mol/L.This
Outside, the solvent in the enveloping agent solution can well known in the art various can be used as reaction media and can dissolve described
The liquid of complexing agent but PbO and insoluble impurities in the insoluble scrap lead containing oxidation, for example, its specific example
Including but not limited to：It is one or more in methanol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol and water, particularly preferably water.In practical behaviour
Refer to the temperature of enveloping agent solution by the temperature that the scrap lead containing oxidation is contacted with complexing agent during work.
In the present invention, the separation of solid and liquid can be according to well known to a person skilled in the art various for detaching solid
It is carried out with the mode of liquid, such as can be press filtration or centrifugation, preferably press filtration.
A kind of specific implementation mode according to the present invention, as shown in Figure 1, described recycle lead oxide from the scrap lead containing oxidation
Method include that the scrap lead containing oxidation is added in enveloping agent solution, PbO and complexing agent in the scrap lead containing oxidation
It reacts and is leached in the form of soluble lead salt, and by reaction product press filtration, obtain leaded filtrate and filter residue；Then contain toward above-mentioned
It being passed through carbon dioxide in lead filtrate so that the soluble lead salt in the filtrate generates ceruse and/or basic lead carbonate precipitation,
And by reaction product press filtration, ceruse and/or basic lead carbonate and complexing agent filtrate are obtained, the complexing agent filtrate cycle is used
It is reacted in the PbO in the scrap lead containing oxidation, and the ceruse and/or basic lead carbonate are then thermal decomposited, and obtain PbO
And carbon dioxide, carbon dioxide recycle with above-mentioned leaded filtrate for reacting.
Method provided by the invention from the existing various scrap leads containing oxidation suitable for recycling lead oxide, as long as wherein containing
There is PbO and needs the insoluble impurities removed.For example, the scrap lead containing oxidation can be leaded flue dust, scrap lead acid
The lead plaster of battery, the PbO waste materials that useless pole plate recycles, other scrap leads containing oxidation of lead-acid battery production process and other
It is one or more in the scrap lead containing oxidation in the production of field.Studies have shown that the content of PbO is deposited in the various scrap leads containing oxidation
In very big difference, for example, it is 2- that the flue dust generated in the smelting process of some copper, iron ore, which generally contains only weight percent,
7% PbO typically contains the PbO that weight percent is 45-70%, some plumbic acids in some zinc, the flue dust of lead ore and scrap lead cream
The weight percent content of PbO is even as high as 75-99% in the scrap lead containing oxidation that battery mechanical milling process generates.In addition, research table
It is bright, reach 3-99% containing the weight percent content for aoxidizing PbO in scrap lead when single or several mixing, it is described insoluble
When the weight percent content of property impurity reaches 1-97%, the PbO can more effectively dissolve in the enveloping agent solution,
And precipitated recycling using precipitating reagent.
In the implementation process of the present invention, the insoluble impurities in the scrap lead containing oxidation can contain Pb, PbCO3、
Pb3O4、PbO2、PbSO4、Pb3(PO4)2, basic lead sulphate, basic lead carbonate, CuO, Al2O3、SnO2And Fe2O3In one kind or
It is a variety of.Wherein, when the insoluble impurities contains Pb, PbCO3、Pb3O4、PbO2、PbSO4、Pb3(PO4)2, basic lead sulphate and alkali
One or more non-PbO groups timesharing in formula ceruse, the method from recycling lead oxide in the scrap lead containing oxidation is preferably also
Be included in will before the scrap lead containing oxidation contact with complexing agent, first by it is described contain aoxidize scrap lead and pre-process so that
The non-PbO components are converted into Pb (OH)2And/or PbO, to significantly improve the total recovery for improving PbO.
The method that this field routine may be used that pre-processes carries out, for example, it can be selected from pro desalting processing plus Pb
Carry out at least one of the pre-heat treatment in redox processing and air.
Specifically, the pro desalting processing is typically referred to the scrap lead containing oxidation and alkaline matter（As potassium hydroxide,
Sodium hydroxide, ammonium hydroxide etc.）Haptoreaction, the alkaline matter described in this way can be with the PbSO in the scrap lead containing oxidation3、
PbSO4、Pb3(PO4)2, the non-PbO component reactions such as basic lead sulphate and basic lead carbonate and generate can be in enveloping agent solution
The Pb (OH) of dissolving2And/or PbO, filtering can be obtained the lead-containing material after pro desalting, the Pb for then again forming pro desalting
(OH)2And/or PbO contacts with complexing agent and carries out the recycling of the lead oxide together with the lead-containing material.For using pre-
When desalination is handled, in order to ensure that the reaction was complete, reaction temperature should usually be controlled at 10-105 DEG C, and by the reaction time
Control is in 1-30min.
Described plus Pb carries out redox processing and typically refers to the leaded oxidation of high-valence state in the scrap lead containing oxidation
Object（Such as Pb3O4、PbO2Deng）Redox reaction is carried out with Pb（Pb+Pb3O4=4PbO, Pb+PbO2=2PbO）, to make described contain
Aoxidize Pb, Pb in scrap lead3O4、PbO2It is converted into PbO.The pre-heat treatment in the air refers in a heated condition, by institute
The easy decomposition stated in the scrap lead containing oxidation contains lead oxides（Such as PbCO3、PbSO4, basic lead sulphate and basic lead carbonate etc.）It decomposes
For PbO.Contain Pb, PbO, PbCO for certain3、Pb3O4、Pb(OH)2And PbO2Containing oxidation scrap lead, this can be contained
Oxidation scrap lead directly carries out the pre-heat treatment in air, at this time Pb, Pb in waste material3O4And PbO2It can be in air atmosphere
Redox reaction occurs and obtains PbO, while the PbCO in waste material3、Pb3O4、Pb(OH)2And PbO2It is sent out in preheating treatment procedure
Raw decomposition reaction, generates PbO, to obtain the lead-containing material based on PbO.In the process, excellent in order to ensure that the reaction was complete
The scrap lead containing oxidation is carried out the pre-heat treatment, the condition packet of the pre-heat treatment of first stage by choosing in two stages in air
It includes：Temperature is 60-290 DEG C, time 1-30min；The condition of the pre-heat treatment of second stage includes：Temperature is 300-1350
DEG C, time 2-90min.
A kind of specific implementation mode according to the present invention, the scrap lead containing oxidation is derived from contains lead fume with smeltery
Road ash, mainly contains 60-70 weight % lead oxide, remaining is a small amount of SnO2、CaSiO3、Al2O3And SiO2It is miscellaneous etc. insoluble
Matter, this, which contains oxidation lead materials, can then direct plunge into step（1）In carry out complexing dissolving.
According to another specific implementation mode in the present invention, the containing from the smelteries Jin Qian of the scrap lead containing oxidation
Lead flue dust mainly contains the PbSO of 60-65 weight %PbO and 5-10 weight %4, remaining is a small amount of Al2O3And SiO2Deng not
The lead materials containing oxidation then first can be carried out pro desalting by solubility impurity using alkaline matter, and after pro desalting is obtained by filtration
Then the lead-containing material is put into step by lead-containing material again（1）Carry out complexing dissolving.
Another kind specific implementation mode according to the present invention, the scrap lead containing oxidation reach containing for company from Henan sky
Scrap lead mainly contains the PbSO of 60-65 weight %PbO, 5-10 weight %4, 3-5 weight %PbCO3And 2-4 weight %
Pb3O4, remaining is a small amount of Al2O3And SiO2The lead materials containing oxidation then first can be used alkaline matter by equal insoluble impurities
Pro desalting is carried out, and the lead-containing material after pro desalting is obtained by filtration, in the lead-containing material then obtained according to lead plaster chemical analysis
Pb3O4Actual content, according to Pb3O4Carry out redox reaction（Pb+Pb3O4=4PbO）The theoretical amount of the metal Pb needed
Supplement corresponding Pb powder（Pb3O4Molar ratio with Pb powder is 1.02-3.0:1）, promote Pb therein3O4It is substantially transitioned to PbO.
Another kind specific implementation mode according to the present invention, the scrap lead containing oxidation are waste and old from blue sky 12V, 12Ah
The lead plaster of battery of electric vehicle also contains Pb, PbSO other than containing PbO4、PbO2And basic lead sulphate, then can first by
This contains oxidation lead materials and carries out pro desalting using alkaline matter, and desalination lead plaster is obtained by filtration, then according to lead plaster chemical analysis
Pb and PbO in obtained desalination lead plaster2Actual content, according to PbO2Carry out redox reaction（Pb+PbO2=2PbO）It needs
The theoretical amount of metal Pb supplement corresponding Pb powder（PbO2Molar ratio with Pb powder is 1.02-3.0:1）, promote therein
PbO2It is substantially transitioned to PbO.Or the high temperature of the pre-heat treatment using second stage（Temperature is 300-1350 DEG C）Make excess PbO2
Directly it is decomposed into PbO（2PbO2=2PbO+O2）.
Another kind specific implementation mode according to the present invention, the source of the scrap lead containing oxidation Mr. Yu's lead-acid battery factory chemical examination
Lead-containing material in workshop mainly contains 70-72 weight %PbO, 10-15 weight % basic lead sulphates, 3-5 weight % ceruses,
Surplus is moisture content and clay, then can the lead-containing material first be carried out pro desalting using alkaline matter, and desalination lead is obtained by filtration
Then cream heats the desalination lead plaster in two stages in air atmosphere, control two phase heat treatment temperature point
Wei not be 60-290 DEG C and 300-650 DEG C, the time of heat treatment is respectively 1-30min and 2-90min, makes PbCO3After heat treatment
It is decomposed into PbO, finally obtains the lead-containing material based on lead oxide, and put into step（1）Carry out complexing dissolving.
The present invention will be described in detail by way of examples below.
Embodiment 1
The embodiment is used to illustrate the method provided by the invention that lead oxide is recycled from the scrap lead containing oxidation.
The scrap lead containing oxidation used in the embodiment（930g）For from the leaded flue dust with smeltery, through point
Analysis mainly contains the PbO that weight percentage is 69%, remaining is a small amount of SnO2、CaSiO3、Al2O3And SiO2Etc. insoluble
Impurity, the amount for converting into PbO are 2.9mol.
It is as follows to recycle lead oxide technique：
（1）The ethylenediamine diacetic acid that 10 liters of temperature are 45 DEG C and a concentration of 0.5mol/L is added in the above-mentioned scrap lead containing oxidation
Aqueous solution is stirred to react 20min, and reaction product is then carried out press filtration, obtains leaded filtrate and filter residue.
（2）Above-mentioned leaded filtrate is heated to 70 DEG C and is passed through 3.0mol sulfur dioxide, then keeps 65 DEG C of reaction temperature
Degree reaction 12min, then carries out press filtration by obtained reaction product, obtains lead salt precipitation and complexing agent filtrate.By above-mentioned complexing
Agent filtrate is back to step（1）In for be complexed dissolving the present embodiment in containing aoxidize scrap lead.
（3）By step（2）Obtained lead salt precipitation is first heat-treated 30min at 60 DEG C, is then heat-treated at 720 DEG C again
90min obtains the PbO of 640g, decomposes the sulfur dioxide gas of generation and can be back to step（2）In be used as precipitating reagent.Through ICP
Method measures, and the purity of PbO is 99.9991%, yield 99.6%.
Embodiment 2
The embodiment is used to illustrate the method provided by the invention that lead oxide is recycled from the scrap lead containing oxidation.
The scrap lead containing oxidation used in the embodiment is the leaded flue dust from the smelteries Jin Qian, through analysis, master
The PbSO for the PbO and 8% to be 63% containing weight percentage4, remaining is a small amount of Al2O3And SiO2Equal insoluble impurities.
Pretreating process（Pro desalting processing）, specific as follows：
Since the bulk composition of the scrap lead containing oxidation is PbO and PbSO4, it is only necessary to oxidation scrap lead will be contained and carry out pre- take off
Salt treatment.Take 1.6 kilograms of above-mentioned scrap leads containing oxidation（Equivalent PbO is 4.942mol）Put into the NaOH of 0.5 liter of concentration 2mol/L
Middle carry out desalination reaction, controlling reaction temperature are 60 DEG C, are filtered after being stirred to react 10min, obtain pretreated lead-containing material.
It is as follows to recycle lead oxide technique：
（1）Smart ammonia of 10 liters of temperature for 65 DEG C and containing a concentration of 1.25mol/L is added in pretreated lead-containing material
In the mixed aqueous solution of sour and a concentration of 0.5mol/L histidines, it is stirred to react 30min, reaction product is then subjected to press filtration,
Obtain leaded filtrate and filter residue.
（2）Above-mentioned leaded filtrate is heated to 55 DEG C and is passed through carbon dioxide（Relative in the above-mentioned leaded filtrate of 1mol
Dissoluble lead ion, the dosage of carbon dioxide is 0.5mol）, then keep 55 DEG C of reaction temperature to react 30min, then will
Obtained reaction product carries out press filtration, obtains lead salt precipitation and complexing agent filtrate.Above-mentioned complexing agent filtrate is back to step（1）
In for be complexed dissolving the present embodiment in pass through pretreated lead-containing material.
（3）By step（2）Obtained lead salt precipitation is first heat-treated 1min at 290 DEG C, is then heat-treated at 550 DEG C again
10min obtains the PbO of 1100g, decomposes the carbon dioxide gas of generation and can be back to step（2）In be used as precipitating reagent.Through
ICP method measures, and the purity of PbO is 99.997%, yield 99.82%.
Embodiment 3
The embodiment is used to illustrate the method provided by the invention that lead oxide is recycled from the scrap lead containing oxidation.
It weighs weight and aoxidizes scrap lead up to containing for company from Henan sky for 2 kilograms, through analyzing, main component
Weight percentage is as follows：63.5%PbO, 9% PbSO4、4%PbCO3And 3.8% Pb3O4, remaining is a small amount of Al2O3With
SiO2Equal insoluble impurities.All kinds of containing lead oxides in above-mentioned 2 kilograms of the scrap lead containing oxidation, equivalent PbO is calculated as
6.65mol。
Pretreating process（The pre-heat treatment+pro desalting in air）, specific as follows：
The above-mentioned scrap lead containing oxidation is directly heated into 15min at 630 DEG C, makes Pb therein3O4And PbCO3It is decomposed into
Then the lead materials containing oxidation after heat treatment are carried out desalination reaction by PbO in the NaOH solution of 1 liter of a concentration of 1.7mol/L,
Controlling reaction temperature is 35 DEG C, is filtered after being kept stirring reaction 6min, obtains pretreated lead-containing material.
It is as follows to recycle lead oxide technique：
（1）Ethylenediamine of 10 liters of temperature for 65 DEG C and containing a concentration of 1.5mol/L is added in pretreated lead-containing material
In the mixed aqueous solution of the sodium acetate of a concentration of 0.5mol/L, it is stirred to react 30min, reaction product is then subjected to press filtration,
Obtain leaded filtrate and filter residue.
（2）Above-mentioned leaded filtrate is heated to 55 DEG C and is passed through carbon dioxide（Relative in the above-mentioned leaded filtrates of 1mol
The dosage of dissoluble lead ion, carbon dioxide is 0.5mol）, after then keeping 55 DEG C of reaction temperature reaction 30min, then will
Obtained reaction product carries out press filtration, obtains lead salt precipitation and complexing agent filtrate.Above-mentioned complexing agent filtrate is back to step（1）
In for be complexed dissolving the present embodiment in pass through pretreated lead-containing material.
（3）By step（2）Obtained lead salt precipitation is first heat-treated 1min at 290 DEG C, is then heat-treated at 550 DEG C again
10min obtains the PbO of 1475g, decomposes the carbon dioxide gas of generation and can be back to step（2）In be used as precipitating reagent.Through
ICP method measures, and the purity of PbO is 99.997%, yield 99.45%.Wherein, the PbO of gained electromicroscopic photograph as shown in Fig. 2,
Needle column feature is presented in the pattern that can be seen that the PbO recycled using the present embodiment from the result of Fig. 2, and width is that 2-4 is micro-
Rice, length are 10-25 microns.
Embodiment 4
The embodiment is used to illustrate the method provided by the invention that lead oxide is recycled from the scrap lead containing oxidation.
The lead plaster from the waste and old battery of electric vehicle of blue sky 12V, 12Ah that weight is 10 kilograms is weighed, through analysis, master
Want the weight percentage of ingredient as follows：20%PbO、11%Pb、35%PbSO4、30%PbO2, remaining is BaSO4、SiO2And water）.
All kinds of containing lead oxides in above-mentioned 10 kilograms of the scrap lead containing oxidation, equivalent PbO is calculated as 38.39mol.
Pretreating process（The pre-heat treatment+pro desalting in air）, specific as follows：
The above-mentioned scrap lead containing oxidation is directly heated into 15min at 630 DEG C, makes a part of PbO2Redox reaction occurs
（Pb+PbO2=2PbO）, while making another part PbO2It is decomposed into PbO.Then by the lead materials containing oxidation after heat treatment at 10 liters
Desalination reaction is carried out in the NaOH solution of a concentration of 2.5mol/L, controlling reaction temperature is 40 DEG C, after being kept stirring reaction 6min
Filtering, obtains pretreated lead-containing material.
It is as follows to recycle lead oxide technique：
（1）It is water-soluble that the ethylenediamine that 25 liters of temperature are 60 DEG C and a concentration of 1.6mol/L is added in pretreated lead-containing material
In liquid, it is stirred to react 30min, reaction product is then subjected to press filtration, obtains leaded filtrate and filter residue.
（2）Above-mentioned leaded filtrate is heated to 55 DEG C and is passed through slightly excessive sulfur dioxide（It is above-mentioned leaded relative to 1mol
The dosage of dissoluble lead ion in filtrate, sulfur dioxide is 1.01mol）, 55 DEG C of reaction temperature is then kept to react 40min
Afterwards, obtained reaction product is centrifuged, obtains lead salt precipitation and complexing agent filtrate.Above-mentioned complexing agent filtrate is returned
To step（1）In for be complexed dissolving the present embodiment in pass through pretreated lead-containing material.
（3）By step（2）Obtained lead salt precipitation is first heat-treated 3min at 110 DEG C, is then heat-treated at 750 DEG C again
15min obtains the PbO of 8550g, decomposes the sulfur dioxide gas of generation and can be back to step（2）In be used as precipitating reagent.Through
ICP method measures, and the purity of PbO is 99.998%, yield 99.87%.
Embodiment 5
The embodiment is used to illustrate the method provided by the invention that lead oxide is recycled from the scrap lead containing oxidation.
The scrap lead containing oxidation between the Hubei gold rickshaw that weight is 1 kilogram is weighed, through analysis, predominant quantity hundred
Divide as follows than content：45.3%PbO、29.5%PbSO4、0.5%Sb2O3、3.9%SnO2、11.2%Fe2O3、8.2%SiO2, surplus is
Moisture.All kinds of lead-containing compounds in above-mentioned 1 kilogram of the scrap lead containing oxidation, equivalent PbO are calculated as 2.995mol.
Pretreating process（Pro desalting processing）, specific as follows：
Since the bulk composition of the scrap lead containing oxidation is PbO and PbSO4, it is only necessary to oxidation scrap lead will be contained and carry out pre- take off
Salt treatment.The above-mentioned scrap lead containing oxidation is put into the NaOH solution of 1.2 liters of a concentration of 2.0mol/L and carry out desalination reaction, controlled
Reaction temperature processed is 35 DEG C, is filtered after being kept stirring reaction 10min, obtains pretreated lead-containing material.
It is as follows to recycle lead oxide technique：
（1）Imidazoles of 3.5 liters of temperature for 75 DEG C and containing a concentration of 1.0mol/L is added in pretreated lead-containing material
In the arginic mixed aqueous solution of a concentration of 0.5mol/L, it is stirred to react 60min, reaction product is then subjected to press filtration,
Obtain leaded filtrate and filter residue.
（2）Above-mentioned leaded filtrate is heated to 65 DEG C and is passed through slightly excessive carbon dioxide（It is above-mentioned leaded relative to 1mol
The dosage of dissoluble lead ion in filtrate, carbon dioxide is 1.02mol）, then keep 65 DEG C of reaction temperature reaction
Then obtained reaction product is centrifuged by 60min, obtains lead salt precipitation and complexing agent filtrate.By above-mentioned complexing agent
Filtrate is back to step（1）In for be complexed dissolving the present embodiment in pass through pretreated lead-containing material.
（3）By step（2）Obtained lead salt precipitation is first heat-treated 10min at 80 DEG C, is then heat-treated at 550 DEG C again
30min obtains the PbO of 665g, decomposes the carbon dioxide gas of generation and can be back to step（2）In be used as precipitating reagent.Through ICP
Method measures, and the purity of PbO is 99.9991%, yield 99.58%.
Embodiment 6
The embodiment is used to illustrate the method provided by the invention that lead oxide is recycled from the scrap lead containing oxidation.
The scrap lead containing oxidation and pretreated method used in the embodiment is same as Example 5, obtains pretreated
Lead-containing material.
It is as follows to recycle lead oxide technique：
（1）Imidazoles of 3.5 liters of temperature for 75 DEG C and containing a concentration of 1.0mol/L is added in pretreated lead-containing material
In the arginic mixed aqueous solution of a concentration of 0.5mol/L, it is stirred to react 60min, reaction product is then subjected to press filtration,
Obtain leaded filtrate and filter residue.
（2）Above-mentioned leaded filtrate is heated to 95 DEG C and the ammonium sulfate of 1.5 liters of a concentration of 2mol/L is added as precipitating reagent,
80 DEG C of reaction temperature is kept to react 60min, volatilization generates ammonia in solution at this time, and it is heavy gradually to generate lead sulfate in solution
It forms sediment.Obtained reaction product is filtered by vacuum, lead salt precipitation and complexing agent filtrate are obtained.The complexing agent filtrate is returned
To step（1）In for be complexed dissolving the present embodiment in pass through pretreated lead-containing material.
（3）It will be from by step（2）The ammonia spirit for a concentration of 2mol/L that the ammonia of generation obtains all is put into while hot
Step（2）In obtained lead salt precipitation, then temperature control is carried out to the desalination reaction of lead sulfate and ammonium hydroxide at 50 DEG C,
Ammonium sulfate and lead oxide solid are obtained after 10min.Then obtained reaction product is subjected to press filtration, obtains solid product and filter
Liquid, then obtained filtrate is returned again into step（2）In be used as precipitating reagent.
Obtained solid product is first heat-treated 10min at 80 DEG C, then 30min is heat-treated at 350 DEG C again, obtains
The PbO of 664g.It is measured through ICP method, the purity of PbO is 99.999%, yield 99.4%.
Embodiment 7
The embodiment is used to illustrate the method provided by the invention that lead oxide is recycled from the scrap lead containing oxidation.
The scrap lead containing oxidation that the embodiment uses should through analysis for the workshop PbO samples sent from Chao Wei companies
PbO sample predominant quantity percentage compositions are as follows：98.3%PbO、0.5%Pb、0.5%Fe2O3% and 0.3%SiO2.Weigh 1 public affairs
The jin oxidation scrap lead, it is 4.43mol to convert into PbO.
Pretreating process（The pre-heat treatment in air）, specific as follows：
The above-mentioned scrap lead containing oxidation is subjected to the pre-heat treatment in two stages in air, the pre-heat treatment of first stage
Condition includes：Temperature is 100 DEG C, time 2min；The condition of the pre-heat treatment of second stage includes：Temperature is 450 DEG C, the time
For 60min, Pb therein is promoted to be oxidized to PbO, obtains pretreated lead-containing material.
It is as follows to recycle lead oxide process：
（1）Acetic acid of 10 liters of temperature for 75 DEG C and containing a concentration of 1.1mol/L is added in pretreated lead-containing material
In the mixed aqueous solution of the sodium diacetate of sodium, the arginine of a concentration of 0.5mol/L and a concentration of 0.5mol/L, stir
Reaction 60min is mixed, reaction product is then subjected to press filtration, obtains leaded filtrate and filter residue.
（2）Above-mentioned leaded filtrate is heated to 75 DEG C and is passed through suitable carbon dioxide（It is above-mentioned leaded relative to every 1mol
The dosage of dissoluble lead ion in filtrate, carbon dioxide is 1mol）, then keep 75 DEG C of reaction temperature to react 30min, connect
It the reaction product that will be obtained to be centrifuged, obtains lead salt precipitation and complexing agent filtrate.Above-mentioned complexing agent filtrate is returned
To step（1）In for be complexed dissolving the present embodiment in pass through pretreated lead-containing material.
（3）By step（2）Obtained lead salt precipitation is first heat-treated 10min at 100 DEG C, then again at 620 DEG C at heat
10min is managed, obtains the PbO of 986g, step can be back to by decomposing the carbon dioxide gas of generation（2）In be used as precipitating reagent.Through
ICP method measures, and the purity of PbO is 99.9991%, yield 99.78%.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (9)
1. a kind of method recycling lead oxide from the scrap lead containing oxidation, this approach includes the following steps：
(1) oxidation scrap lead will be contained to contact with enveloping agent solution, and the mixture after contact will be separated by solid-liquid separation, obtain leaded filtrate
And filter residue；
(2) above-mentioned leaded filtrate is reacted with precipitating reagent, and obtained reaction product is separated by solid-liquid separation, obtain lead salt precipitation
With regenerated complexing agent filtrate, and by the course of dissolution of the complexing agent filtrate return to step (1)；
(3) above-mentioned lead salt is precipitated and carries out desalination decomposition to obtain PbO；
The complexing agent is one or more in histidine, lysine and arginine；
Insoluble impurities in the scrap lead containing oxidation contains Pb, Pb3O4、PbO2、PbCO3、PbSO3、PbSO4、Pb3(PO4)2
And one or more non-PbO components in their alkali formula lead salt；This method further include will the scrap lead containing oxidation with
Before enveloping agent solution contact, first the scrap lead containing oxidation is pre-processed so that the non-PbO components are converted into Pb
(OH)2And/or PbO.
2. according to the method described in claim 1, wherein, the precipitating reagent be selected from carbon dioxide, sulfur dioxide, sulfur trioxide with
It is one or more in aqueous solution and alkali metal acid salt and ammonium sulfate, ammonium oxalate and ammonium carbonate corresponding to above-mentioned substance.
3. according to the method described in claim 2, wherein, the precipitating reagent is selected from carbon dioxide, sulfur dioxide and sulfur trioxide
In it is one or more；This method further includes that the lead salt precipitation described in step (3) is carried out the gas circulation that desalination is decomposed
As the precipitating reagent described in step (2).
4. according to the method described in claim 2, wherein, the precipitating reagent in ammonium sulfate, ammonium oxalate and ammonium carbonate one
Kind is a variety of；This method further includes that the ammonia spirit that the ammonia that step (2) reaction generates is formed is used for the desalination point of step (3)
Solution preocess, and the product that desalination is decomposed is separated by solid-liquid separation, then the ammonium sulfate, the oxalic acid that are obtained after desalination is decomposed
One or more precipitation processes for being re-used for step (2) in ammonium salt solution and sal volatile.
5. according to the method described in claim 1, wherein, the pretreated method is selected from pro desalting processing plus Pb oxidations also
It manages and at least one of the pre-heat treatment in air original place.
6. according to the method described in claim 1, wherein, in step (1), the scrap lead containing oxidation is connect with enveloping agent solution
Tactile condition includes：Temperature is 5-102 DEG C, time 1-150min；It is in step (2), the leaded filtrate and precipitating reagent is anti-
The condition answered includes：Temperature is -2 DEG C to 80 DEG C, time 1-300min.
7. according to the method described in claim 1, wherein, a concentration of 0.1-4.5mol/L of the enveloping agent solution.
8. according to the method described in claim 3, wherein, when the precipitating reagent is selected from carbon dioxide, sulfur dioxide and three oxidations
When one or more in sulphur, it is to precipitate the lead salt to carry out heat point that the lead salt, which is precipitated, and carries out the mode of desalination decomposition
Solution, the thermal decomposition include two stages carried out successively；The condition of first stage includes：Temperature is 60-290 DEG C, and the time is
1-30min；The condition of second stage includes：Temperature is 300-1350 DEG C, time 2-90min.
9. according to the method described in claim 4, wherein, when the precipitating reagent is in ammonium sulfate, ammonium oxalate and ammonium carbonate
When one or more, the condition that the lead salt is precipitated to progress desalination decomposition includes：Temperature is 45-100 DEG C, time 1-
150min, a concentration of 0.1-5.5mol/L of the ammonia spirit.
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| CN201410019975.9A CN104789776B (en) | 2014-01-16 | 2014-01-16 | A method of from recycling lead oxide in the scrap lead containing oxidation |
| CN201711286817.XA CN108018423A (en) | 2014-01-16 | 2014-01-16 | A kind of method that lead oxide is recycled from the scrap lead containing oxidation |
| CN201810654799.4A CN108842063A (en) | 2014-01-16 | 2014-01-16 | A method of from recycling lead oxide in the scrap lead containing oxidation |
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| CN201711286817.XA Division CN108018423A (en) | 2014-01-16 | 2014-01-16 | A kind of method that lead oxide is recycled from the scrap lead containing oxidation |
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| CN107641714B (en) * | 2016-07-20 | 2020-07-17 | 北京中金瑞丰环保科技有限公司 | Wet recovery processing method for lead-containing raw material |
| CN107164636B (en) * | 2017-05-27 | 2019-03-26 | 湘潭大学 | A kind of method that high-purity lead oxide is recycled in waste lead acid battery processing |
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| CN112442602A (en) * | 2020-10-09 | 2021-03-05 | 超威电源集团有限公司 | Waste lead plaster recovery method |
| CN112426796A (en) * | 2020-11-16 | 2021-03-02 | 张克军 | System for purifying and recycling complexing liquid for recycling lead oxide |
| CN113136492B (en) * | 2021-03-30 | 2023-03-10 | 广西大学 | Method for recovering lead from waste lead paste |
| CN114606393A (en) * | 2022-01-26 | 2022-06-10 | 超威电源集团有限公司 | Waste lead paste recovery method |
| CN117737791A (en) * | 2024-02-21 | 2024-03-22 | 东北大学 | Method for preparing elemental lead from lead sulfate-containing waste |
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- 2014-01-16 CN CN201810654799.4A patent/CN108842063A/en active Pending
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- 2014-01-16 CN CN201410019975.9A patent/CN104789776B/en active Active
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| GB867819A (en) * | 1959-05-08 | 1961-05-10 | Sherritt Gordon Mines Ltd | Process for the production of lead |
| CN102206750A (en) * | 2011-05-04 | 2011-10-05 | 中南大学 | Method for recovering lead from lead-containing material by matching leaching-electrowinning method |
| CN103509949A (en) * | 2012-06-15 | 2014-01-15 | 杨春晓 | Methods and equipment for recovering waste diachylon by wet method and manufacturing electrode active material of high performance lead acid battery by wet method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108842063A (en) | 2018-11-20 |
| CN108018423A (en) | 2018-05-11 |
| CN104789776A (en) | 2015-07-22 |
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