CN110857454B - Method for recovering lead from lead-containing waste - Google Patents

Method for recovering lead from lead-containing waste Download PDF

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CN110857454B
CN110857454B CN201810965441.3A CN201810965441A CN110857454B CN 110857454 B CN110857454 B CN 110857454B CN 201810965441 A CN201810965441 A CN 201810965441A CN 110857454 B CN110857454 B CN 110857454B
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lead
complexing agent
acid
reaction
precipitate
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CN110857454A (en
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潘军青
张轩
孙艳芝
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B13/00—Obtaining lead
    • C22B13/04—Obtaining lead by wet processes
    • C22B13/045—Recovery from waste materials
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/18—Electrolytic production, recovery or refining of metals by electrolysis of solutions of lead
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention discloses a method for recovering lead from lead-containing waste, which comprises the following steps: 1) reacting the lead-containing waste with a complexing agent aqueous solution to completely dissolve lead oxide and/or lead sulfate in the lead-containing waste, and separating a supernatant containing lead ions and a lead salt-free precipitate after the reaction is finished; 2) reacting the supernatant with a precipitator to ensure that lead ions in the supernatant are completely precipitated, and separating a lead-containing salt precipitate and a regenerated complexing agent aqueous solution after the reaction is finished; 3) carrying out a dissolution reaction on the lead-containing salt precipitate and an aqueous solution of the electrolyte A to completely dissolve the lead-containing salt precipitate, and producing a lead-containing electrolyte B and a precipitator after the reaction is finished; recovering the precipitant; and carrying out electrolytic reaction on the lead-containing electrolyte B to obtain metallic lead, oxygen and regenerated electrolyte A. The complexing agent, the precipitator and the electrolyte A used in the recovery process of the method can be recycled, and the method accords with the characteristics of atomic economic reaction, thereby realizing zero consumption and zero emission and saving the production cost.

Description

Method for recovering lead from lead-containing waste
Technical Field
The invention relates to a method for recycling wastes. And more particularly to a method for recovering lead from lead-containing waste.
Background
Since 1859 lead-acid batteries invented by planter, a french engineer, lead-acid batteries have long been the dominant market for secondary batteries, particularly in the automobile starting and electric bicycle markets, due to their low cost, broad temperature range of use and outstanding stability. According to battery statistics, the total consumption of refined lead in China in 2012 exceeds 464.6 ten thousand tons, wherein the consumption of the lead-acid battery is 330 ten thousand tons, which accounts for about 71 percent of the total consumption of lead. Due to the rapid development of automobile consumption in China, the problems that the lead consumption is continuously increased and the lead resource is increasingly short are expected to be still faced for a long time in the future. At present, the main mode of mass production of lead is pyrometallurgy. According to the statistical data of enterprises such as Yuguang enterprises, a small amount of lead-containing dust is generally mixed in the flue gas generated in the pyrometallurgical process, and the lead-containing dust particles usually account for 7-12% of the lead yield after being subjected to electric field or cloth bag adsorption dust removal. Thus, for a lead-smelting enterprise producing 40 million tons per year, each year means that nearly 4 million tons of lead-containing flue dust need to be treated. Similarly, in the existing lead-acid battery production enterprises, a great amount of waste materials containing lead oxide are generated in the process of performing island body ball milling on lead powder, the process of coating paste on polar plates, the process of brushing polar lugs of the battery and the process of welding the polar plates, so that the search for a method for efficiently, economically and environmentally recycling the waste materials containing lead oxide generated in smelting plants and the production links of lead-acid batteries becomes urgent to solve the problem of high-efficiency utilization of resources.
In the prior art, a large amount of lead-containing flue ash generated in the pyrometallurgical process of refined lead generally contains 30-70% of lead oxide, and simultaneously contains a small amount of silicon dioxide, aluminum oxide and trace metal compounds such as iron, copper, tin and the like. The existing treatment modes of the lead-containing flue dust are divided into a fire method and a wet method. Among them, the pyrogenic process uses lead-containing flue dust as a raw material for lead smelting. Specifically, a small amount of water glass or lime milk and other substances are added into the lead-containing flue dust to pre-bond the lead-containing flue dust, so that the raise dust generated in the smelting process is reduced, and the lead recovery efficiency is improved. Although wet recovery of lead oxide is considered to be a cleaner way for recovering lead oxide than the pyrogenic process, according to the analysis of the existing data, the currently reported wet recovery of lead oxide basically belongs to consumable recovery, namely, when the recovery process is not based on atomic economic reaction, an atomic economic reaction and a recycling mode are constructed to realize zero raw material consumption of the extraction process. Because most of the existing recovered lead oxide needs a large amount of chemical raw materials to realize the recovery of the lead oxide, not only is high recovery cost brought in the recovery process, but also secondary lead pollution is brought to the environment.
The typical wet recovery method comprises the steps of firstly dissolving lead oxide in lead-containing flue dust by adopting fluosilicic acid to obtain lead fluosilicate filtrate and filter residue, then adding quantitative sulfuric acid into the lead fluosilicate filtrate to separate out lead sulfate precipitate, finally reacting lead sulfate with sodium carbonate to obtain lead carbonate, filtering again and roasting at high temperature to obtain lead oxide, and then selling the lead oxide. However, the main drawbacks of this method are as follows:
(1) in the process of dissolving lead-containing flue dust by using strong-acid fluosilicic acid, a large amount of metal compounds such as aluminum, iron, copper, tin and the like contained in the lead-containing flue dust are also dissolved in the fluosilicic acid, so that the content of impurities in the lead fluosilicate filtrate is continuously accumulated;
(2) silicon dioxide contained in the lead-containing flue dust can also generate side reaction with fluosilicic acid, so that the consumption of the fluosilicic acid is increased;
(3) the sulfuric acid and sodium carbonate used in the reaction process cannot be recycled, and every 1mol of lead oxide is produced, theoretically, 1mol of sulfuric acid and 1mol of sodium carbonate are consumed at least, and 1mol of sodium sulfate and 1mol of carbon dioxide are discharged at the same time.
To overcome this problem, some scholars have tried to dissolve flue dust using a nitric acid solution instead of fluosilicic acid, but there are also problems of consumption of a large amount of nitric acid, ammonium carbonate and sodium carbonate, and severe corrosion of equipment by nitric acid and continuous accumulation of impurity metals. For example, the process study (environmental engineering, 2000, 18(5):44-46) reported by Juglan et al for the preparation of lead monoxide from lead-containing flue dust mentioned below: (1) washing flue dust with water to obtain lead sulfate; (2) precipitating with ammonium carbonate to obtain lead carbonate; (3) dissolving lead carbonate by nitric acid to convert into lead nitrate; (4) precipitating lead nitrate by using sodium carbonate to obtain basic lead carbonate; (5) roasting the basic lead carbonate to obtain the lead oxide. Guo Cuixiang and the like make a introduction of a comparison system for wet recovery of other lead in the current situation of lead-containing waste in China and the research progress of lead recovery technology (nonferrous metallurgy design and research, 2007, 28(2-3), 46-54).
In addition, the Yankee subject group of Huazhong science and technology university recently tried to recycle lead-containing waste materials by using citric acid and hydrogen peroxide, and the main problem of the method is the high cost and pollution caused by the consumption of high-temperature roasting of the citric acid in the recycling process. The Pan army blue subject group of Beijing chemical university tries to realize the dissolving and recrystallization process of lead oxide-containing waste materials by using a sodium hydroxide solution, and experimental research shows that the method has very excellent recovery effect on the lead oxide-containing waste materials obtained by directly converting a single-variety lead-acid battery, but has more remarkable dissolving and consuming phenomena in an alkaline sodium hydroxide solution of alumina, silicon dioxide, tin dioxide and the like in the recovery process on the lead oxide-containing waste materials of various mixed waste lead-acid batteries with complex components such as lead paste, flue ash and the like, particularly 10-30% of silicon-aluminum composite oxide. The existence of these problems has forced researchers to find a more suitable process for recovering lead from lead-containing wastes.
Disclosure of Invention
The invention aims to provide a method for recovering lead from lead-containing waste, which accords with the characteristics of atomic economic reaction, thereby greatly eliminating secondary pollution generated in the process of recovering lead-containing materials in the industry of regenerated lead, and being a novel process for recovering lead with energy conservation, environmental protection, cleanness and high efficiency.
A method for recovering lead from lead-containing waste materials comprises the following steps:
1) reacting the lead-containing waste with a complexing agent aqueous solution to completely dissolve lead oxide and/or lead sulfate in the lead-containing waste, and generating a supernatant containing lead ions and a lead salt-free precipitate after the reaction is finished; separating the lead ion-containing supernatant from the lead salt-free precipitate;
2) reacting the supernatant with a precipitator to completely precipitate lead ions in the supernatant, and generating a lead-containing salt precipitate and a regenerated complexing agent aqueous solution after the reaction is finished; separating the lead-containing salt precipitate from the regenerated complexing agent aqueous solution;
3) carrying out a dissolution reaction on the lead-containing salt precipitate and an electrolyte A aqueous solution to completely dissolve the lead-containing salt precipitate, and producing a lead-containing electrolyte B and a precipitator after the reaction is finished; recovering the precipitant; and carrying out electrolytic reaction on the lead-containing electrolyte B to obtain metallic lead, oxygen and regenerated electrolyte A.
In the present invention, the precipitant recovered after the dissolution reaction in step 3) may be recycled for use as the precipitant in step 2).
The complexing agent can be divided into a complexing agent A, a complexing agent B and a complexing agent C; the role played by different kinds of complexing agents is different; the complexing agent A mainly performs a complexing reaction with lead oxide in the lead-containing waste material to dissolve the lead oxide in the lead-containing waste material; the complexing agent B mainly performs a complexing reaction with lead sulfate in the lead-containing waste material to dissolve the lead sulfate in the lead-containing waste material; the complexing agent C is mainly used for simultaneously carrying out complexing reaction with lead oxide and lead sulfate in the lead-containing waste material, and simultaneously dissolving the lead oxide and the lead sulfate in the lead-containing waste material.
Preferably, the method for recovering lead from the lead-containing waste material comprises the steps of adopting a complexing agent A to carry out complexing dissolution on lead oxide in the lead-containing waste material, and then adopting a complexing agent B to carry out complexing dissolution on lead sulfate in a precipitate obtained after the previous complexing dissolution; the method specifically comprises the following steps:
1) carrying out complexation reaction on the lead-containing waste and a complexing agent A water solution at the temperature of 5-102 ℃ for 1-150min so as to completely dissolve lead oxide in the lead-containing waste; supernatant A containing lead ions and precipitate A containing insoluble lead salts are generated after the reaction is finished; separating the supernatant A and the precipitate A; carrying out a complexing reaction on the precipitate A and an aqueous solution of a complexing agent B at the temperature of 20-40 ℃ for 10-30min to completely dissolve lead sulfate in the precipitate A, and generating a supernatant B containing lead ions and a precipitate B containing no lead salt after the reaction is finished; separating the supernatant B from the precipitate B;
2) respectively reacting the supernatant A and the supernatant B with a precipitator at 40-70 ℃ for 1-5h to completely precipitate lead ions in the supernatant A and the supernatant B, and generating a lead salt-containing precipitate D, a regenerated complexing agent A aqueous solution and a regenerated complexing agent B aqueous solution after the reaction is finished; separating the precipitate D, the regenerated complexing agent A aqueous solution and the regenerated complexing agent B aqueous solution;
3) carrying out a dissolution reaction on the precipitate D and an aqueous solution of the electrolyte A to completely dissolve the precipitate D, and generating a lead-containing electrolyte B and a precipitator after the reaction is finished; recovering the precipitant; and carrying out electrolytic reaction on the lead-containing electrolyte B to obtain metallic lead, oxygen and regenerated electrolyte A.
Preferably, the method for recovering lead from the lead-containing waste material comprises the steps of firstly complexing and dissolving lead oxide in the lead-containing waste material by using a complexing agent B, and then complexing and dissolving lead sulfate in a precipitate obtained after the previous complexing and dissolving by using a complexing agent A; the method comprises the following steps:
1) carrying out complexation reaction on the lead-containing waste and a complexing agent B water solution at the temperature of 20-40 ℃ for 10-30min so as to completely dissolve lead sulfate in the lead-containing waste; producing supernatant B containing lead ions and precipitate B containing insoluble lead salt after the reaction is finished; separating the supernatant B from the precipitate B; carrying out a complexing reaction on the precipitate B and a complexing agent A water solution at the temperature of 5-102 ℃ for 1-150min to completely dissolve lead oxide in the precipitate B, and generating a supernatant A and a precipitate A after the reaction is finished; separating the supernatant A and the precipitate A;
2) respectively reacting the supernatant A and the supernatant B with a precipitator at 40-70 ℃ for 1-5h to completely precipitate lead ions in the supernatant A and the supernatant B, and generating a lead salt-containing precipitate D, a regenerated complexing agent A aqueous solution and a regenerated complexing agent B aqueous solution after the reaction is finished; separating the precipitate D, the regenerated complexing agent A aqueous solution and the regenerated complexing agent B aqueous solution;
3) carrying out a dissolution reaction on the precipitate D and an aqueous solution of the electrolyte A to completely dissolve the precipitate D, and generating a lead-containing electrolyte B and a precipitator after the reaction is finished; recovering the precipitant; carrying out electrolytic reaction on the lead-containing electrolyte B to obtain metal lead, oxygen and regenerated electrolyte A;
preferably, the method for recovering lead from the lead-containing waste material simultaneously performs complex dissolution on lead oxide and lead sulfate in the lead-containing waste material; the method specifically comprises the following steps:
1) carrying out complexation reaction on the lead-containing waste and a complexing agent C aqueous solution at the temperature of 5-80 ℃ for 5-120min so as to completely dissolve lead sulfate and lead oxide in the lead-containing waste; after the reaction is finished, supernatant C containing lead ions and precipitate C containing no lead salt are generated; separating the supernatant C and the lead salt-free precipitate C;
2) reacting the supernatant C with a precipitator at 40-70 ℃ for 1-5h to completely precipitate lead ions in the supernatant C, and generating a lead salt-containing precipitate D and a regenerated complexing agent C aqueous solution after the reaction is finished; separating the precipitate D and the regenerated complexing agent C aqueous solution;
3) carrying out a dissolution reaction on the precipitate D and an aqueous solution of the electrolyte A to completely dissolve the precipitate D, and generating a lead-containing electrolyte B and a precipitator after the reaction is finished; recovering the precipitant; and carrying out electrolytic reaction on the lead-containing electrolyte B to obtain metallic lead, oxygen and regenerated electrolyte A.
Preferably, if only the lead-containing salt precipitate D is directly desalted and decomposed to obtain lead oxide and a precipitator from the lead-containing waste, the precipitator is recovered, so that the lead oxide is recovered from the lead-containing waste.
Preferably, before the lead-containing waste material reacts with the complexing agent A, the complexing agent B or the complexing agent C, the method further comprises the following steps: pretreating the lead-containing waste so that lead compounds or lead in the lead-containing waste are converted into Pb (OH)2And/or PbO, as well as lead sulfate and non-lead impurities. For example, the insoluble impurities in the lead oxide-containing waste material of the present invention contain Pb and Pb3O4、PbO2、PbCO3、PbSO3、PbSO4、Pb3(PO4)2And one or more of their basic lead salts; conversion of the non-PbO components to Pb (OH) by pre-treatment of lead-containing waste2And/or PbO, as well as lead sulfate and non-lead impurities.
Preferably, in order to more quickly convert part of the lead-containing waste into lead oxide or lead sulfate, which facilitates quick dissolution of the complexing agent A, the complexing agent B or the complexing agent C, especially high-activity alpha-lead oxide; therefore, the lead-containing waste is placed in a muffle furnace under inert gas or N2Under the protection of (3), roasting. The roasting temperature is 270-640 ℃, and the roasting time is 0.5-2 h; the roasting for a long time can lead part of lead oxide to be sintered, which is not beneficial to the subsequent leaching process; in order that the non-PbO component can be completely converted into PbO and/or Pb (OH)2Basic lead sulfate, etc., more preferably, the roasting temperature is 550-585 ℃, and the roasting time is 0.5-1 h.
Preferably, the complexing agent A is selected from one or more of acetic acid, glycine, trichloroacetic acid, lead perchlorate, lead nitrate, lead amino acid, lead acetate, glyoxylic acid, ethylenediamine diacetic acid, propylenediamine tetraacetic acid, nitrilotriacetic acid, alanine, glutamic acid, 2-aminophenylpropionic acid, p-chlorophenylalanine, imidazole-5-alpha-alanine, imidazole-2-carboxylic acid, imidazole-1-acetic acid, 2-chlorophenylglycine, arginine, ethanolamine, phenylacetic acid, methylamine, ethylamine, ethylenediamine, propylenediamine, triethanolamine, and sodium, potassium, ammonium and quaternary ammonium salts corresponding to the above acids; the complexing agentThe concentration of the aqueous solution A is 0.1-4.5mol L-1. In order to effectively and completely complex and dissolve lead oxide in the lead-containing waste material, the complexing agent A is more preferably one or more of lead perchlorate, lead amino acid, lead acetate and glutamic acid.
Preferably, the complexing agent B is a conjugate solution consisting of X-Y; in the X-Y conjugated solution, X is one or two of ammonia, ethylenediamine, propylenediamine, ethylenediamine diacetic acid, ethylenediamine tetraacetic acid, propylenediamine diacetic acid, diethanolamine and triethanolamine; y is one or two of ammonium chloride, ammonium bisulfate, ammonium sulfate, ammonium nitrate, ammonium carbonate, ammonium bicarbonate, ammonium monohydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate; the concentration of the complexing agent B aqueous solution is X: 0.5-12.5mol L-1；Y：0.1-3.0mol L-1. In order to effectively and completely complex and dissolve lead sulfate in the lead-containing waste, the complexing agent B is preferably one or more of ammonia-ammonium bisulfate, ammonia-ammonium sulfate, ethylenediamine-ammonium sulfate and ethylenediamine tetraacetic acid-ammonium bisulfate conjugate solution.
Preferably, the complexing agent C is a compound formed by weakly acidic sodium chloride, ammonium chloride, potassium chloride, sodium tetrachlorozincate, potassium hexachlorocuprate or sodium tetrachloroaluminate and the complexing agent A and/or the complexing agent B; more preferably, the complexing agent C is a complex formed by weakly acidic sodium chloride and the complexing agent A and/or the complexing agent B, and the pH value of the aqueous solution of the complexing agent C is 0.5-6.8, preferably 1.0-5.8.
The chloride ions or polychlorinated complex ions contained in the compound can play a role in activating the surface of the lead-containing waste material in a weakly acidic environment, can promote or accelerate the migration and diffusion processes of the lead-containing complex ions, and improve the solubility of the lead complex ions in the lead-containing waste material, thereby improving the recovery rate and the yield of the lead-containing waste material to a certain extent.
Preferably, the electrolyte A is one or more of NaOH \ KOH methanesulfonic acid, perchloric acid, fluosilicic acid, acetic acid, trichloroacetic acid, phosphoric acid, pyrophosphoric acid and sulfamic acid; the concentration of the aqueous solution of the electrolyte A is 0.02-15.9mol L-1。
Preferably, the precipitating agent is selected from carbon dioxide, sulfur trioxide, and aqueous solutions corresponding to the above acid oxides, alkali metal acid salts, and one or more of ammonium sulfate, ammonium oxalate, and ammonium carbonate. In order to effectively precipitate lead ions in the supernatant and recover the later-stage precipitator, the method is more environment-friendly and energy-saving; more preferably, the precipitant is carbon dioxide.
Preferably, Ca can be quantitatively added into sulfate ions accumulated in the regenerated complexing agent B water solution in the recycling process2+，Sr2+Or Ba2+And sulfate precipitates with low solubility are formed and removed, and calcium sulfate, strontium sulfate or barium sulfate is obtained as a byproduct.
The invention has the following beneficial effects:
1. the method adopts complexing agent to perform complexing dissolution on lead oxide and/or lead sulfate in the lead-containing waste, then adopts precipitator to perform precipitation reaction on lead-containing supernatant, adopts electrolyte A to perform dissolution reaction on the precipitate, and utilizes electrolyte B to perform electrolysis reaction to obtain metallic lead or performs desalination decomposition reaction on the precipitate to obtain lead oxide; compared with the prior process for recovering lead oxide from the waste containing lead oxide, the method provided by the invention shortens the process flow to the greatest extent, the complexing agent, the precipitator and the electrolyte A used in the recovery process can be recycled, no waste liquid is generated in the whole process, and the method accords with the characteristics of atom economic reaction, thereby greatly eliminating secondary pollution generated in the process of recovering lead-containing materials in the lead regeneration industry, and being a novel process for recovering lead with energy conservation, environmental protection, cleanness and high efficiency.
2. In the method, the complexing agent A and the complexing agent B can be used for selectively complexing and dissolving lead oxide and lead sulfate in the lead-containing waste material, and the complexing agent C can also be used for simultaneously complexing and dissolving lead oxide and lead sulfate in the lead-containing waste material; the method of the invention realizes the atomic economic reaction in the lead recovery process on the basis of obtaining high-yield and high-purity PbO, thereby realizing zero consumption and zero emission, saving production cost and having more industrial application prospect.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Example 1
Selecting lead-containing waste materials of certain lead-acid battery factories in Zhejiang.
A method for recovering lead from lead-containing waste comprises the following specific steps:
the method comprises the following steps: placing the lead-containing waste in a muffle furnace and in N2Or roasting for 0.5h at 600 ℃ under the protection of inert gas to obtain roasted lead paste with main components of lead oxide and lead sulfate; physical and chemical measurements show that the roasted lead paste contains 95 wt% of lead oxide, and the balance is a small amount of lead sulfate and clay;
step two: adding 1kg of roasted lead plaster into a 10L reaction kettle, adding 5.5L of lead perchlorate with the concentration of 0.4mol/L and 0.8mol/L of imidazole-5-alpha-alanine into the reaction kettle as a complexing agent A, heating the reaction kettle to 60 ℃, and continuously stirring for 1h at the stirring speed of 300 r/min; lead oxide in the roasted lead paste is completely dissolved; after the reaction is finished, carrying out solid-liquid separation to obtain a filtrate A containing lead ions and a precipitate A of part of undissolved lead salt;
step three: adding the precipitate A in the second step into a 2L reaction kettle, adding 1L conjugate solution containing 12mol/L ammonia and 2.0mol/L ammonium sulfate into the reaction kettle as a complexing agent B, heating the reaction kettle to 50 ℃, and continuously stirring for 0.5h at the stirring speed of 380 r/min; so that the lead sulfate in the precipitate A is completely dissolved; after the reaction is finished, carrying out solid-liquid separation to obtain lead-containing filtrate B and precipitate B (namely insoluble impurities) without lead salt;
step four: respectively introducing carbon dioxide into the filtrate A and the filtrate B, and carbonizing for 2 hours at 48 ℃ to completely precipitate lead ions in the filtrate A and the filtrate B; after the reaction is finished, carrying out solid-liquid separation to obtain a regenerated complexing agent A aqueous solution, a regenerated complexing agent B aqueous solution and PbCO3A precipitate; the regenerated complexing agent A aqueous solution and regenerated complexThe mixture B aqueous solution can be respectively returned to the step two and the step three for recycling;
step five: mixing PbCO3Directly dissolving in electrolyte A (4.5mol/L perchloric acid aqueous solution) to make PbCO3Completely dissolving to obtain lead-containing electrolyte B (the main components are perchloric acid and lead perchlorate) and carbon dioxide; the carbon dioxide is recycled as the precipitator in the fourth step; the electrolyte B is subjected to direct current electrolytic reaction to obtain metallic lead, oxygen and regenerated electrolyte A; the regenerated electrolyte A can be recycled as the electrolyte for dissolving the next batch of lead carbonate.
872g of metallic lead product was finally obtained by the method for recovering lead described in this example. The purity of the refined lead is 99.998% by ICP analysis.
Example 2
Selecting lead-containing waste materials of certain lead-acid battery factories in Zhejiang.
A method for recovering lead from lead-containing waste comprises the following specific steps:
the method comprises the following steps: placing the lead-containing waste in a muffle furnace and in N2Or roasting for 0.5h at 600 ℃ under the protection of inert gas to obtain roasted lead paste with main components of lead oxide and lead sulfate; physical and chemical measurements show that the roasted lead paste contains 95 wt% of lead oxide, and the balance is a small amount of lead sulfate and clay;
step two: adding 1kg of the roasted lead paste into a 2L reaction kettle, adding 1L of conjugate solution containing 10mol/L ammonia and 2.0mol/L ammonium sulfate into the reaction kettle to serve as a complexing agent B, heating the reaction kettle to 50 ℃, and continuously stirring for 0.5h at the stirring speed of 380 r/min; lead sulfate in the roasted lead paste is completely dissolved; after the reaction is finished, carrying out solid-liquid separation to obtain a supernatant B containing lead ions and a precipitate B containing insoluble lead salt;
step three: adding the precipitate B in the second step into a 10L reaction kettle, adding 5.5L lead perchlorate with the concentration of 0.4mol/L and 0.6mol/L lead acetate into the reaction kettle as a complexing agent A, heating the reaction kettle to 60 ℃, and continuously stirring for 1h at the stirring speed of 300 r/min; lead oxide in the roasted lead paste is completely dissolved; after the reaction is finished, carrying out solid-liquid separation to obtain lead-containing supernatant A and precipitate A (insoluble impurities) without lead salt;
step four: respectively introducing carbon dioxide into the supernatant A and the supernatant B, carbonizing for 2h at 48 ℃ to completely precipitate lead ions in the supernatant A and the supernatant B, and performing solid-liquid separation after the reaction is finished to obtain PbCO3The precipitate, the regenerated complexing agent A water solution and the regenerated complexing agent B water solution; the regenerated complexing agent A water solution and the regenerated complexing agent B water solution can be recycled in the second step and the third step;
step five: mixing PbCO3Directly dissolved in perchloric acid aqueous solution of electrolyte A to generate dissolution reaction, so that PbCO is obtained3Completely dissolving; after the reaction is finished, lead-containing electrolyte B (the main components of which are perchloric acid and lead perchlorate) and carbon dioxide are generated; recovering carbon dioxide as a precipitator of the step four for recycling; the electrolyte B is subjected to electrolytic reaction to obtain metallic lead, oxygen and regenerated electrolyte A; the regenerated electrolyte A can be recycled by the fifth step.
In addition, the step five can also be carried out by the following steps: mixing PbCO3Directly desalting and decomposing at 390 ℃ to obtain lead oxide and carbon dioxide, and recovering the carbon dioxide to obtain the lead oxide.
914g of metallic lead product was finally obtained by the method for recovering lead described in this example. The purity of the refined lead is 99.997 percent by ICP analysis.
By adopting the method for recovering lead oxide in the embodiment, 989g of lead oxide product is finally obtained, and the purity of the lead oxide is 99.997% by ICP analysis.
Example 3
Selecting lead-containing waste materials of certain lead-acid battery factories in Zhejiang.
A method for recovering lead from lead-containing waste comprises the following specific steps:
the method comprises the following steps: placing the lead-containing waste in a muffle furnace and in N2Or roasting for 0.5h at 600 ℃ under the protection of inert gas to obtain roasted lead paste with main components of lead sulfate and lead oxide; the roasted lead paste contains 90 wt% of lead sulfate, 9.5 wt% of lead oxide and the rest 0.5 wt% of impurities through physical and chemical measurement;
step two: adding 1kg of the roasted lead paste into a 2L reaction kettle, adding 0.95L of lead perchlorate with the concentration of 0.4mol/L as a complexing agent A into the reaction kettle, heating the reaction kettle to 60 ℃, and continuously stirring for 0.5h at the stirring speed of 300 r/min; lead oxide in the roasted lead paste is completely dissolved; after the reaction is finished, carrying out solid-liquid separation to obtain a supernatant A containing lead ions and a precipitate A containing insoluble lead salts;
step three: adding the precipitate A in the second step into a 25L reaction kettle, adding 16L conjugate solution containing 10mol/L ammonia, 0.2mol/L ethylene diamine tetraacetic acid, 1.5mol/L ammonium chloride and 1.5mol/L ammonium sulfate into the reaction kettle as a complexing agent B, heating the reaction kettle to 50 ℃, and continuously stirring for 1.5h at the stirring speed of 370 r/min; so that the lead sulfate in the precipitate A is completely dissolved; after the reaction is finished, carrying out solid-liquid separation to obtain lead-containing supernatant B and lead-salt-free precipitate B (namely insoluble impurities);
step four: respectively introducing carbon dioxide into the supernatant A and the supernatant B, carbonizing for 2h at 48 ℃ to completely precipitate lead ions in the supernatant A and the supernatant B, and performing solid-liquid separation after the reaction is finished to obtain PbCO3The precipitate, the regenerated complexing agent A water solution and the regenerated complexing agent B water solution; the regenerated complexing agent A water solution and the regenerated complexing agent B water solution can be recycled in the second step and the third step;
step five: mixing PbCO3Directly dissolved in perchloric acid aqueous solution of electrolyte A to generate dissolution reaction, so that PbCO is obtained3Completely dissolving; after the reaction is finished, lead-containing electrolyte B (the main components of which are perchloric acid and lead perchlorate) and carbon dioxide are generated; recovering carbon dioxide as a precipitator of the step four for recycling; the electrolyte B is subjected to electrolytic reaction to obtain metallic lead, oxygen and regenerated electrolyte A; the regenerated electrolyte A can be recycled by the fifth step.
In addition, the step five can also be carried out by the following steps: mixing PbCO3Directly desalting and decomposing at 390 ℃ to obtain lead oxide and carbon dioxide, and recovering the carbon dioxide to obtain the lead oxide.
662g of metallic lead product is finally obtained by adopting the method for recovering lead in the embodiment. The purity of the refined lead is 99.999 percent by ICP analysis.
719g of lead oxide product was finally obtained by the method for recovering lead oxide described in this example, and the purity of lead oxide was 99.998% by ICP analysis.
Example 4
Selecting lead-containing waste materials of certain lead-acid battery factories in Zhejiang.
A method for recovering lead from lead-containing waste comprises the following specific steps:
the method comprises the following steps: placing the lead-containing waste in a muffle furnace and in N2Or roasting for 0.5h at 600 ℃ under the protection of inert gas to obtain roasted lead paste with main components of lead oxide and lead sulfate; the roasted lead paste contains 90 wt% of lead sulfate, 9.5 wt% of lead oxide and the rest 0.5 wt% of impurities through physical and chemical measurement;
step two: adding 1kg of the roasted lead paste into a 25L reaction kettle, adding 16L of conjugate solution containing 10mol/L ammonia and 2.5mol/L ammonium sulfate into the reaction kettle to serve as a complexing agent B, heating the reaction kettle to 50 ℃, and continuously stirring for 1.5h at the stirring speed of 380 r/min; so that the lead sulfate in the precipitate A is completely dissolved; after the reaction is finished, carrying out solid-liquid separation to obtain a supernatant B containing lead ions and a precipitate B containing insoluble lead salt;
step three: adding the precipitate B in the second step into a 2L reaction kettle, adding 0.55L lead perchlorate with the concentration of 0.4mol/L as a complexing agent A into the reaction kettle, heating the reaction kettle to 60 ℃, and continuously stirring for 0.5h at the stirring speed of 300 r/min; lead oxide in the roasted lead paste is completely dissolved; after the reaction is finished, carrying out solid-liquid separation to obtain lead-containing supernatant A and precipitate A (insoluble impurities) without lead salt;
step four: respectively introducing carbon dioxide into the supernatant A and the supernatant B, carbonizing for 2h at 48 ℃ to completely precipitate lead ions in the supernatant A and the supernatant B, and performing solid-liquid separation after the reaction is finished to obtain PbCO3The precipitate, the regenerated complexing agent A water solution and the regenerated complexing agent B water solution; the regenerated complexing agent A water solution and the regenerated complexing agent B water solution can be recycled in the second step and the third step;
step five: mixing PbCO3Directly desalting and decomposing at 445 deg.C to obtain lead oxide and carbon dioxide. By analysis, 727g of alpha-lead oxide product with a purity of 99.994% was obtained in the experiment.
Example 5
The waste valve-controlled sealed lead-acid battery with the market specification of 12V and 7Ah is crushed and separated by a conventional method to obtain the lead-containing waste.
A method for recovering lead from lead-containing waste comprises the following specific steps:
the method comprises the following steps: placing the lead-containing waste in a muffle furnace and in N2Or roasting for 1h at 600 ℃ under the protection of inert gas to obtain roasted lead paste with main components of lead oxide and lead sulfate; through chemical titration analysis, the roasted lead plaster contains 40.2 wt% of lead sulfate, 59.4% of lead oxide and 0.4% of other impurities;
step two: adding 1kg of the roasted lead paste into a 6L reaction kettle, adding 3L of lead acetate with the concentration of 0.75mol/L into the reaction kettle as a complexing agent A, heating the reaction kettle to 60 ℃, and continuously stirring for 1h at the stirring speed of 300 r/min; lead oxide in the roasted lead paste is completely dissolved; after the reaction is finished, carrying out solid-liquid separation to obtain a supernatant A containing lead ions and a precipitate A containing insoluble lead salts;
step three: adding the precipitate A in the second step into a 15L reaction kettle, adding 8L conjugate solution containing 10mol/L ammonia and 2.0mol/L ammonium sulfate into the reaction kettle as a complexing agent B, heating the reaction kettle to 50 ℃, and continuously stirring for 1h at the stirring speed of 380 r/min; so that the lead sulfate in the precipitate A is completely dissolved; after the reaction is finished, carrying out solid-liquid separation to obtain lead-containing supernatant B and lead-salt-free precipitate B (namely insoluble impurities);
step four: respectively introducing carbon dioxide into the supernatant A and the supernatant B, carbonizing for 2h at 48 ℃ to completely precipitate lead ions in the supernatant A and the supernatant B, and performing solid-liquid separation after the reaction is finished to obtain PbCO3The precipitate, the regenerated complexing agent A water solution and the regenerated complexing agent B water solution; the regenerated complexing agent A water solution and the regenerated complexing agent B water solution can be recycled in the second step and the third step;
step five: mixing PbCO3Directly dissolved in perchloric acid aqueous solution of electrolyte A to generate dissolution reaction, so that PbCO is obtained3Completely dissolving; after the reaction is finished, lead-containing electrolyte B (the main components of which are perchloric acid and lead perchlorate) and carbon dioxide are generated; recovering carbon dioxide as a precipitator of the step four for recycling; the electrolyte B is subjected to electrolytic reaction to obtain metallic lead, oxygen and regenerated electrolyte A; the regenerated electrolyte A can be recycled by the fifth step.
In addition, the step five can also be carried out by the following steps: mixing PbCO3Directly desalting and decomposing at 390 ℃ to obtain lead oxide and carbon dioxide, and recovering the carbon dioxide to obtain the lead oxide.
784g of metallic lead product was finally obtained by the method for recovering lead described in this example. The purity of the refined lead is 99.998% by ICP analysis.
By adopting the method for recovering lead oxide in the embodiment, 848g of lead oxide product is finally obtained, and the purity of the lead oxide is 99.997% by ICP analysis.
Example 6
Selecting lead-containing waste materials of certain lead-acid battery factories in Zhejiang.
The waste valve-controlled sealed lead-acid battery with the market specification of 12V and 7Ah is crushed and separated by a conventional method to obtain the lead-containing waste.
A method for recovering lead from lead-containing waste comprises the following specific steps:
the method comprises the following steps: placing the lead-containing waste in a muffle furnace and in N2Or roasting for 1h at 600 ℃ under the protection of inert gas to obtain roasted lead paste with main components of lead oxide and lead sulfate; through chemical titration analysis, the roasted lead plaster contains 40.2 wt% of lead sulfate, 59.4% of lead oxide and 0.4% of other impurities;
step two: adding 1kg of the roasted lead paste into a 15L reaction kettle, adding 8L of conjugate solution containing 10mol/L ammonia and 2.0mol/L ammonium sulfate into the reaction kettle to serve as a complexing agent B, heating the reaction kettle to 50 ℃, and continuously stirring for 1h at the stirring speed of 380 r/min; so that the lead sulfate in the precipitate A is completely dissolved; after the reaction is finished, carrying out solid-liquid separation to obtain a supernatant B containing lead ions and a precipitate B containing insoluble lead salt;
step three: adding the precipitate B in the second step into a 6L reaction kettle, adding 3L of lead nitrate with the concentration of 0.45mol/L and 0.55mol/L of lead perchlorate into the reaction kettle as a complexing agent A, heating the reaction kettle to 60 ℃, and continuously stirring for 1h at the stirring speed of 300 r/min; lead oxide in the roasted lead paste is completely dissolved; after the reaction is finished, carrying out solid-liquid separation to obtain lead-containing supernatant A and precipitate A (insoluble impurities) without lead salt;
step four: respectively introducing carbon dioxide into the supernatant A and the supernatant B, carbonizing for 2h at 48 ℃ to completely precipitate lead ions in the supernatant A and the supernatant B, and performing solid-liquid separation after the reaction is finished to obtain PbCO3The precipitate, the regenerated complexing agent A water solution and the regenerated complexing agent B water solution; the regenerated complexing agent A water solution and the regenerated complexing agent B water solution can be recycled in the second step and the third step;
step five: the PbCO is mixed with3Directly desalt and decompose at 550 ℃ to obtain lead oxide and carbon dioxide.
Through analysis, 854g of beta-lead oxide product with the purity of 99.998 percent is finally obtained by adopting the method for recovering the lead oxide.
Example 7
The waste valve-controlled sealed lead-acid battery with the market specification of 12V and 7Ah is crushed and separated by a conventional method to obtain the lead-containing waste.
A method for recovering lead from lead-containing waste comprises the following specific steps:
the method comprises the following steps: placing the lead-containing waste in a muffle furnace and in N2Or roasting for 1h at 600 ℃ under the protection of inert gas to obtain roasted lead paste with main components of lead oxide and lead sulfate; through chemical titration analysis, the roasted lead plaster contains 40.2 wt% of lead sulfate, 59.4% of lead oxide and 0.4% of other impurities;
step two: adding 1kg of the roasted lead paste into a 20L reaction kettle, adding 10L of a mixed solution which is composed of 4.2mol/L sodium chloride, 2.0mol/L ammonium acetate and a conjugate solution of 10mol/L ammonia and 2.0mol/L ammonium sulfate into the reaction kettle and serves as a complexing agent C, then adjusting the pH value of the solution by using acid, finally controlling the pH value to be 5.0, then heating the reaction kettle to 50 ℃, and continuously stirring for 1.5h at the stirring speed of 350 r/min; lead oxide and lead sulfate components in the roasted lead paste are gradually dissolved; after the reaction is finished, carrying out solid-liquid separation to obtain a supernatant C containing lead ions and a precipitate C containing insoluble lead salt;
step three: introducing carbon dioxide into the supernatant C, carbonizing for 2h at 48 ℃ to completely precipitate lead ions in the supernatant C, and performing solid-liquid separation after the reaction is finished to obtain PbCO3The precipitate and the aqueous solution of (a); adding the separated water solution into a calcium hydroxide solution, removing redundant sulfate ions generated in the complexing process, and performing solid-liquid separation to obtain a regenerated complexing agent C which can be recycled in the second step;
step four: mixing PbCO3Directly desalting and decomposing at 390 ℃ to obtain lead oxide and carbon dioxide, and recovering the carbon dioxide to obtain the lead oxide.
By adopting the method for recovering lead oxide in the embodiment, 856g of lead oxide product is finally obtained.
Example 8
The waste valve-controlled sealed lead-acid battery with the market specification of 12V and 7Ah is crushed and separated by a conventional method to obtain the lead-containing waste.
A method for recovering lead from lead-containing waste comprises the following specific steps:
the method comprises the following steps: placing the lead-containing waste in a muffle furnace and in N2Or roasting for 1h at 600 ℃ under the protection of inert gas to obtain roasted lead paste with main components of lead oxide and lead sulfate; through chemical titration analysis, the roasted lead plaster contains 40.2 wt% of lead sulfate, 59.4% of lead oxide and 0.4% of other impurities;
step two: adding 1kg of the roasted lead paste into a 20L reaction kettle, adding 10L of mixed solution containing 4.0mol/L sodium chloride and 2.3mol/L histidine into the reaction kettle as a complexing agent C, adjusting the pH value of the solution to be 4.0-5.2, heating the reaction kettle to 50 ℃, continuously stirring for 1.5h, and stirring at the speed of 350 r/min; lead oxide and lead sulfate in the roasted lead paste are completely dissolved; after the reaction is finished, carrying out solid-liquid separation to obtain a supernatant C containing lead ions and a precipitate C containing insoluble lead salt;
step three: introducing carbon dioxide into the supernatant C, carbonizing for 2h at 48 ℃ to completely precipitate lead ions in the supernatant C, and performing solid-liquid separation after the reaction is finished to obtain PbCO3The precipitate and the aqueous solution of (a); adding the separated water solution into a calcium hydroxide solution, removing redundant sulfate ions generated in the complexing process, and performing solid-liquid separation to obtain a regenerated complexing agent C which can be recycled in the second step;
step four: mixing PbCO3Directly dissolved in perchloric acid aqueous solution of electrolyte A to generate dissolution reaction, so that PbCO is obtained3Completely dissolving; after the reaction is finished, lead-containing electrolyte B (the main components of which are perchloric acid and lead perchlorate) and carbon dioxide are generated; recovering carbon dioxide as a precipitator of the third step for recycling; the electrolyte B is subjected to electrolytic reaction to obtain metallic lead, oxygen and regenerated electrolyte A; the regenerated electrolyte A can be recycled by the fifth step.
792g of metallic lead product is finally obtained by adopting the method for recovering lead. The purity of the refined lead was 99.9991% by ICP analysis.
Example 9
The waste valve-controlled sealed lead-acid battery with the market specification of 12V and 7Ah is crushed and separated by a conventional method to obtain the lead-containing waste.
A method for recovering lead from lead-containing waste comprises the following specific steps:
the method comprises the following steps: placing the lead-containing waste in a muffle furnace and in N2Or roasting for 1h at 600 ℃ under the protection of inert gas to obtain roasted lead paste with main components of lead oxide and lead sulfate; through chemical titration analysis, the roasted lead plaster contains 40.2 wt% of lead sulfate, 59.4% of lead oxide and 0.4% of other impurities;
step two: adding 1kg of the roasted lead paste into a 20L reaction kettle, adding 10L of mixed solution containing 3.0mol/L ammonium chloride, 0.66mol/L sodium acetate, 0.3mol/L arginine, 10mol/L ammonia and 2.0mol/L ammonium sulfate as a complexing agent C into the reaction kettle, heating the reaction kettle to 50 ℃, and continuously stirring for 1.5h at the stirring speed of 350 r/min; lead oxide and lead sulfate in the roasted lead paste are completely dissolved; after the reaction is finished, carrying out solid-liquid separation to obtain a supernatant C containing lead ions and a precipitate C containing insoluble lead salt;
step three: introducing carbon dioxide into the supernatant C, carbonizing for 2h at 40 ℃ to completely precipitate lead ions in the supernatant C, and performing solid-liquid separation after the reaction is finished to obtain PbCO3The precipitate and the aqueous solution of (a); adding the separated water solution into a calcium hydroxide solution, removing redundant sulfate ions generated in the complexing process, and performing solid-liquid separation to obtain a regenerated complexing agent C which can be recycled in the second step;
step four: mixing PbCO3Directly dissolved in the fluosilicic acid aqueous solution of the electrolyte A to carry out dissolution reaction, so that PbCO is obtained3Completely dissolving; after the reaction is finished, lead-containing electrolyte B (the main components are fluosilicic acid and lead fluosilicate) and carbon dioxide are generated; recovering carbon dioxide as a precipitator of the third step for recycling; the electrolyte B is subjected to electrolytic reaction to obtain metallic lead, oxygen and regenerated electrolyte A; the regenerated electrolyte A can be recycled by the fifth step.
788g of metal lead product is finally obtained by adopting the method for recovering lead. The purity of the refined lead is 99.997 percent by ICP analysis.
Example 10
The waste valve-controlled sealed lead-acid battery with the market specification of 12V and 7Ah is crushed and separated by a conventional method to obtain the lead-containing waste.
A method for recovering lead from lead-containing waste comprises the following specific steps:
the method comprises the following steps: placing the lead-containing waste in a muffle furnace and in N2Or roasting for 1h at 600 ℃ under the protection of inert gas to obtain roasted lead paste with main components of lead oxide and lead sulfate; through chemical titration analysis, the roasted lead plaster contains 40.2 wt% of lead sulfate, 59.4% of lead oxide and 0.4% of other impurities;
step two: adding 1kg of the roasted lead paste into a 6L reaction kettle, adding 3L of concentrated mixed solution containing 1.0mol/L lead acetate, 1.0mol/L lead perchlorate and 0.5mol/L arginine into the reaction kettle to serve as a complexing agent A, heating the reaction kettle to 65 ℃, and continuously stirring for 1.5h at the stirring speed of 300 r/min; lead oxide in the roasted lead paste is completely dissolved; after the reaction is finished, carrying out solid-liquid separation to obtain a supernatant A containing lead ions and a precipitate A containing insoluble lead salts;
step three: adding the precipitate A in the second step into a 15L reaction kettle, adding 8L conjugate solution containing 10mol/L ammonia and 2.0mol/L ammonium sulfate into the reaction kettle as a complexing agent B, heating the reaction kettle to 50 ℃, and continuously stirring for 1h at the stirring speed of 380 r/min; so that the lead sulfate in the precipitate A is completely dissolved; after the reaction is finished, carrying out solid-liquid separation to obtain lead-containing supernatant B and lead-salt-free precipitate B (namely insoluble impurities);
step four: respectively introducing carbon dioxide into the supernatant A and the supernatant B, carbonizing for 2h at 48 ℃ to completely precipitate lead ions in the supernatant A and the supernatant B, and performing solid-liquid separation after the reaction is finished to obtain PbCO3The precipitate, the regenerated complexing agent A water solution and the regenerated complexing agent B water solution; the regenerated complexing agent A water solution and the regenerated complexing agent B water solution can be recycled in the second step and the third step;
step five: mixing PbCO3Directly dissolved in perchloric acid solution of electrolyte A to generate dissolution reaction, so that PbCO is obtained3Completely dissolving; after the reaction is finished, lead-containing electrolyte B (the main components of which are perchloric acid and lead perchlorate) and carbon dioxide are generated; recovering carbon dioxide as a precipitator of the step four for recycling; the electrolyte B is subjected to electrolytic reaction to obtain metallic lead, oxygen and regenerated electrolyte A; the regenerated electrolyte A can be recycled by the fifth step.
779g of metallic lead product is finally obtained by adopting the method for recovering lead. The purity of the refined lead was 99.9991% by ICP analysis.
Example 11
Selecting lead-containing waste materials of certain lead-acid battery factories in Zhejiang.
The waste valve-controlled sealed lead-acid battery with the market specification of 12V and 7Ah is crushed and separated by a conventional method to obtain the lead-containing waste.
A method for recovering lead from lead-containing waste comprises the following specific steps:
the method comprises the following steps: placing the lead-containing waste in a muffle furnace and in N2Or roasting for 1h at 600 ℃ under the protection of inert gas to obtain roasted lead paste with main components of lead oxide and lead sulfate; through chemical titration analysis, the roasted lead plaster contains 40.2 wt% of lead sulfate, 59.4% of lead oxide and 0.4% of other impurities;
step two: adding 1kg of the roasted lead paste into a 15L reaction kettle, adding 8L of conjugate solution containing 10mol/L ammonia and 2.0mol/L ammonium sulfate into the reaction kettle to serve as a complexing agent B, heating the reaction kettle to 50 ℃, and continuously stirring for 1h at the stirring speed of 380 r/min; so that the lead sulfate in the precipitate A is completely dissolved; after the reaction is finished, carrying out solid-liquid separation to obtain a supernatant B containing lead ions and a precipitate B containing insoluble lead salt;
step three: adding the precipitate B in the second step into a 6L reaction kettle, adding 3L concentrated mixed solution containing imidazole with the concentration of 1.0mol/L and arginine with the concentration of 0.5mol/L into the reaction kettle as a complexing agent A, heating the reaction kettle to 60 ℃, and continuously stirring for 1h at the stirring speed of 350 r/min; lead oxide in the roasted lead paste is completely dissolved; after the reaction is finished, carrying out solid-liquid separation to obtain lead-containing supernatant A and precipitate A (insoluble impurities) without lead salt;
step four: respectively introducing carbon dioxide into the supernatant A and the supernatant B, carbonizing for 2h at 48 ℃ to completely precipitate lead ions in the supernatant A and the supernatant B, and performing solid-liquid separation after the reaction is finished to obtain PbCO3The precipitate, the regenerated complexing agent A water solution and the regenerated complexing agent B water solution; the regenerated complexing agent A water solution and the regenerated complexing agent B water solution can be recycled in the second step and the third step;
step five: mixing PbCO3Directly dissolved in perchloric acid solution of electrolyte A to generate dissolution reaction, so that PbCO is obtained3Completely dissolving; after the reaction is finished, lead-containing electrolyte B (the main components of which are perchloric acid and lead perchlorate) and carbon dioxide are generated; recovering carbon dioxide as step fourThe precipitant is recycled; the electrolyte B is subjected to electrolytic reaction to obtain metallic lead, oxygen and regenerated electrolyte A; the regenerated electrolyte A can be recycled by the fifth step.
780g of metallic lead product was finally obtained by the method for recovering lead described in this example. The purity of the refined lead is 99.999 percent by ICP analysis.
Example 12
The waste valve-controlled sealed lead-acid battery with the market specification of 12V and 7Ah is crushed and separated by a conventional method to obtain the lead-containing waste. The method for recovering the lead-containing waste comprises the following specific steps:
the method comprises the following steps: placing the lead-containing waste in a muffle furnace and in N2Or roasting for 1h at 600 ℃ under the protection of inert gas to obtain roasted lead paste with main components of lead oxide and lead sulfate; through chemical titration analysis, the roasted lead plaster contains 40.2 wt% of lead sulfate, 59.4% of lead oxide and 0.4% of other impurities;
step two: adding 1kg of the roasted lead paste into a 6L reaction kettle, adding 3L of complexing agent A lead perchlorate with the concentration of 0.45mol/L into the reaction kettle, heating the reaction kettle to 60 ℃, and continuously stirring for 1h at the stirring speed of 300 r/min; lead oxide in the roasted lead paste is completely dissolved; after the reaction is finished, carrying out solid-liquid separation to obtain a filtrate A containing lead ions and a precipitate A containing undissolved lead salt;
step three: adding the precipitate A in the second step into a 10L reaction kettle, adding 5.5L conjugate solution containing 10.5mol/L ammonia and 2.5mol/L ammonium sulfate into the reaction kettle as a complexing agent B, heating the reaction kettle to 45 ℃, and continuously stirring for 1h at the stirring speed of 380r/min to completely dissolve lead sulfate in the precipitate A; after the reaction is finished, carrying out solid-liquid separation to obtain lead-containing filtrate B and precipitate B (namely insoluble impurities) without lead salt;
step four: and respectively introducing carbon dioxide into the filtrate A and the filtrate B, and carbonizing for 2 hours at the temperature of 50 ℃ to ensure that lead ions in the filtrate A and the filtrate B completely form lead carbonate precipitates. After the reaction is finished and the reaction is crystallized for 1 hour, carrying out solid-liquid separation to respectively obtain a regenerated complexing agent A aqueous solution, a regenerated complexing agent B aqueous solution and PbCO3And (4) precipitating.The regenerated complexing agent A aqueous solution and the regenerated complexing agent B aqueous solution can be respectively returned to the second step and the third step for recycling;
step five: mixing PbCO3Directly dissolved in electrolyte A (5mol/L perchloric acid aqueous solution) to carry out dissolution reaction, so that PbCO is obtained3Carrying out a dissolution reaction to obtain lead-containing electrolyte B (lead perchlorate and residual perchloric acid), and recovering generated carbon dioxide which can be used as a precipitator and returned to the step four for recycling; carrying out pulse electrolysis reaction on the lead-containing electrolyte B to obtain metal lead, oxygen and regenerated electrolyte A; the regenerated electrolyte A can be returned to the step five for recycling.
Experiments show that 797g of metal lead product is finally obtained by adopting the method for recovering lead. The purity of the refined lead was 99.9991% by ICP analysis.
Example 13
The lead carbonate obtained from the lead-containing waste of example 1 after the same first, second, third and fourth treatment steps was treated as follows, step five, specifically:
mixing PbCO3Directly desalt and decompose at 480 ℃ to obtain lead oxide and carbon dioxide. By ICP analysis, 944g of 99.997% pure lead oxide product was obtained.
Example 14
The lead carbonate obtained from the lead-containing waste of example 6 after the same first, second, third and fourth treatment was treated as follows, step five, specifically:
step five: the PbCO is mixed with3Directly dissolving the PbCO into electrolyte A (1mol/L fluosilicic acid +2mol/L perchloric acid solution) to lead PbCO to be3Completely dissolving to obtain lead-containing electrolyte B (the main components are lead fluosilicate and lead perchlorate, and the rest is fluosilicic acid and perchloric acid) and regenerated carbon dioxide; recovering the carbon dioxide as a precipitator of the step four for recycling; the electrolyte B is subjected to constant-pressure electrolytic reaction to obtain metallic lead, oxygen and regenerated electrolyte A; the regenerated electrolyte A can be used for the leaching process of the step five of the next batch of materials again, and the recycling of the electrolyte is realized.
After analysis, 789g of metallic lead product was finally obtained by using the method for recovering lead described in this example. The purity of the refined lead is 99.9992% by ICP analysis.
Example 15
The waste valve-controlled sealed lead-acid battery with the market specification of 12V and 7Ah is crushed and separated by a conventional method to obtain the lead-containing waste.
A method for recovering lead from lead-containing waste comprises the following specific steps:
the method comprises the following steps: placing the lead-containing waste in a muffle furnace and in N2Or roasting for 1h at 600 ℃ under the protection of inert gas to obtain roasted lead paste with main components of lead oxide and lead sulfate; through chemical titration analysis, the roasted lead plaster contains 40.2 wt% of lead sulfate, 59.4% of lead oxide and 0.4% of other impurities;
step two: adding 1kg of the roasted lead paste into a 20L reaction kettle, adding 10L of mixed solution which is composed of 4.2mol/L sodium chloride and 2.0mol/L ammonium acetate into the reaction kettle and is used as a complexing agent C, then adjusting the pH value of the solution by using acid, finally controlling the pH value to be 5.2, then heating the reaction kettle to 50 ℃, and continuously stirring for 1.5h at the stirring speed of 350 r/min; lead oxide and lead sulfate components in the roasted lead paste are gradually dissolved; after the reaction is finished, carrying out solid-liquid separation to obtain a supernatant C containing lead ions and a precipitate C containing insoluble lead salt;
step three: introducing carbon dioxide into the supernatant C, carbonizing for 2h at 48 ℃ to completely precipitate lead ions in the supernatant C, and performing solid-liquid separation after the reaction is finished to obtain PbCO3The precipitate and the aqueous solution of (a); adding the separated water solution into a calcium hydroxide solution, removing redundant sulfate ions generated in the complexing process, and performing solid-liquid separation to obtain a regenerated complexing agent C which can be recycled in the second step;
step four: mixing PbCO3Directly desalting and decomposing at 420 deg.C to obtain lead oxide and carbon dioxide, and recovering carbon dioxide to obtain lead oxide.
781 g of lead oxide product with purity > 99.992% was obtained by the method for recovering lead oxide described in this example.
Example 16
The waste valve-controlled sealed lead-acid battery with the market specification of 12V and 7Ah is crushed and separated by a conventional method to obtain the lead-containing waste.
A method for recovering lead from lead-containing waste comprises the following specific steps:
the method comprises the following steps: placing the lead-containing waste in a muffle furnace and in N2Or roasting for 1h at 600 ℃ under the protection of inert gas to obtain roasted lead paste with main components of lead oxide and lead sulfate; through chemical titration analysis, the roasted lead plaster contains 40.2 wt% of lead sulfate, 59.4% of lead oxide and 0.4% of other impurities;
step two: adding 1kg of the roasted lead paste into a 20L reaction kettle, adding 10L of a mixed solution which is composed of 4.2mol/L sodium chloride, 10mol/L ammonia and 2.0mol/L ammonium sulfate conjugate solution into the reaction kettle and serves as a complexing agent C, then adjusting the pH value of the solution with acid, finally controlling the pH value to be 6.7, then heating the reaction kettle to 50 ℃, and continuously stirring for 1.5h at the stirring speed of 350 r/min; lead oxide and lead sulfate components in the roasted lead paste are gradually dissolved; after the reaction is finished, carrying out solid-liquid separation to obtain a supernatant C containing lead ions and a precipitate C containing insoluble lead salt;
step three: introducing carbon dioxide into the supernatant C, carbonizing for 2h at 48 ℃ to completely precipitate lead ions in the supernatant C, and performing solid-liquid separation after the reaction is finished to obtain PbCO3The precipitate and the aqueous solution of (a); adding the separated water solution into a calcium hydroxide solution, removing redundant sulfate ions generated in the complexing process, and performing solid-liquid separation to obtain a regenerated complexing agent C which can be recycled in the second step;
step four: mixing PbCO3Directly desalting and decomposing at 490 deg.C to obtain lead oxide and carbon dioxide, and recovering carbon dioxide to obtain lead oxide.
781 g of lead oxide product with 99.992% purity was obtained by the method of this example.
It should be understood that the above-mentioned embodiments of the present invention are only examples for illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations and modifications can be made on the basis of the above-mentioned description, and not exhaustive enumeration of all embodiments, and obvious variations and modifications can be made without departing from the scope of the present invention.

Claims (12)

1. A method for recovering lead from lead-containing waste is characterized by comprising the following steps:
1) carrying out complexation reaction on the lead-containing waste and a complexing agent C aqueous solution at the temperature of 5-80 ℃ for 5-120min so as to completely dissolve lead sulfate and lead oxide in the lead-containing waste; after the reaction is finished, supernatant C containing lead ions and precipitate C containing no lead salt are generated; separating the supernatant C and the lead salt-free precipitate C;
2) reacting the supernatant C with a precipitator at 40-70 ℃ for 1-5h to completely precipitate lead ions in the supernatant C, and generating a lead salt-containing precipitate D and a regenerated complexing agent C aqueous solution after the reaction is finished; separating the precipitate D and the regenerated complexing agent C aqueous solution;
3) carrying out a dissolution reaction on the precipitate D and an aqueous solution of the electrolyte A to completely dissolve the precipitate D, and generating a lead-containing electrolyte B and a precipitator after the reaction is finished; recovering the precipitant; carrying out electrolytic reaction on the lead-containing electrolyte B to obtain metal lead, oxygen and regenerated electrolyte A;
the complexing agent C is a compound formed by weakly acidic sodium chloride, ammonium chloride, potassium chloride, sodium tetrachlorozincate, potassium hexachlorocuprate or sodium tetrachloroaluminate and the complexing agent A and/or the complexing agent B;
the complexing agent A is selected from one or more of acetic acid, aminoacetic acid, trichloroacetic acid, lead perchlorate, lead nitrate, lead aminoacid, lead acetate, glyoxylic acid, ethylenediamine diacetic acid, propylenediamine tetraacetic acid, nitrilotriacetic acid, alanine, glutamic acid, 2-aminophenylpropionic acid, p-chlorophenylalanine, imidazole-5-alpha-alanine, imidazole-2-carboxylic acid, imidazole-1-acetic acid, 2-chlorophenylglycine, arginine, ethanolamine, phenylacetic acid, methylamine, ethylamine, ethylenediamine, propylenediamine, triethanolamine and corresponding sodium salt, potassium salt, ammonium salt and quaternary ammonium salt;
the complexing agent B is a conjugated solution consisting of X-Y; in the X-Y conjugated solution, X is one or two of ammonia, ethylenediamine, propylenediamine, ethylenediamine diacetic acid, ethylenediamine tetraacetic acid, propylenediamine diacetic acid, diethanolamine and triethanolamine; y is one or two of ammonium chloride, ammonium bisulfate, ammonium sulfate, ammonium nitrate, ammonium carbonate, ammonium bicarbonate, ammonium monohydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate.
2. The method according to claim 1, wherein the lead salt-containing precipitate D is directly desalted and then decomposed to obtain lead oxide and a precipitant, and the precipitant is recovered, thereby realizing the recovery of lead oxide from lead-containing waste materials.
3. The method according to claim 2, wherein before the lead-containing waste material is reacted with the complexing agent A, the complexing agent B or the complexing agent C, the method further comprises the following steps: pretreating the lead-containing waste material.
4. The method of claim 3, wherein the pre-treating comprises placing the lead-containing waste in a muffle furnace under N2Roasting under the protection of (1); the roasting temperature is 270-640 ℃, and the roasting time is 0.5-2 h.
5. The method according to claim 1, wherein the concentration of the aqueous solution of complexing agent A is 0.1-4.5mol L-1。
6. The method according to claim 1, wherein the complexing agent A is one or more of lead perchlorate, glycine, sodium acetate, lead acetate and glutamic acid.
7. The method according to claim 1, wherein the concentration of the aqueous solution of complexing agent B is X: 1.0-12.5 mol L-1；Y：0.1-3.0 mol L-1。
8. The method according to claim 1, wherein the complexing agent C is a complex formed by the weakly acidic sodium chloride and the complexing agent A and/or the complexing agent B.
9. The method as claimed in claim 1, wherein the electrolyte A is one or more of NaOH \ KOH methanesulfonic acid, perchloric acid, fluosilicic acid, acetic acid, trichloroacetic acid, phosphoric acid, pyrophosphoric acid, sulfamic acid; the concentration of the aqueous solution of the electrolyte A is 0.02-15.9mol L-1。
10. The method of claim 1, wherein the precipitating agent is selected from the group consisting of carbon dioxide, sulfur trioxide, and corresponding aqueous solutions, alkali metal acid salts, and one or more of ammonium sulfate, ammonium oxalate, and ammonium carbonate.
11. The method of claim 1, wherein the precipitating agent is carbon dioxide.
12. The method according to claim 1, wherein the complexing agent B is one or more of ammonia-ammonium bisulfate, ammonia-ammonium sulfate, ethylenediamine-ammonium sulfate and ethylenediamine tetraacetic acid-ammonium bisulfate conjugate solution.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4283224A (en) * 1980-05-05 1981-08-11 Southwire Company Separative treatment of anode slime
CN104141045A (en) * 2014-08-20 2014-11-12 北京化工大学 Method for recovering lead oxide from waste lead plaster
CN104789776A (en) * 2014-01-16 2015-07-22 北京化工大学 Method for recovering lead oxide from waste containing lead oxide
CN106916952A (en) * 2017-01-04 2017-07-04 北京化工大学 A kind of round-robin method of sulfur acid scrap lead sulfur removal technology and its desulphurization mother solution
CN107779603A (en) * 2016-08-29 2018-03-09 北京化工大学 A kind of method that ceruse is prepared in the scrap lead from oxidation

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4283224A (en) * 1980-05-05 1981-08-11 Southwire Company Separative treatment of anode slime
CN104789776A (en) * 2014-01-16 2015-07-22 北京化工大学 Method for recovering lead oxide from waste containing lead oxide
CN104141045A (en) * 2014-08-20 2014-11-12 北京化工大学 Method for recovering lead oxide from waste lead plaster
CN107779603A (en) * 2016-08-29 2018-03-09 北京化工大学 A kind of method that ceruse is prepared in the scrap lead from oxidation
CN106916952A (en) * 2017-01-04 2017-07-04 北京化工大学 A kind of round-robin method of sulfur acid scrap lead sulfur removal technology and its desulphurization mother solution

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