CN114606393A - Waste lead paste recovery method - Google Patents
Waste lead paste recovery method Download PDFInfo
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- CN114606393A CN114606393A CN202210093912.2A CN202210093912A CN114606393A CN 114606393 A CN114606393 A CN 114606393A CN 202210093912 A CN202210093912 A CN 202210093912A CN 114606393 A CN114606393 A CN 114606393A
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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
- C22B13/02—Obtaining lead by dry processes
- C22B13/025—Recovery from waste materials
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G21/00—Compounds of lead
- C01G21/02—Oxides
- C01G21/06—Lead monoxide (PbO)
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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
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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
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention relates to the technical field of waste lead plaster recovery and conversion, and provides a waste lead plaster recovery method aiming at the problems of environmental pollution and low efficiency of waste lead plaster recovery: reacting waste lead plaster with ammonium acetate, filtering and separating to obtain lead acetate solution a and lead slag b, adding ammonia and CO into a2Reacting, filtering and separating to obtain high-purity lead carbonate solid c1 and a mixed solution d of ammonium acetate and ammonium sulfate, wherein d is circularly used for dissolving the waste lead plaster; b roasting to obtain crude lead oxide e, reacting with purifying reagent to obtain complex lead liquid f, f and CO2Reacting, filtering and separating to obtain high-purity lead carbonate c2 and a complexing solution g which replaces a purifying reagent to be recycled for purifying e; c1 and c2 are heatedLead oxide h and CO2H grinding to obtain battery-grade lead oxide product, CO2And circulating for the previous steps. The method is reasonably designed, so that the lead oxide prepared by recovering the waste lead paste has high purity, and other products can be recycled except solid impurities generated after the crude lead oxide is purified in the whole process, so that the method is environment-friendly.
Description
Technical Field
The invention relates to the technical field of waste lead paste recovery and conversion, in particular to a waste lead paste recovery method.
Background
At present, lead is mainly produced from galena with lead content of more than 50 percent, low-grade multi-metal ore and lead-containing waste are comprehensively recycled and recycled with the continuous consumption and reduction of mineral resources, and the recycling of secondary lead becomes an indispensable important component for realizing the sustainable development strategy of the lead industry. The production energy consumption of the lead recovered from the waste acid storage battery is about 1/3 lower than that of the original lead, and simultaneously, the harm of mining, selection and metallurgy to the environment and human bodies can be reduced, so that the yield of the secondary lead in China can be increased and reaches or exceeds the production level of the original lead. The lead storage battery industry has rapidly developed, and the number of waste lead storage batteries produced each year is increasing. The lead-acid storage battery is the battery with the largest output and the widest application in various batteries in the world, and the consumed lead amount accounts for 82 percent of the total global lead consumption amount. In order to save limited mineral resources and avoid the pollution of waste lead materials to the environment, the recycling of the waste lead materials is very important at home and abroad, and governments in various countries strongly support the research on the secondary lead production and the new secondary lead production technology for recovering lead from waste lead storage batteries. Meanwhile, the recovery of lead can generate great economic and social benefits, and a plurality of lead production enterprises and battery production enterprises are added into the lead recovery industry.
The complex components of the waste lead paste always form a key and difficult problem to be solved in the lead recovery. In the traditional technology, waste lead paste is generally calcined by a pyrogenic process to prepare lead oxide, although the process is relatively simple, the environmental pollution is serious, the purity of the obtained lead oxide is too low, and the particle size of the product is large, so that the subsequent treatment process is complicated. Chinese patent CN10138692B discloses that the components after the desulfurization of lead plaster are mixed with an aqueous solution containing an oxidant to prepare lead dioxide, but the lead dioxide is a reaction between a solid phase and a liquid phase, the particle size of the product is larger, and the finally obtained lead dioxide has more impurities. Accordingly, an ideal solution is needed.
Disclosure of Invention
The invention provides a method for recovering waste lead paste, aiming at overcoming the problems of environmental pollution and low efficiency of the recovery of the waste lead paste.
In order to achieve the purpose, the invention adopts the following technical scheme:
a waste lead paste recovery method comprises the following steps:
(1) dissolving and purifying lead sulfate in the waste lead paste: reacting the waste lead plaster with ammonium acetate, filtering and separating to obtain a lead acetate solution and undissolved lead slag;
the reaction takes place as follows: PbSO4+2CH3COONH4→(CH3COO)2Pb+(NH4)2SO4
(2) Preparing lead carbonate: adding ammonia or ammonia water into the lead acetate solution obtained in the step (1) and introducing carbon dioxide, reacting to obtain a lead carbonate mixed solution, filtering and separating to obtain a high-purity lead carbonate solid and a mixed solution of ammonium acetate and ammonium sulfate, wherein the mixed solution of ammonium acetate and ammonium sulfate is circularly used for dissolving the waste lead plaster in the step (1);
the reaction takes place as follows: (CH)3COO)2Pb+CO2+2NH3+H2O→PbCO3+2CH3COONH4
(3) Roasting undissolved lead slag to prepare crude lead oxide: roasting, cooling and grinding the undissolved lead slag obtained in the step (1) to obtain crude lead oxide;
the reaction takes place as follows: PbO2+Pb→PbO，2PbO2→2PbO+O2
(4) And (3) purifying crude lead oxide: reacting the crude lead oxide obtained in the step (3) with a purification reagent, filtering and separating to remove impurities in the crude lead oxide to obtain pure complex lead liquid;
the purification reagent is denoted by R, and the reaction takes place as follows: PbO + R + H2O→PbR2++2OH-
(5) Preparing lead carbonate by complexing lead liquid: introducing carbon dioxide gas into the complex lead liquid obtained in the step (4), stirring and reacting for 0.5-1h at the temperature of 60-70 ℃, carrying out solid-liquid separation to obtain high-purity lead carbonate and a complex solution, wherein the complex solution can be used for replacing a purification reagent and circularly purifying the crude lead oxide in the step (4);
the reactions that occur are as follows: CO 22+PbR2++2OH-→PbCO3+R+H2O
(6) Preparing battery-grade lead oxide from lead carbonate: and (3) combining the high-purity lead carbonate obtained in the step (2) and the step (4), heating to react to obtain lead oxide and carbon dioxide gas, grinding the lead oxide to obtain a battery-grade lead oxide product, and recycling the carbon dioxide gas for the step (2) and the step (5).
The reactions that occur are as follows: PbCO3→PbO+CO2
Preferably, the molar mass ratio of the lead sulfate to the ammonium acetate in the waste lead paste in the step (1) is 1 (2.5-5), and the reaction condition is that the temperature is kept between 50 ℃ and 90 ℃ for 0.5-1 h. Detecting the content of lead sulfate in the waste lead plaster, calculating the molar mass of lead sulfate in a certain amount of waste lead plaster according to the content of lead sulfate, and putting a certain amount of waste lead plaster (calculated according to the molar mass of lead sulfate in the waste lead plaster) and ammonium acetate with the mass concentration of 10-20% into a reactor according to the molar mass ratio of 1 (2.5-5).
Preferably, the mixed solution of ammonium acetate and ammonium sulfate in the step (2) is continuously used for dissolving the waste lead plaster in the step (1), calcium oxide or calcium hydroxide is added into the mixed solution of ammonium acetate and ammonium sulfate after the mixed solution is circularly dissolved for 2-3 times, after the reaction is finished, the mixed solution of gypsum solid and ammonium acetate and ammonia is obtained by filtration and separation, and the mixed solution of ammonium acetate and ammonia is continuously and circularly used for dissolving the waste lead plaster in the step (1).
The reaction formula is as follows: (NH)4)2SO4+Ca(OH)2→CaSO4+2NH3.H2O
More preferably, the amount of calcium oxide or calcium hydroxide added is 1 to 1.5 times the molar mass of sulfate radical in the mixed solution, and the reaction conditions are stirring reaction at normal temperature for 1 to 2 hours.
Preferably, the roasting condition in the step (3) is 550-650 ℃ roasting for 1-2 h.
Preferably, the purification reagent in step (4) is one of an organic acid, an alpha amino acid or an organic amine.
Preferably, the purification reaction in step (4) is carried out under stirring at 60-100 deg.C for 1-3 h.
Preferably, the heating reaction in the step (6) is carried out under the conditions of 400 ℃ and 480 ℃ for 1-3 h. As a further preference, the high-purity lead carbonate is pre-dried at the temperature of 100 ℃ and 150 ℃ for 1-2h before the heating reaction in the step (6).
Preferably, step (6) grinds the lead oxide to a particle size of 1-3 μm.
Therefore, the beneficial effects of the invention are as follows: (1) the method is an environment-friendly, low-consumption and high-efficiency waste lead paste recovery method, the synthesis cost is low, solid impurities generated after the whole process of removing the crude lead oxide and purifying by-products can be recycled by screening the reagent added in each step, zero waste is basically realized, and the total lead recovery rate is more than 99%; (2) the purity of the prepared lead oxide is as high as more than 99.9 percent, and the lead oxide can be directly used for preparing batteries; (3) the separation can be realized through simple filtration in the process, the energy is saved, the environment is protected, and the method is suitable for large-scale production.
Drawings
FIG. 1 is a flow chart of the recovery of waste lead paste according to the present invention.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
In the present invention, unless otherwise specified, all the raw materials and equipment used are commercially available or commonly used in the art, and the methods in the examples are conventional in the art unless otherwise specified.
General examples
A method for recovering waste lead paste, as shown in fig. 1, comprising the steps of:
(1) dissolving and purifying lead sulfate in the waste lead paste: detecting the content of lead sulfate in the waste lead plaster, calculating the molar mass of a certain amount of lead sulfate in the waste lead plaster according to the content of lead sulfate, putting the waste lead plaster (calculated according to the molar mass of lead sulfate in the waste lead plaster) and ammonium acetate with the mass concentration of 10-20% into a reactor according to the molar mass ratio of 1 (2.5-5), heating to 50-90 ℃, carrying out heat preservation reaction for 0.5-1h, filtering and separating after the reaction is finished to obtain a clarified lead acetate solution and undissolved lead slag;
the reaction takes place as follows: PbSO4+2CH3COONH4→(CH3COO)2Pb+(NH4)2SO4
(2) Preparing lead carbonate: adding ammonia or ammonia water into the lead acetate solution obtained in the step (1), introducing carbon dioxide, reacting for 0.5-1h to obtain a lead carbonate mixed solution, filtering and separating to obtain a high-purity lead carbonate solid and a mixed solution of ammonium acetate and ammonium sulfate, circularly using the mixed solution of ammonium acetate and ammonium sulfate for dissolving the waste lead plaster obtained in the step (1), adding calcium oxide or calcium hydroxide (the addition amount of the calcium oxide is 1-1.5 times of the molar mass of sulfate) into the mixed solution of ammonium acetate and ammonium sulfate after circularly dissolving for 2-3 times, stirring and reacting for 1-2h at normal temperature, filtering and separating after the reaction is finished to obtain a mixed solution of gypsum solid, ammonium acetate and ammonia, and circularly using the mixed solution of ammonium acetate and ammonia for dissolving lead sulfate;
the reaction takes place as follows: (CH)3COO)2Pb+CO2+2NH3+H2O→PbCO3+2CH3COONH4
(NH4)2SO4+Ca(OH)2→CaSO4+2NH3.H2O
(3) Roasting undissolved lead slag to prepare crude lead oxide: putting the undissolved lead slag obtained in the step (1) into an atmosphere furnace or a rotary kiln, heating to 550-650 ℃, roasting for 1-2h, cooling, and grinding to obtain crude lead oxide;
the reaction takes place as follows: PbO2+Pb→PbO
2PbO2→2PbO+O2
(4) And (3) purifying crude lead oxide: stirring the crude lead oxide obtained in the step (3) and a purification reagent at 60-100 ℃ for reacting for 1-3h, filtering and separating after the reaction is finished to remove impurities in the crude lead oxide to obtain a pure complex lead solution, wherein the purification reagent is organic acid, alpha amino acid or organic amine;
the purification reagent is denoted by R, and the reaction takes place as follows: PbO + R + H2O→PbR2++2OH-
(5) Preparing lead carbonate by complexing lead liquid: introducing carbon dioxide gas into the complex lead liquid obtained in the step (4), stirring and reacting for 0.5-1h at the temperature of 60-70 ℃, carrying out solid-liquid separation to obtain high-purity lead carbonate and a complex solution, wherein the complex solution can be used for replacing a purification reagent and circularly purifying the crude lead oxide in the step (4);
the reactions that occur are as follows: CO 22+PbR2++2OH-→PbCO3+R+H2O
(6) Preparing battery-grade lead oxide from lead carbonate: and (3) combining the high-purity lead carbonate obtained in the step (2) and the step (4), putting the combined high-purity lead carbonate into a rotary kiln, heating to 100-150 ℃, pre-drying for 1-2h, then heating to 400-480 ℃, reacting for 1-3h to obtain lead oxide and carbon dioxide gas, grinding the lead oxide to obtain a battery-grade lead oxide product with the diameter of 1-3 mu m, and recycling the carbon dioxide gas for the step (2) and the step (5).
The reactions that occur are as follows: PbCO3→PbO+CO2
The purity of the prepared lead oxide product is more than 99.9 percent, and the total lead recovery rate is more than 99 percent.
Example 1
A method for recovering waste lead paste comprises the following steps:
1. 100g of waste lead plaster, detecting the lead sulfate content to be about 40%, putting the waste lead plaster into a reactor, then adding 204g of ammonium acetate solution with the mass concentration of 10% into the reactor, heating to 65 ℃, keeping the temperature, reacting for 1h, filtering and separating after the reaction is finished to obtain 54.2g of clarified lead acetate solution and undissolved lead slag;
2. adding 23g of ammonia water into the clarified lead acetate solution at normal temperature, introducing carbon dioxide, reacting for 0.5h, precipitating to obtain a lead carbonate mixed solution, and filtering and separating to obtain 46.9g of high-purity lead carbonate solid and a mixed solution of ammonium acetate and ammonium sulfate. Preparing battery-grade lead oxide for lead carbonate, continuously using a mixed solution of ammonium acetate and ammonium sulfate for secondary dissolution of lead sulfate in waste lead paste, adding 39g of calcium hydroxide into the mixed solution of ammonium acetate and ammonium sulfate after dissolution, stirring and reacting at normal temperature for 1h, filtering and separating after the reaction is finished to obtain 19.3g of gypsum and a mixed solution of ammonium acetate and ammonia, and circularly using the mixed solution of ammonium acetate and ammonia for lead sulfate dissolution;
3. putting 54.2g of the undissolved lead slag obtained in the step 1 into an atmosphere furnace, heating to 550 ℃, roasting for 2h, cooling and grinding to obtain 42.6g of crude lead oxide;
4. adding 42.6g of crude lead oxide into a purification reaction kettle, adding 160g/L of a purification reagent alpha amino acid, stirring and reacting for 3 hours at 60 ℃, filtering and separating to remove impurities in the crude lead oxide after the reaction is finished so as to obtain pure complex lead liquid;
5. introducing carbon dioxide gas into the complexing lead liquid, stirring and reacting for 1h at 60 ℃, carrying out solid-liquid separation to obtain 55.7g of high-purity lead carbonate and a complexing solution, wherein the high-purity lead carbonate and the high-purity lead carbonate prepared in the step 2 are used together for preparing battery-grade lead oxide, and the complexing solution contains alpha amino acid, so that the purifying reagent in the step 4 can be replaced for purifying crude lead oxide;
6. and (3) combining 102.6g of high-purity lead carbonate obtained in the step (2) and the step (5), putting into a rotary kiln, heating to 150 ℃, pre-drying for 1h, heating to 440 ℃, reacting for 2h to obtain lead oxide and a byproduct carbon dioxide gas, grinding the lead oxide to obtain 74.1g of battery-grade lead oxide product with the particle size of 1.84 microns and the purity of 99.92%, recovering 99.2% of total lead, and recycling the carbon dioxide gas for preparing the lead carbonate in the step (2) and the step (5).
Example 2
A method for recovering waste lead paste comprises the following steps:
1. 100g of waste lead plaster, detecting the lead sulfate content to be about 35%, putting the waste lead plaster into a reactor, then adding the ammonium acetate solution recycled in the step 2 in the embodiment 1 into the reactor, heating to 75 ℃, keeping the temperature, reacting for 0.5h, filtering and separating after the reaction is finished to obtain a clarified lead acetate solution and 61.9g of undissolved lead slag;
2. and (3) introducing the carbon dioxide generated in the step 6 in the example 1 into the clarified lead acetate solution at normal temperature, reacting for 1h, precipitating to obtain a lead carbonate mixed solution, and filtering and separating to obtain high-purity lead carbonate solid 41g and a mixed solution of ammonium acetate and ammonium sulfate. Preparing battery-grade lead oxide by using lead carbonate for later use, continuously dissolving the mixed solution of ammonium acetate and ammonium sulfate for the second time of lead sulfate in the waste lead paste, adding 41g of calcium hydroxide into the mixed solution of ammonium acetate and ammonium sulfate after dissolving, stirring and reacting at normal temperature for 1h, filtering and separating after the reaction is finished to obtain 16.9g of gypsum, and the mixed solution of ammonium acetate and ammonia for circularly dissolving lead sulfate;
3. putting 61.9g of undissolved lead paste obtained in the step 1 into a rotary kiln, heating to 650 ℃, roasting for 1h, cooling and grinding to obtain 55.7g of crude lead oxide;
4. adding 55.7g of crude lead oxide into a purification reaction kettle, adding the complexing solution obtained in the step 5 in the example 1, stirring and reacting for 2 hours at 70 ℃, filtering and separating to remove impurities in the crude lead oxide after the reaction is finished, and obtaining pure complexing lead liquid;
5. introducing carbon dioxide gas generated in the step 6 in the example 1 into the complex lead liquid, stirring and reacting for 1h at 65 ℃, carrying out solid-liquid separation to obtain 63.7g of high-purity lead carbonate and a complex solution, preparing battery-grade lead oxide by using the lead carbonate and the lead carbonate prepared in the step 2 together, and circularly using the complex solution for purifying crude lead oxide in the step 4;
6. and (3) putting 110.6g of the obtained high-purity lead carbonate into a rotary kiln, heating to 100 ℃, pre-drying for 2h, heating to 480 ℃, reacting for 1h to obtain lead oxide and a byproduct carbon dioxide gas, grinding the lead oxide to obtain 80.4g of a battery-grade lead oxide product with the particle size of 1.97 microns and the purity of 99.96%, and recycling the carbon dioxide gas with the lead recovery rate of 99.8% for preparing the lead carbonate in the steps 2 and 5.
Comparative example 1
A method for recovering waste lead paste comprises the following steps:
1. mixing the lead plaster with 10 wt% of sodium hydroxide solution for desulfurization reaction, wherein the dosage of the sodium hydroxide solution is controlled as follows: the molar ratio of lead sulfate in the lead plaster is 2.5:1, the temperature of the desulfurization reaction is controlled at 30 ℃, the reaction time is 8min, the desulfurization reaction is carried out under the condition of stirring, a pulse electric field is applied while stirring, the stirring speed is 800rmp, the pulse voltage of the pulse magnetic field is 100V, and the pulse frequency is 25 Hz; carrying out filter pressing on the desulfurized lead plaster, and recycling filtrate;
2. the method for recycling the filtrate comprises the following steps: adding sodium hydroxide into the filtrate to adjust the pH value to 10, then concentrating the filtrate to 40% of the original volume, cooling and crystallizing, recycling sodium sulfate as crystal obtained by filtering, adding sodium hydroxide tablets into the filtrate obtained by filtering to adjust the mass concentration to 10%, and then circularly using the filtrate for desulfurization reaction;
3. mixing the treated lead plaster with acetic acid, heating to 100 ℃, and carrying out reflux reaction for 3 hours. The dosage of the acetic acid is based on PbO in the lead plaster2And adding the molar ratio of the total lead after the lead sulfate is desulfurized and converted into PbO to the acetic acid in a ratio of 1: 4. After the reflux reaction is finished, keeping the reflux reaction temperature, and slowly dropwise adding 5% H2O2Adding excessive PbO2Reduction of H2O2The dosage is dropwise added until no bubbles appear, H2O2After the dropwise addition, continuing to perform heat preservation reaction for 1.5h, then cooling to 40 ℃, filtering, recycling filter residues to the reflux reaction in the step, adjusting the pH of filtrate to 7 by using a sodium hydroxide solution, then dropwise adding a 30 wt% sodium hydroxide solution, reacting while stirring to separate out lead oxide until no solid is separated out, stopping dropwise adding the 30 wt% sodium hydroxide solution, and continuing to stir for 20min to obtain a solid-liquid mixture; filtering the solid-liquid mixture, evaporating and concentrating the filtrate to prepare CH3COONa, washing the filter residue, drying and crushing to obtain the high-purity lead oxide solid.
Comparative example 1 is a method for recovering waste lead paste used before, compared with the method: the recovery rate is low, about 95 percent; the purity is 99.0 percent; and the energy consumption is high, the cost is high, the solid lead sulfate in the waste lead plaster is converted into solid lead oxide, the lead sulfate can not be purified and purified by one step, and simultaneously, the reagent consumption is high in the process.
Comparative example 2
A method for recovering waste lead paste comprises the following steps:
mixing the lead paste with 15 wt% of ammonium carbonate solution for desulfurization reaction, wherein the molar ratio of the ammonium carbonate to lead sulfate in the lead paste is 2.5:1, the temperature of the desulfurization reaction is controlled at 30 ℃, the reaction time is 1h, the desulfurization reaction is carried out under the conditions of stirring, shearing and grinding, the lead sulfate in the waste lead paste is converted into lead carbonate, then the lead carbonate is roasted at the temperature of 400-.
Comparative example 2 ammonium acetate of the present invention was replaced with ammonium carbonate to convert solid lead sulfate into solid lead carbonate or lead oxide, and lead sulfate could not be purified directly, and ammonium acetate was a lead acetate which directly dissolves and dissolves solid lead sulfate and can be purified and separated directly. Therefore, the method adopts the ammonium acetate to directly react with the lead sulfate in the waste lead plaster to prepare the soluble lead acetate, directly adopts the carbon dioxide and the ammonia water/ammonia to directly prepare the high-purity lead carbonate after filtering, obtains the high-purity lead oxide after roasting the lead carbonate, and has simple process and less reagent recycling consumption. Each reagent of the invention is determined after a large amount of screening, and the reagents are matched with each other to achieve the optimal effect.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. The method for recovering the waste lead paste is characterized by comprising the following steps of:
(1) dissolving and purifying lead sulfate in the waste lead paste: reacting the waste lead plaster with ammonium acetate, filtering and separating to obtain a lead acetate solution and undissolved lead slag;
(2) preparing lead carbonate: adding ammonia or ammonia water into the lead acetate solution obtained in the step (1) and introducing carbon dioxide, reacting to obtain a lead carbonate mixed solution, filtering and separating to obtain a high-purity lead carbonate solid and a mixed solution of ammonium acetate and ammonium sulfate, wherein the mixed solution of ammonium acetate and ammonium sulfate is circularly used for dissolving the waste lead plaster in the step (1);
(3) roasting undissolved lead slag to prepare crude lead oxide: roasting, cooling and grinding the undissolved lead slag obtained in the step (1) to obtain crude lead oxide;
(4) and (3) purifying crude lead oxide: reacting the crude lead oxide obtained in the step (3) with a purification reagent, filtering and separating to remove impurities in the crude lead oxide to obtain pure complex lead liquid;
(5) preparing lead carbonate by complexing lead liquid: introducing carbon dioxide gas into the complex lead liquid obtained in the step (4), stirring and reacting for 0.5-1h at the temperature of 60-70 ℃, carrying out solid-liquid separation to obtain high-purity lead carbonate and a complex solution, and circularly using the complex solution in the step (4) to replace a purification reagent to purify crude lead oxide;
(6) preparing battery-grade lead oxide from lead carbonate: and (3) combining the high-purity lead carbonate obtained in the step (2) and the step (4), heating to react to obtain lead oxide and carbon dioxide gas, grinding the lead oxide to obtain a battery-grade lead oxide product, and recycling the carbon dioxide gas in the step (2) and the step (5).
2. The method for recovering waste lead plaster according to claim 1, wherein the molar mass ratio of the lead sulfate to the ammonium acetate in the waste lead plaster in the step (1) is 1 (2.5-5), and the reaction conditions are 50-90 ℃ for 0.5-1h of heat preservation reaction.
3. The method for recovering the waste lead plaster as claimed in claim 1 or 2, wherein the mixed solution of ammonium acetate and ammonium sulfate in the step (2) is continuously used for dissolving the waste lead plaster in the step (1), calcium oxide or calcium hydroxide is added into the mixed solution of ammonium acetate and ammonium sulfate after the mixed solution is circularly dissolved for 2-3 times, after the reaction is finished, the mixed solution of ammonium acetate and ammonia is obtained by filtration and separation, and the mixed solution of ammonium acetate and ammonia is continuously and circularly used for dissolving the waste lead plaster in the step (1).
4. The method for recovering waste lead paste according to claim 3, wherein the amount of calcium oxide or calcium hydroxide added is 1 to 1.5 times of the molar mass of sulfate radicals in the mixed solution, and the reaction conditions are stirring reaction at normal temperature for 1 to 2 hours.
5. The method as claimed in claim 1, wherein the roasting condition in step (3) is 550-650 ℃ for 1-2 h.
6. The method for recovering waste lead paste according to claim 1, wherein the purification reagent in the step (4) is one of organic acid, alpha amino acid or organic amine.
7. The method for recovering waste lead paste according to claim 1 or 6, wherein the purification reaction condition in the step (4) is stirring reaction at 60-100 ℃ for 1-3 h.
8. The method as claimed in claim 1, wherein the heating reaction in step (6) is carried out at 400-480 ℃ for 1-3 h.
9. The method as claimed in claim 8, wherein the high purity lead carbonate is pre-dried at 100-150 ℃ for 1-2h before the heating reaction in step (6).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115369257A (en) * | 2022-07-12 | 2022-11-22 | 超威电源集团有限公司 | Solvent-circulated waste lead paste recovery method |
| CN115557530A (en) * | 2022-09-14 | 2023-01-03 | 超威电源集团有限公司 | Method for preparing battery-grade lead oxide from waste lead paste |
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| CN115557530A (en) * | 2022-09-14 | 2023-01-03 | 超威电源集团有限公司 | Method for preparing battery-grade lead oxide from waste lead paste |
| CN115557530B (en) * | 2022-09-14 | 2023-08-22 | 超威电源集团有限公司 | Method for preparing battery-grade lead oxide from waste lead paste |
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