CN113046787A - Electrolyte, system and method for wet lead recovery of waste lead storage battery lead plaster ternary system - Google Patents

Electrolyte, system and method for wet lead recovery of waste lead storage battery lead plaster ternary system Download PDF

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CN113046787A
CN113046787A CN202110271747.0A CN202110271747A CN113046787A CN 113046787 A CN113046787 A CN 113046787A CN 202110271747 A CN202110271747 A CN 202110271747A CN 113046787 A CN113046787 A CN 113046787A
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lead
waste
electrolyte
storage battery
plaster
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赵坤
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/06—Operating or servicing
    • 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
    • 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

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  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrolytic Production Of Metals (AREA)

Abstract

The invention relates to a system and a method for recovering lead in a waste lead storage battery, in particular to electrolyte, system and method for recovering lead by a lead plaster ternary system wet method for the waste lead storage battery. The invention aims to solve the technical problems of environmental pollution, high equipment corrosion, low recovery rate and high cost of the existing treatment method of lead plaster in waste lead-acid storage batteries, and provides a ternary system wet-process lead recovery electrolyte, a system and a method for lead plaster of waste lead-acid storage batteries. The electrolytic liquid system adopted by the lead recovery system is a ternary system of sulfuric acid, sodium sulfate and ferrous sulfate, so that the selection of lead for the anode and the plating of titanium-based lead dioxide are feasible, the recovery rate is high, the occurrence of side reaction of the anode is effectively inhibited, the generation of oxygen is avoided, the volatilization of electrolyte caused by oxygen overflow is inhibited, and the production operation environment is improved. The concentration of the adopted sulfuric acid is less than 10g/L, so that the corrosion of equipment is low, and the cost is effectively saved.

Description

Electrolyte, system and method for wet lead recovery of waste lead storage battery lead plaster ternary system
Technical Field
The invention relates to a system and a method for recovering lead in a waste lead storage battery, in particular to electrolyte, system and method for recovering lead by a lead plaster ternary system wet method for the waste lead storage battery.
Background
The existing treatment methods of lead plaster in waste lead storage batteries generally comprise the following steps:
1. pyrogenic process
The typical process of the pyrogenic process is a side-blown converter reduction smelting-silicofluoric acid electrolytic refining process, and the process has the defect that a carbonaceous reducing agent is required, so that waste gases such as lead-containing smoke dust, sulfur dioxide, carbon dioxide and the like are inevitably generated, serious environmental pollution is easily caused, and the physical health of operators is easily damaged.
2. Wet recovery process
1) Lead plaster conversion-leaching-electrodeposition method: the method comprises the steps of carrying out desulfurization conversion on lead plaster, dissolving lead sulfate and lead oxide in the lead plaster in an acidic (or alkaline) solution to prepare a lead salt electrolyte, adopting a graphite or titanium plate as an insoluble anode and a stainless steel plate as a cathode, and carrying out electrolytic deposition in an electrolytic bath to obtain lead powder at the cathode. The process has the problems of low recovery rate, high equipment corrosion and the like.
2) Lead paste leaching-electrodeposition method: the method comprises the steps of leaching lead plaster in hot sodium chloride solution to generate soluble lead chloride solution, purifying the lead chloride solution, and then sending the lead chloride solution into an electrolytic cell cathode chamber separated by a cation exchange membrane to separate lead out on a cathode, wherein the generated electrolytic lead falls into a cell bottom to be collected. The lead powder can be used for manufacturing lead paste of a new storage battery or be fused and cast into a lead ingot. The technology is simple to operate, but a large amount of chlorine gas is generated in the electrolytic process, so that equipment corrosion and environmental pollution are caused.
3) Direct lead paste electrolysis: the method comprises the steps of slurrying lead plaster with sodium hydroxide, coating the slurried lead plaster on a stainless steel cathode grid frame, electrolyzing the slurried lead plaster in 15% sodium hydroxide solution to generate electrolytic lead at a cathode, and obtaining a pure lead ingot after fusion casting. The process consumes a large amount of sulfuric acid and sodium hydroxide, and generates a large amount of sodium sulfate with low added value, so that the production cost is increased.
4) Solid-phase electrolysis of sodium hydroxide: the method comprises the steps of coating lead plaster in a stainless steel frame, using the stainless steel as an anode, using a sodium hydroxide solution with the mass fraction of 5% -20% as an electrolyte, electrolyzing at the temperature of 40-60 ℃, and casting to produce lead ingots after lead briquetting is electrolyzed. The method has the disadvantages that the volatilization of sodium hydroxide causes environmental pollution, and the separation of sodium hydroxide and sodium sulfate causes high unit consumption of sodium hydroxide.
Disclosure of Invention
The invention aims to solve the technical problems of environmental pollution, high equipment corrosion, low recovery rate and high cost of the existing treatment method of lead plaster in waste lead-acid storage batteries, and provides a ternary system wet-process lead recovery electrolyte, a system and a method for lead plaster of waste lead-acid storage batteries.
In order to solve the technical problems, the technical solution provided by the invention is as follows:
the invention provides a wet lead recovery electrolyte for a waste lead storage battery lead plaster ternary system, which is characterized in that: the electrolyte is a mixed solution of sulfuric acid, sodium sulfate and ferrous sulfate.
Further, the concentration of the sulfuric acid is 0.05-10 g/L, the concentration of the sodium sulfate is 71-300g/L, and the concentration of the ferrous sulfate is 0.1-5 g/L.
The invention also provides a lead wet recovery system for the waste lead storage battery lead plaster ternary system, which comprises an electrolytic bath; it is characterized in that:
the electrolytic cell also comprises a plurality of cathode frames and a plurality of anode plates which are arranged in the electrolytic cell; the cathode frame is a shutter type cathode frame, a closed frame is formed by four battens in a surrounding mode, and a plurality of battens which are parallel to each other and form the same included angle with the plane of the closed frame are arranged in the closed frame;
the cathode frames and the anode plates are parallel to each other and arranged at intervals and are arranged in the electrolytic bath;
lead paste is coated in the cathode frames;
the cathode frame is made of stainless steel;
the anode plate is a lead plate or a titanium-based lead dioxide plated plate;
the electrolytic bath is filled with electrolyte, and the electrolyte is a mixed solution of sulfuric acid, sodium sulfate and ferrous sulfate.
Further, the concentration of the sulfuric acid is 0.05-10 g/L, the concentration of the sodium sulfate is 71-300g/L, and the concentration of the ferrous sulfate is 0.1-5 g/L.
Further, the lead plaster is directly coated in the cathode frame or is coated in the cathode frame after being granulated.
Further, the coating thickness of the lead paste is 8-12 mm.
The invention also provides a method for wet recovery of lead from the waste lead storage battery lead plaster ternary system, which is characterized in that the wet recovery lead system based on the waste lead storage battery lead plaster ternary system comprises the following steps:
1) the cathode frame and the anode plate are electrified with direct current, and the current density is controlled to be 60-250A/m2Electrolyzing for 28-90 hours at 15-45 ℃;
2) after the electrolysis is finished, taking the electrolytic lead out of the cathode frame, washing the electrolytic lead with hot water at the temperature of 40-80 ℃ and pressing the electrolytic lead into lead clusters;
3) and (4) casting the lead mass to obtain a lead ingot.
Further, the step 2) is followed by the following steps:
A1) and neutralizing the electrolyzed solution with sodium carbonate until the pH value is 5-6.5, and then opening a part of the electrolyzed solution to prepare sodium sulfate.
Further, step a1) is followed by the following steps:
A2) and returning the rest neutralized electrolyzed solution to the electrolyte of the electrolytic cell for continuous electrolysis.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the electrolyte, the system and the method for recovering lead by the wet process for the ternary system of lead plaster of the waste lead storage battery, provided by the invention, the adopted electrolytic liquid system is a ternary system of sulfuric acid, sodium sulfate and ferrous sulfate, so that the selection of lead and titanium-based plated lead dioxide for the anode becomes feasible, the recovery rate is high, the occurrence of anode side reaction is effectively inhibited, the generation of oxygen is avoided, the volatilization of the electrolyte caused by the overflow of the oxygen is inhibited, and the production operation environment is improved.
2. According to the electrolyte, the system and the method for recovering lead by the wet process for the waste lead storage battery lead plaster ternary system, the concentration of sulfuric acid is less than 10g/L, the electrolyte is weakly acidic, the corrosivity is low, the corrosivity of sodium sulfate salt is also low, the equipment corrosion is low, and the cost is effectively saved.
3. According to the wet lead recovery electrolyte, the system and the method for the waste lead storage battery lead plaster ternary system, sulfate radicals in a solid phase enter a liquid phase in a sulfuric acid form to be enriched under the action of direct current, and are separated from the system in a sodium sulfate byproduct form, so that the aim of electrolytic desulfurization is fulfilled, and the method is a novel process for electrolytic desulfurization.
4. The electrolyte, the system and the method for recovering lead by the wet process for the lead paste ternary system of the waste lead storage battery have wide application range, and can be used for treating acid batteries, valve-controlled batteries and the like in waste silica gel batteries and waste lead storage batteries.
5. The existing wet method for treating the waste lead storage battery has no large-scale factory, the groove pressure is increased after the silica gel in the waste silica gel battery is enriched, the electrolytic efficiency is poor, and the cost is high, so the method stays in the research and development stage all the time. The electrolyte, the system and the method for recovering lead by the wet process of the ternary system of lead plaster of the waste lead storage battery have the advantages of low acidity of the electrolyte solution, low dissolution rate of silicon, no influence on the electrolysis efficiency and affordable cost for industrialization, so that the industrialization is feasible, and the wet recovery of a silica gel battery is feasible.
Drawings
FIG. 1 is a schematic structural diagram of a wet lead recovery system of a ternary system of lead plaster of a waste lead storage battery according to the present invention;
description of reference numerals:
1-electrolytic bath, 2-cathode frame, 3-anode plate, 4-lead plaster and 5-electrolyte.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
The waste lead storage battery adopts a silica gel battery, the lead paste 4 contains 76.94% of lead component, and the lead matrix phase comprises (%):
pb Total PbO PbSO4 PbO2 Pb
76.94 13.24 26.23 26.12 11.35
1. 22.5L of electrolyte 5 is prepared in a 25L electrolytic tank 1, the concentration of sulfuric acid in the electrolyte 5 is 0.1g/L, the concentration of sodium sulfate is 183g/L, and the concentration of ferrous sulfate is 0.89 g/L;
2. after 1392g (dry weight) of lead paste 4 is coated in a stainless steel cathode frame 2, the size of the cathode frame 2 is 200 x 10mm, the cathode frame 2 is a louver type cathode frame, four battens enclose a closed frame, and a plurality of battens which are parallel to each other and form the same included angle with the plane of the closed frame are arranged in the closed frame;
3. putting the lead-coated cathode frame 2 aged for 1 hour into an electrolytic bath 1, putting 200 × 3mm titanium-based lead dioxide plated anode plates 3 into two sides of the cathode frame 2 respectively, and keeping the same polar distance of 100 mm;
4. connecting wires, loading direct current, adopting constant current mode, and keeping current density 125A/m2The average cell pressure is 2.59v, after electrolysis is carried out for 45 hours at 25 ℃, power is cut off, electrolytic lead in a cathode frame 2 is taken out, 1512.6g (moisture content is 25.92 percent and lead content is 95.12 percent) is weighed, the electrolytic lead is soaked in hot water at 50 ℃ for 30 minutes and then pressed into lead clusters, the lead clusters are cast in a muffle furnace at 650 ℃ for 40 minutes, and finally 922.51g (lead content is 99.93 percent) of lead ingots are obtained, and dross 182.38 (lead content is 71.83 percent) is obtained;
after the electrolysis, the electrolyzed solution contains 7.26g/l of sulfuric acid, 173.63g of sodium carbonate is added, the pH value of the solution is adjusted to 6.5, one part of the solution is opened for preparing sodium sulfate, and the rest part of the solution is returned to the electrolyte 5 for continuous electrolysis (continuous circulation).
Example 2
The waste lead storage battery adopts a silica gel battery, the lead paste 4 contains 76.94% of lead component, and the lead matrix phase comprises (%):
pb Total PbO PbSO4 PbO2 Pb
76.94 13.24 26.23 26.12 11.35
1. 22.5L of electrolyte 5 is prepared in a 25L electrolytic tank 1, the concentration of sulfuric acid in the electrolyte 5 is 0.05g/L, the concentration of sodium sulfate is 217g/L, and the concentration of ferrous sulfate is 3 g/L;
2. after 1292g (dry weight) of lead paste 4 is coated in a stainless steel cathode frame 2, the size of the cathode frame 2 is 200 x 9mm, the cathode frame 2 is a louver type cathode frame, four battens enclose a closed frame, and a plurality of battens which are parallel to each other and form the same included angle with the plane of the closed frame are arranged in the closed frame;
3. loading a plate-coated cathode frame 2 which is finished for 1 hour into an electrolytic bath 1, and loading two pieces of 200 x 3mm anode plates 3 at two sides of the cathode frame 2, wherein the anode is a metal anode and keeps the same polar distance of 100 mm;
4. connecting wires, loading direct current, adopting constant current mode, and keeping current density 150A/m2Average cell pressure is 2.71v, after electrolysis is carried out for 32 hours at 30 ℃, power is cut off, electrolytic lead in a cathode frame 2 is taken out, 1386g (moisture is 24.92 percent and lead content is 94.84 percent) is weighed, after soaking in hot water at 50 ℃ for 30 minutes, briquetting is carried out, then briquetting lead is cast in a muffle furnace at 650 ℃ for 40 minutes, and finally 852.46g of lead ingot (lead content is 99.91 percent) is obtained, and scum 196.32 (lead content is 70.29 percent) is obtained;
5. after the electrolysis is finished, the sulfuric acid concentration of the electrolyzed solution is 6.29g/L, 156.3g of sodium carbonate is added, the pH value of the solution is adjusted to 6.0, one part of the solution is returned to the electrolyte 5 for continuous electrolysis, and the rest part is recycled for preparing sodium sulfate.
Example 3
The lead plaster (4) is an acid waste lead battery material, contains 74.43% of lead component and (%):
pb Total PbO PbSO4 PbO2 Pb
74.43 12.71 37.24 20.64 3.84
1. 22.5L of electrolyte 5 is prepared in a 25L electrolytic tank 1, the concentration of sulfuric acid in the electrolyte 5 is 5g/L, the concentration of sodium sulfate is 296g/L, and the concentration of ferrous sulfate is 0.1 g/L;
2. after 1392g (dry weight) of lead paste 2 is coated in a stainless steel cathode frame 2, the size of the cathode frame 2 is 200 x 9mm, the cathode frame 2 is a louver type cathode frame, four battens enclose a closed frame, and a plurality of battens which are parallel to each other and form the same included angle with the plane of the closed frame are arranged in the closed frame;
3. loading a lead-coated cathode frame 2 aged for 1 hour into an electrolytic bath 1, loading two pieces of 200 x 3mm anode plates 3 at two sides of the cathode frame 2, wherein the anode is titanium-based iridium-coated tantalum and keeps the same polar distance of 100 mm;
4. connecting wires, loading direct current, adopting constant current mode, and keeping current density at 60A/m2The average cell pressure is 2.39V, after electrolysis is carried out for 90 hours at the temperature of 45 ℃, power is cut off, electrolytic lead in a cathode frame 2 is taken out, 1498g (containing 28.18% of moisture and 95.03% of lead) is weighed, after the electrolytic lead is soaked in hot water at the temperature of 80 ℃ for 30 minutes, briquetting is carried out, then the briquetting lead is cast in a muffle furnace at the temperature of 650 ℃ for 40 minutes, and finally 941g of lead ingot (containing 99.74%) is obtained, and scum 118 (containing 71.27%) is obtained;
5. after the electrolysis is finished, the sulfuric acid concentration of the electrolyzed solution is 15.25g/L, 444g of sodium carbonate is added, the pH value of the solution is adjusted to 6.0, one part of the solution is opened for preparing sodium sulfate, and the rest part of the solution is returned to the electrolyte 5 for continuous electrolysis (continuous circulation).
Example 4
The lead plaster (4) is an acid waste lead battery material, contains 74.43% of lead component and (%):
pb Total PbO PbSO4 PbO2 Pb
74.43 12.71 37.24 20.64 3.84
1. 22.5L of electrolyte 5 is prepared in a 25L electrolytic tank 1, the concentration of sulfuric acid in the electrolyte 5 is 10g/L, the concentration of sodium sulfate is 71g/L, and the concentration of ferrous sulfate is 5 g/L;
2. after 1531g (dry weight) of lead paste 4 is coated in a stainless steel cathode frame 2, the size of the cathode frame 2 is 200 x 12mm, the cathode frame 2 is a louver type cathode frame, a closed frame is enclosed by four battens, and a plurality of battens which are parallel to each other and form the same included angle with the plane of the closed frame are arranged in the closed frame;
3. putting the lead-coated cathode frame 2 aged for 1 hour into an electrolytic bath 1, putting two pieces of 200 x 3mm anode plates 3 at two sides of the cathode frame 2, wherein the anode is a metal lead anode and keeps the same polar distance of 100 mm;
4. connecting wires, loading direct current, adopting constant current mode, and keeping current density at 250A/m2Average cell pressure is 3.17v, after electrolysis is carried out for 28 hours at 15 ℃, power is cut off, electrolytic lead in a cathode frame 2 is taken out, 1678g of electrolytic lead is weighed (water content is 29.41 percent, lead content is 94.25 percent), after the electrolytic lead is soaked in hot water at 40 ℃ for 60 minutes, the electrolytic lead is pressed into lead clusters, the lead clusters are cast in a muffle furnace at 650 ℃ for 40 minutes, and finally 1007g of lead ingot (lead content is 99.08 percent) is obtained, and dross 182 (lead content is 72.45 percent) is obtained;
5. after the electrolysis is finished, the electrolyzed solution contains 21.28g/L of sulfuric acid, 520g of sodium carbonate is added, the pH value of the solution is adjusted to 5.0, one part of the solution is opened for preparing sodium sulfate, and the rest part of the solution is returned to the electrolyte 5 for continuous electrolysis (continuous circulation).
Finally, it should be noted that: the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same, and it is obvious for a person skilled in the art to modify the specific technical solutions described in the foregoing embodiments or to substitute part of the technical features, and these modifications or substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions protected by the present invention.

Claims (9)

1. The wet lead recovery electrolyte for the waste lead storage battery lead plaster ternary system is characterized by comprising the following components in parts by weight: the electrolyte is a mixed solution of sulfuric acid, sodium sulfate and ferrous sulfate.
2. The ternary system wet lead recovery electrolyte for waste lead storage battery lead paste according to claim 1, which is characterized in that:
the concentration of the sulfuric acid is 0.05-10 g/L, the concentration of the sodium sulfate is 71-300g/L, and the concentration of the ferrous sulfate is 0.1-5 g/L.
3. A wet lead recovery system for a waste lead storage battery lead plaster ternary system comprises an electrolytic bath (1); the method is characterized in that:
also comprises a plurality of cathode frames (2) and a plurality of anode plates (3) which are arranged in the electrolytic bath (1); the cathode frame (2) is a shutter type cathode frame, four battens are enclosed to form a closed frame, and a plurality of battens which are parallel to each other and form the same included angle with the plane of the closed frame are arranged in the closed frame;
the cathode frames (2) and the anode plates (3) are parallel to each other and arranged at intervals and are arranged in the electrolytic tank (1);
lead plaster (4) is coated in each cathode frame (2);
the cathode frame (2) is made of stainless steel;
the anode plate (3) is a lead plate or a titanium-based lead dioxide plated plate;
electrolyte (5) is contained in the electrolytic tank (1), and the electrolyte (5) is a mixed solution of sulfuric acid, sodium sulfate and ferrous sulfate.
4. The ternary system wet lead recovery system for waste lead storage battery lead plaster according to claim 3, characterized in that:
the concentration of the sulfuric acid is 0.05-10 g/L, the concentration of the sodium sulfate is 71-300g/L, and the concentration of the ferrous sulfate is 0.1-5 g/L.
5. The ternary system wet lead recovery system for waste lead storage battery lead plaster according to claim 4, characterized in that:
the lead plaster (4) is directly coated in the cathode frame (2) or is coated in the cathode frame (2) after granulation.
6. The ternary system wet lead recovery system for waste lead storage battery lead plaster according to claim 5, characterized in that:
the coating thickness of the lead plaster is 8-12 mm.
7. A method for recovering lead from a waste lead storage battery by a ternary system wet process lead is characterized in that the method is based on the ternary system wet process lead recovery system for the lead of the waste lead storage battery of any one of claims 3 to 6 and comprises the following steps:
1) the cathode frame (2) and the anode plate (3) are electrified with direct current, and the current density is controlled to be 60-250A/m2Electrolyzing for 28-90 hours at 15-45 ℃;
2) after the electrolysis is finished, taking out the electrolytic lead from the cathode frame (2), washing the electrolytic lead with hot water at the temperature of 40-80 ℃ and pressing the electrolytic lead into lead clusters;
3) and (4) casting the lead mass to obtain a lead ingot.
8. The ternary system wet lead recovery method for lead plaster of waste lead storage batteries according to claim 7, characterized in that the following steps are included after step 2):
A1) and neutralizing the electrolyzed solution with sodium carbonate until the pH value is 5-6.5, and then opening a part of the electrolyzed solution to prepare sodium sulfate.
9. The ternary system wet lead recovery method for lead plaster of waste lead storage batteries according to claim 8, characterized in that step A1) is followed by the following steps:
A2) returning the remaining neutralized post-electrolysis solution to the electrolyte solution (5) of the electrolytic cell (1) for further electrolysis.
CN202110271747.0A 2021-03-12 2021-03-12 Electrolyte, system and method for wet lead recovery of waste lead storage battery lead plaster ternary system Pending CN113046787A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115094484A (en) * 2022-06-12 2022-09-23 马光甲 Process for treating waste lead storage battery by rotating cathode and four rows of anodes in sulfuric acid solution through continuous solid phase, ionic electrolysis, oxidation and mechanical separation

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101608264A (en) * 2009-06-30 2009-12-23 张天任 A kind of waste lead recovering method for lead-acid storage batteries
JP2010222625A (en) * 2009-03-23 2010-10-07 Nippon Mining & Metals Co Ltd Electrolytic method (2) for lead
CN101949031A (en) * 2010-10-18 2011-01-19 中南大学 Composite porous electrode for sulfuric acid system and preparation method thereof
CN110129568A (en) * 2019-03-25 2019-08-16 厦门潼源科技有限公司 A kind of lead-acid accumulator resource recycling method
CN111485251A (en) * 2020-06-02 2020-08-04 赵坤 System and method for recovering lead in waste lead-acid storage battery

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010222625A (en) * 2009-03-23 2010-10-07 Nippon Mining & Metals Co Ltd Electrolytic method (2) for lead
CN101608264A (en) * 2009-06-30 2009-12-23 张天任 A kind of waste lead recovering method for lead-acid storage batteries
CN101949031A (en) * 2010-10-18 2011-01-19 中南大学 Composite porous electrode for sulfuric acid system and preparation method thereof
CN110129568A (en) * 2019-03-25 2019-08-16 厦门潼源科技有限公司 A kind of lead-acid accumulator resource recycling method
CN111485251A (en) * 2020-06-02 2020-08-04 赵坤 System and method for recovering lead in waste lead-acid storage battery

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115094484A (en) * 2022-06-12 2022-09-23 马光甲 Process for treating waste lead storage battery by rotating cathode and four rows of anodes in sulfuric acid solution through continuous solid phase, ionic electrolysis, oxidation and mechanical separation

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