CN113089024A - Method for recovering metallic lead by reducing waste lead dioxide - Google Patents

Method for recovering metallic lead by reducing waste lead dioxide Download PDF

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Publication number
CN113089024A
CN113089024A CN202011253419.XA CN202011253419A CN113089024A CN 113089024 A CN113089024 A CN 113089024A CN 202011253419 A CN202011253419 A CN 202011253419A CN 113089024 A CN113089024 A CN 113089024A
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CN
China
Prior art keywords
lead
lead dioxide
pole
waste
waste lead
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202011253419.XA
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Chinese (zh)
Inventor
胡彪
王海北
娄可柏
朱炳龙
蒋开喜
戢习武
陈甦
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tianjin University of Technology
BGRIMM Technology Group Co Ltd
Zhejiang Tianneng Power Materials Co Ltd
Original Assignee
Tianjin University of Technology
BGRIMM Technology Group Co Ltd
Zhejiang Tianneng Power Materials Co Ltd
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Publication date
Application filed by Tianjin University of Technology, BGRIMM Technology Group Co Ltd, Zhejiang Tianneng Power Materials Co Ltd filed Critical Tianjin University of Technology
Priority to CN202011253419.XA priority Critical patent/CN113089024A/en
Publication of CN113089024A publication Critical patent/CN113089024A/en
Pending legal-status Critical Current

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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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)

Abstract

A method for recovering metallic lead by reducing waste lead dioxide relates to a resource utilization technology of lead-containing waste in the field of resource recycling. Acid-resistant conductive materials are used as positive and negative electrodes, waste lead dioxide with the grain diameter less than or equal to 2mm is attached to a cathode, water or dilute sulfuric acid is used as electrolyte for electrolytic reduction, the waste lead dioxide is reduced into lead, and metallic lead is recovered from the cathode. The invention has the advantages that: the method can reduce the waste lead dioxide to recover the metallic lead, has short process flow, low energy consumption and no salt by-product in the treatment process.

Description

Method for recovering metallic lead by reducing waste lead dioxide
Technical Field
The invention relates to a resource utilization technology of lead-containing waste in the field of resource recycling, in particular to a method for recovering metallic lead by reducing waste lead dioxide.
Background
The waste lead dioxide is mainly derived from waste lead-acid storage batteries and waste lead dioxide chemical products, the lead dioxide in the waste lead-acid storage batteries accounts for about 8-12%, and metal lead is recovered from the lead dioxide, so that the method is a key problem for realizing resource utilization of lead-containing waste materials. The traditional pyrogenic process related to the treatment of waste lead dioxide is divided into two processes, one is a smelting furnace for direct high-temperature reduction to obtain metallic lead, and the other is a process for treating and recovering waste lead dioxide waste and lead concentrate in the primary lead smelting process. The wet process technology related to the treatment of waste lead dioxide can be divided into the following two types. One is the leaching-electrodeposition method. The method comprises the steps of leaching lead dioxide, dissolving the lead dioxide in an acidic (or alkaline) solution to prepare a lead salt electrolyte, taking graphite as an anode and a stainless steel plate as a cathode, and obtaining metal lead on the surface of the cathode after electrolytic deposition; the other is a direct electrolysis method represented by a solid-phase electrolytic reduction method, in which a sodium hydroxide solution is used as an electrolyte, lead dioxide is attached to the surface of an electrode, and metallic lead is obtained at a cathode after electrolysis.
Preparing cathode and anode with stainless steel plate, attaching folding tank on both sides of cathode plate, coating lead dioxide slurried with electrolyte on folding tank for electrolysis, and collecting spongy lead at cathode.
In the prior art, the defects of low recovery rate, serious secondary pollution, large energy consumption and the like exist in the pyrogenic process treatment and recovery, and the defects of waste acid and wastewater discharge, high energy consumption, complex system flow, high price of auxiliary polar plate materials, high purification cost of byproducts and the like exist in the wet process treatment and recovery.
Disclosure of Invention
The invention aims to provide a method for recovering metallic lead by reducing waste lead dioxide, which directly recovers the metallic lead from the waste lead dioxide by a wet method without conversion treatment and realizes efficient and environment-friendly recovery of the waste lead dioxide.
A method for recovering metallic lead by reducing waste lead dioxide comprises the following steps:
the method comprises the steps of concentrating waste lead dioxide with the granularity less than or equal to 2mm and adding a first kind of conductive material to form a first pole. The waste lead dioxide is concentrated by tabletting, briquetting, stacking and bagging. The first conductive material may be a carbonaceous material including graphite, 304, 309S, 310S, 316L, 317L, 904L stainless steel, titanium and its alloy, lead and its alloy, gold and its alloy, platinum and its alloy, and the structural shape of the first conductive material may be plate-like, cylindrical, arc-like, net-like, fork-like. The A kind of conductive material can be embedded during the production of the waste lead dioxide tablet and briquette, or stacked on the tablet pole material, and the waste lead dioxide is inserted into the tablet pole material.
(2) The anode is made of a conductive material B. The anode material can be carbon material containing graphite, lead and its alloy, gold and its alloy, platinum and its alloy, and the structure shape can be plate, cylinder, arc, net, and mesh.
And thirdly, placing the anode A and the anode B into the container according to a certain positional relationship. The position relation of the A pole and the B pole in the container can be vertical parallel, horizontal parallel, vertical coaxial cylindrical surface and horizontal coaxial cylindrical surface, and the A pole and the B pole in the horizontal parallel state can be up and down mutually.
And fourthly, the first pole is connected with the negative pole of the power supply, and the second pole is connected with the positive pole of the power supply.
And adding distilled water into the container, wherein the distilled water is added in an amount capable of immersing the anode and the cathode, adjusting the pH value to be between 1 and 3 by using sulfuric acid, and the density at 25 ℃ is 1.010 to 1.100 g/cubic centimeter.
Sixthly, starting a power supply to electrify, wherein the electrified voltage and current can be adjusted, the electrified voltage is more than or equal to 2 volts, and the electrified processing time range is more than or equal to 5-600 minutes. The power supply can be a steady direct current power supply, a half-wave ballast power supply, a full-wave ballast power supply and a positive pulse power supply; the pulse alternating power supply can also be a pulse alternating power supply, the pulse alternating power supply is formed by alternately compounding positive pulses and negative pulses, the positive effective value of the pulses is larger than the effective value of the negative pulses, and the ratio of the effective value of the positive pulses to the effective value of the negative pulses is larger than 1.
And converting waste lead dioxide on the treated formants into metallic lead, and recovering the metallic lead from the formants.
The invention has the advantages that: the method can reduce the waste lead dioxide to recover the metallic lead, has short process flow, low energy consumption and no salt by-product in the treatment process, and the recovered lead is easily reused in the production process of the lead-acid storage battery, thereby being an alternative technology for the pyrogenic process and the wet treatment process needing conversion.
Detailed Description
Example 1:
an implementation method for recovering metallic lead by reducing waste lead dioxide comprises the following steps:
the method comprises the steps of loading waste lead dioxide with the granularity of less than or equal to 0.15 mm into a square electrode bag, inserting a lead net into the electrode bag during bagging to be made of first-kind conductive materials, uniformly compacting after the electrode bag is filled, and enabling the bag thickness to be about 20 mm.
And the lead plate is used as a second conductive material to form a second pole, and the projection areas of the second pole and the first pole are correspondingly equal.
Thirdly, the A pole and the B pole are vertically placed into the container in a parallel mode, the distance is kept at 10 mm, and if the A pole and the B pole are provided with a plurality of pieces, the A pole and the B pole can be alternately placed in a parallel mode.
And fourthly, connecting the first pole with the negative pole of the power supply, connecting the second pole with the positive pole of the power supply, and connecting the first pole and the second pole in parallel with the negative pole and the positive pole of the power supply respectively in the case of multiple poles.
And fifthly, adding distilled water into the container in an amount capable of immersing the anode and the cathode, adjusting the pH value to be 1-3 by using sulfuric acid, and enabling the density to be 1.010-1.050 g/cc at 25 ℃.
Sixthly, starting a power supply to be electrified, wherein the electrified voltage and current can be adjusted, the electrified voltage is more than or equal to 2V, the average current density between each pair of the A pole and the B pole is 600 amperes/square meter, the electrified processing time is 320 minutes, and the used power supply is a stable direct current power supply.
And converting waste lead dioxide on the treated formants into metallic lead, and recovering the metallic lead from the formants.
Example 2:
an implementation method for recovering metallic lead by reducing waste lead dioxide comprises the following steps:
the method comprises the steps of loading waste lead dioxide with the granularity of less than or equal to 0.25 mm into a square electrode bag, inserting a lead net into the electrode bag during bagging to be made into a first kind of conductive material, uniformly compacting after the electrode bag is filled, keeping the electrode and the material to be reliably contacted, and ensuring the bagging thickness to be about 20 mm.
And the lead plate is used as a second conductive material to form a second pole, and the projection areas of the second pole and the first pole are correspondingly equal.
Thirdly, the A pole and the B pole are horizontally placed into the container in parallel, the distance is kept about 10 mm, and if the A pole and the B pole are provided with a plurality of pieces, the A pole and the B pole can be alternately placed in parallel.
Fourth, under the condition of multiple poles, all poles are respectively connected with the negative pole and the positive pole of the power supply in series according to the first pole and the second pole, the first pole plate and the last pole plate are respectively connected with the negative pole and the positive pole of the power supply,
and fifthly, adding distilled water into the container in an amount capable of immersing the anode and the cathode, adjusting the pH value to be 1-3 by using sulfuric acid, and enabling the density to be 1.010-1.050 g/cc at 25 ℃.
Sixthly, starting a power supply to be electrified, wherein the electrified voltage and current can be adjusted, the distance between the pole pieces of the first pole and the pole pieces of the second pole is adjusted, the voltage between the adjacent pole pieces is equal to or more than 2V, the average current density between each pair of the pole pieces of the first pole and the pole pieces of the second pole is equal to or more than 550 and 600 ampere/square meters, the electrifying processing time is 320 minutes, and the used power supply is a steady direct-current power supply.
And converting waste lead dioxide on the treated formants into metallic lead, and recovering the metallic lead from the formants.
Example 3:
an implementation method for recovering metallic lead from reduction waste lead dioxide comprises the following steps:
the method comprises the steps of piling waste lead dioxide with the granularity less than or equal to 0.5 mm on a plate-shaped square electrode, and uniformly spreading and compacting materials on a methyl shift.
And the lead plate is used as a second conductive material to form a second pole, and the areas of the second pole and the first pole are correspondingly equal.
Thirdly, horizontally placing the anode added with the mixed material of the waste lead sulfate and the lead dioxide into the lower part of the container, keeping the anode parallel and horizontally placing the cathode on the lower part of the container, and placing the anode plate on the anode with the distance of 10 mm.
The first pole and the second pole are respectively connected with a negative pole and a positive pole of the power supply.
And fifthly, adding distilled water into the container in an amount capable of immersing the anode and the cathode, adjusting the pH value to be 1-3 by using sulfuric acid, and controlling the density to be 1.010-1.050 g/cc at 25 ℃.
Sixthly, starting a power supply to be electrified, wherein the electrified voltage can be adjusted to ensure that the voltages between adjacent pole pieces are equal and more than or equal to 2V, the average current density between each pair of a pole A and a pole B is more than or equal to 550 and 600 amperes/square meter, the electrifying processing time is 320 minutes, and the used power supply is a stable and constant direct-current power supply.
And converting the lead dioxide on the formazan after the treatment into metallic lead, and recovering the metallic lead from the formazan.
Example 4:
an implementation method for recovering metallic lead by reducing waste lead dioxide comprises the following steps:
the manufacturing method comprises the steps of manufacturing a lead plate and a shell type conductive material into a cylindrical shell pole.
And manufacturing a cylindrical anode by using a lead-carrying plate as a conductive material of the second kind, wherein the outer diameter of the cylindrical anode is 50 mm smaller than that of a barrel armor, the height of the cylindrical anode is equal to that of the cylindrical anode, manufacturing an anode isolation cover and an anode isolation cover by using an acid-resistant electrode bag material, wherein the inner diameter of the anode isolation cover is 10 mm larger than the outer diameter of the anode, the radial thickness of the isolation cover is 10 mm, and the height of the isolation cover is equal to that of the anode and the. The anode, the shield and the cathode are coaxially assembled, waste lead dioxide with the granularity less than or equal to 0.5 mm is filled between the anode and the shield, and the volume of the filled mixture accounts for 50% of the space between the anode and the shield.
Thirdly, distilled water is added into the space between the anode and the cathode, a small amount of sulfuric acid is added to adjust the pH value to 1, the distilled water is uniformly mixed with the lead dioxide material and can be in a flowing slurry state, the two ends of the anode and the cathode are fixed by end covers and can be breathable and placed horizontally, and power is applied to enable the assembly body to rotate along the axis.
The first pole and the second pole are respectively connected with a negative pole and a positive pole of the power supply.
And fifthly, starting the power supply for electrifying, wherein the electrified voltage can be adjusted to ensure that the voltages between the adjacent pole pieces are equal and more than or equal to 2 volts, the average current density between each pair of the first pole and the second pole is more than or equal to 550-600 amperes/square meter, the electrifying processing time is 320 minutes, and the used power supply is a stable and constant direct-current power supply.
Sixthly, converting the waste lead dioxide on the processed anode into metal lead, and recycling the metal lead from the cylindrical anode.

Claims (8)

1. A method for recovering metallic lead by reducing waste lead dioxide is characterized by comprising the following steps:
the manufacturing method comprises the steps of crushing waste lead dioxide, wherein the granularity is less than or equal to 2mm, and concentrating the waste lead dioxide and adding a first electrode made of a first conductive material;
forming a second pole by using a second conductive material;
thirdly, placing the anode A and the anode B into the container according to a certain position relation;
(4) connecting the A pole with the negative pole of a power supply, and connecting the B pole with the positive pole of the power supply;
(5) adding distilled water into a container in an amount capable of immersing the anode and the cathode, adjusting the pH value to 1-3 by using sulfuric acid, wherein the relative density of dilute sulfuric acid is 1.010-1.400 g/cubic centimeter;
sixthly, starting a power supply to electrify, wherein the electrified voltage and current can be adjusted, the electrified voltage is more than or equal to 2 volts, and the electrified processing time range is more than or equal to 5-600 minutes;
and converting the lead dioxide on the formazan after the treatment into metallic lead, and recovering the metallic lead from the formazan.
2. The method for recovering lead from waste lead dioxide according to claim 1, characterized in that the method for concentrating the waste lead dioxide in the step is tabletting, briquetting, stacking and bagging.
3. The method for recovering lead from waste lead dioxide according to claim 1, wherein in step c, the first conductive material comprises but is not limited to carbonaceous materials including graphite, 304, 309S, 310S, 316L, 317L, 904L stainless steel, titanium and its alloy, lead and its alloy, gold and its alloy, platinum and its alloy; the structural shape of the first conductive material includes, but is not limited to, plate, cylinder, arc, mesh, fork.
4. The method for recovering lead from waste lead dioxide according to claim 1, characterized in that the manner of adding the first conductive material in the step is embedding the waste lead dioxide into the waste lead dioxide tablets or briquettes, or stacking the waste lead dioxide tablets on sheet-shaped pole materials, or inserting the waste lead dioxide tablets or briquettes into the waste lead dioxide tablets or briquettes.
5. The method for recovering lead from waste lead dioxide as claimed in claim 1, wherein the second conductive material in the second step includes but is not limited to carbonaceous materials including graphite, or 304, 309S, 310S, 316L, 317L, 904L stainless steel, or titanium and alloy, lead and alloy, gold and alloy, platinum and alloy; the structural shape of the conductive material B includes, but is not limited to, plate, cylinder, arc, and net.
6. The method for recovering lead from waste lead dioxide as claimed in claim 1, wherein the positional relationship between the anode and the cathode in the step three is one of vertical parallel, horizontal parallel, vertical coaxial cylindrical surface and horizontal coaxial cylindrical surface, and the anode and the cathode in the horizontal parallel state can be located above and below each other.
7. The method for recovering lead from waste lead dioxide according to claim 1, wherein the power source in the step (4) is one of a steady direct current power source, a half-wave rectification power source, a full-wave rectification power source, a positive pulse power source, or a pulse alternating power source, the pulse alternating power source is formed by alternately compounding positive pulses and negative pulses, the positive effective value of the pulses is greater than the negative effective value of the pulses, and the ratio of the positive effective value of the positive pulses to the negative effective value of the pulses is greater than 1.
8. The method for recovering lead from waste lead dioxide as claimed in claim 1, wherein the step (5) is replaced by: dilute sulfuric acid is added to the vessel in an amount to immerse the anode and the cathode, the dilute sulfuric acid having a relative density of 1.010 to 1.400 g/cc.
CN202011253419.XA 2020-11-11 2020-11-11 Method for recovering metallic lead by reducing waste lead dioxide Pending CN113089024A (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0150032A2 (en) * 1984-01-24 1985-07-31 HAGEN Batterie AG Process for the recovery of lead from accumulator scraps and reduction plate therefor

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0150032A2 (en) * 1984-01-24 1985-07-31 HAGEN Batterie AG Process for the recovery of lead from accumulator scraps and reduction plate therefor

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