CN105950868A - Copper-lead separation process for waste lead-acid storage battery - Google Patents
Copper-lead separation process for waste lead-acid storage battery Download PDFInfo
- Publication number
- CN105950868A CN105950868A CN201610359945.1A CN201610359945A CN105950868A CN 105950868 A CN105950868 A CN 105950868A CN 201610359945 A CN201610359945 A CN 201610359945A CN 105950868 A CN105950868 A CN 105950868A
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- CN
- China
- Prior art keywords
- lead
- copper
- waste
- heating
- storage battery
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Classifications
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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
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
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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
-
- 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
- C22B15/00—Obtaining copper
-
- 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
- C22B7/001—Dry processes
- C22B7/004—Dry processes separating two or more metals by melting out (liquation), i.e. heating above the temperature of the lower melting metal component(s); by fractional crystallisation (controlled freezing)
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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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- 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
Abstract
The invention relates to the technical field of non-ferrous metal metallurgy, in particular to a copper-lead separation process for a waste lead-acid storage battery. The copper-lead separation process for the waste lead-acid storage battery mainly comprises the following steps of a, discharging electrolyte of the waste lead-acid storage battery; b, feeding the waste lead-acid storage battery into a crushing machine, firstly cutting and crushing the waste lead-acid storage battery to prepare crushed aggregates, and enabling the crushed aggregates to enter a water power separator; c, collecting and transferring the crushed aggregates containing lead and copper such as lead grids and terminals selected from the water power separator according to the proportion into a recycle pool; d, mixing the crushed aggregates and a separating flotation inhibitor solution, adding ammonium hydroxide, mixing and leaching for 3 hours at the room temperature, to obtain lead-copper dross slag materials; e, heating the lead-copper dross slag materials, and condensing volatile matters after collecting the volatile matters during heating to acquire metal lead, wherein the remaining solid is metal copper without the lead. According to the separation process provided by the invention, the recovery rate of the copper and the lead is high, the adaptability to raw materials is higher, and the recovered copper and lead content is high. During the separation process, zero release of pollutants is realized, and the pollution on the environment is reduced as much as possible.
Description
Technical field
The present invention relates to non-ferrous metal metallurgy technical field, particularly relate to the Cu-Pb separation technique of a kind of waste and old lead acid accumulator.
Background technology
The advantages such as lead battery is high with its cost performance, high temperature performance is superior, safe and reliable to operation occupy an important position in energy storage field, and the key areas in national economy such as transportation, communication, electric power mesh is all widely used.In recent years, along with automobile consumption amount strengthens, vehicle lead-acid battery consumption also steeply rises, and cut-off will be to the end of the year 2015, and China's only vehicle guaranteeding organic quantity has reached 2.6 hundred million the most, only this item purposes, lead-acid accumulator just has huge consumption figure, and a large amount of consumption of lead-acid accumulator necessarily lead to a considerable amount of scrapping, and containing plurality of heavy metal lead and high-concentration sulfuric acid solution in lead-acid accumulator, if do not carried out efficient recovery and scientific disposal, biological and environment certainly will be threatened.Research shows, acid pickle once enters soil will cause water pollution, destroys the soil organism and causes soil fertility to decline, and lead then can cause people's anemia, stomachache, pulse weakened, can cause death time serious.Lead-acid accumulator, except having danger, wherein also has a lot of resources to recycle, and if lead itself is a kind of non-ferrous metal, has important economic worth.Along with the continuous exploitation of lead ore, primary lead is fewer and feweri, has been difficult to meet industrial growing lead demand.If do not recycled the lead-acid accumulator accounting for lead total quantity consumed 80%, lead resource will appear from phenomenon in short supply, and the recovery value of copper is the highest, therefore says from protection environment and resource view, and recycling lead-acid accumulator is the most significant.
Summary of the invention
It is an object of the invention to provide a kind of environmental protection and the Cu-Pb separation technique of the high waste and old lead acid accumulator of the response rate.
For reaching above-mentioned purpose, the present invention adopts the following technical scheme that
The Cu-Pb separation technique of waste and old lead acid accumulator, separating step is as follows:
A. being discharged by the electrolyte of waste and old lead acid accumulator, electrolyte, after submerged pump is transferred to pressure filter, delivers to meltshop；
B. first cut during used and scrapped battery delivers to disintegrating machine, after crush, make particle, particle enters in seperator, is collected isolated lead plaster, and other particles enter in hydrodynamic force seperator；
The particle of the leaded cuprics such as the lead grid c. screened according to proportion in hydrodynamic force seperator and terminal is collected and is transferred in recovery pond；
D. complete to size mixing in recovery pond by the particle described in step c and separating flotation suppression solution, add ammonia, leaching 3 hours under room temperature, it is thus achieved that lead bronze scum silica frost material；
E. take refining lead bronze scum silica frost material, with the heating rate of 10 ~ 15 DEG C/min, be warming up to 110 ~ 120 DEG C, be incubated 1h, then be continuously heating to the heating rate of 15 ~ 20 DEG C/min
140 ~ 160 DEG C, it is incubated 1 ~ 3h, then stops heating so that it is near room temperature；Volatile matter during heating condenses after collecting, it is thus achieved that metallic lead, remaining solid is the metallic copper sloughing lead.
As preferred technical scheme, in described step e, take refining lead bronze scum silica frost material, with the heating rate of 13 DEG C/min, it is warming up to 118 DEG C, is incubated 1h, then is continuously heating to 160 DEG C with the heating rate of 15 DEG C/min, insulation 3h, then stops heating so that it is near room temperature；Volatile matter during heating condenses after collecting, it is thus achieved that metallic lead, remaining solid is the metallic copper sloughing lead.
Further: the separating flotation suppression solution of described step d is made up of the sulfite solution that mass concentration is 10.0% ~ 20.0% and the glycerine water solution mixing that mass concentration is 0.5% ~ 5%, and wherein said sulfite solution is 1:1 ~ 2 with the mass ratio of glycerine water solution.
As preferred technical scheme, the separating flotation suppression solution of described step d is made up of the sulfite solution that mass concentration is 17% and the glycerine water solution mixing that mass concentration is 4%, and wherein said sulfite solution is 1:1 with the mass ratio of glycerine water solution.
It is an advantage of the current invention that:
Copper, the response rate height of lead, relatively strong to the adaptability of raw material, the copper-lead content of recovery is high.Separation process realizes zero release of pollutant, reduces the pollution to environment as far as possible；
Detailed description of the invention:
Embodiment one:
The Cu-Pb separation technique of waste and old lead acid accumulator, separating step is as follows:
A. being discharged by the electrolyte of waste and old lead acid accumulator, electrolyte, after submerged pump is transferred to pressure filter, delivers to meltshop；
B. first cut during used and scrapped battery delivers to disintegrating machine, after crush, make particle, particle enters in seperator, is collected isolated lead plaster, and other particles enter in hydrodynamic force seperator；
The particle of the leaded cuprics such as the lead grid c. screened according to proportion in hydrodynamic force seperator and terminal is collected and is transferred in recovery pond；
D. complete to size mixing in recovery pond by the particle described in step c and separating flotation suppression solution, add ammonia, leaching 3 hours under room temperature, it is thus achieved that lead bronze scum silica frost material；
E. take refining lead bronze scum silica frost material, with the heating rate of 13 DEG C/min, be warming up to 118 DEG C, be incubated 1h, then be continuously heating to 160 DEG C with the heating rate of 15 DEG C/min, be incubated 3h, then stop heating so that it is near room temperature；Volatile matter during heating condenses after collecting, it is thus achieved that metallic lead, remaining solid is the metallic copper sloughing lead.
Wherein, the separating flotation suppression solution of described step d is made up of the sulfite solution that mass concentration is 17% and the glycerine water solution mixing that mass concentration is 4%, and wherein said sulfite solution is 1:1 with the mass ratio of glycerine water solution.
The leaded weight ratio of gained metallic lead is 86%, and metallic copper cupric weight ratio is 88%
Embodiment two:
In step e, take refining lead bronze scum silica frost material, with the heating rate of 15 DEG C/min, be warming up to 120 DEG C, be incubated 1h, then be continuously heating to 160 DEG C with the heating rate of 20 DEG C/min, be incubated 3h, then stop heating so that it is near room temperature；Volatile matter during heating condenses after collecting, it is thus achieved that metallic lead, remaining solid is the metallic copper sloughing lead.
In step d, separating flotation suppression solution is 5% by the sulfite solution that mass concentration is 20.0% and mass concentration
Glycerine water solution mixing composition, the mass ratio of wherein said sulfite solution and glycerine water solution is 1:2.
In addition to above-mentioned difference, other steps are consistent with embodiment one.
The leaded weight ratio of gained metallic lead is 83%, and metallic copper cupric weight ratio is 84%
Embodiment three:
In step e, take refining lead bronze scum silica frost material, with the heating rate of 10 DEG C/min, be warming up to 110 DEG C, be incubated 1h, then be continuously heating to 140 DEG C with the heating rate of 15 DEG C/min, be incubated 1h, then stop heating so that it is near room temperature；Volatile matter during heating condenses after collecting, it is thus achieved that metallic lead, remaining solid is the metallic copper sloughing lead.
In step d, separating flotation suppression solution is made up of the sulfite solution that mass concentration is 10.0% and the glycerine water solution mixing that mass concentration is 1%, and wherein said sulfite solution is 1:1.5 with the mass ratio of glycerine water solution.
In addition to above-mentioned difference, other steps are consistent with embodiment one.
The leaded weight ratio of gained metallic lead is 80%, and metallic copper cupric weight ratio is 82%.
Claims (4)
1. the Cu-Pb separation technique of waste and old lead acid accumulator, it is characterised in that:
A. being discharged by the electrolyte of waste and old lead acid accumulator, electrolyte, after submerged pump is transferred to pressure filter, delivers to meltshop；
B. first cut during used and scrapped battery delivers to disintegrating machine, after crush, make particle, particle enters in seperator, is collected isolated lead plaster, and other particles enter in hydrodynamic force seperator；
The particle of the leaded cuprics such as the lead grid c. screened according to proportion in hydrodynamic force seperator and terminal is collected and is transferred in recovery pond；
D. complete to size mixing in recovery pond by the particle described in step c and separating flotation suppression solution, add ammonia, leaching 3 hours under room temperature, it is thus achieved that lead bronze scum silica frost material；
E. take refining lead bronze scum silica frost material, with the heating rate of 10 ~ 15 DEG C/min, be warming up to 110 ~ 120 DEG C, be incubated 1h, then be continuously heating to 140 ~ 160 DEG C with the heating rate of 15 ~ 20 DEG C/min, be incubated 1 ~ 3h, then stop heating so that it is near room temperature；Volatile matter during heating condenses after collecting, it is thus achieved that metallic lead, remaining solid is the metallic copper sloughing lead.
The Cu-Pb separation technique of waste and old lead acid accumulator the most according to claim 1, it is characterized in that: in described step e, take refining lead bronze scum silica frost material, with the heating rate of 13 DEG C/min, it is warming up to 118 DEG C, is incubated 1h, it is continuously heating to 160 DEG C again with the heating rate of 15 DEG C/min, insulation 3h, then stops heating so that it is near room temperature；Volatile matter during heating condenses after collecting, it is thus achieved that metallic lead, remaining solid is the metallic copper sloughing lead.
The Cu-Pb separation technique of waste and old lead acid accumulator the most according to claim 1, it is characterized in that: the separating flotation suppression solution of described step d is made up of the sulfite solution that mass concentration is 10.0% ~ 20.0% and the glycerine water solution mixing that mass concentration is 0.5% ~ 5%, and wherein said sulfite solution is 1:1 ~ 2 with the mass ratio of glycerine water solution.
The Cu-Pb separation technique of waste and old lead acid accumulator the most according to claim 1, it is characterized in that: the separating flotation suppression solution of described step d is made up of the sulfite solution that mass concentration is 17% and the glycerine water solution mixing that mass concentration is 4%, and wherein said sulfite solution is 1:1 with the mass ratio of glycerine water solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610359945.1A CN105950868A (en) | 2016-05-27 | 2016-05-27 | Copper-lead separation process for waste lead-acid storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610359945.1A CN105950868A (en) | 2016-05-27 | 2016-05-27 | Copper-lead separation process for waste lead-acid storage battery |
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| CN105950868A true CN105950868A (en) | 2016-09-21 |
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| CN201610359945.1A Pending CN105950868A (en) | 2016-05-27 | 2016-05-27 | Copper-lead separation process for waste lead-acid storage battery |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108342581A (en) * | 2018-04-28 | 2018-07-31 | 江苏新春兴再生资源有限责任公司 | The separation melting systems and method of scrap lead aperture plate in a kind of recycling of lead-acid accumulator |
| CN108649290A (en) * | 2018-04-28 | 2018-10-12 | 江苏新春兴再生资源有限责任公司 | A kind of filtering ponds water detaches the separator and method of copper piece terminal in lead ash |
-
2016
- 2016-05-27 CN CN201610359945.1A patent/CN105950868A/en active Pending
Non-Patent Citations (4)
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| 李仕庆: "《铅锑冶炼》", 30 September 2008 * |
| 郑子樵: "《材料科学基础（第二版）》", 31 August 2013, 中南大学出版社 * |
| 陈宝璠: "《实用建筑安装电工手册》", 31 January 2013, 中国电力出版社 * |
| 马行驰: "《工程材料》", 31 August 2015, 西安电子科技大学出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108342581A (en) * | 2018-04-28 | 2018-07-31 | 江苏新春兴再生资源有限责任公司 | The separation melting systems and method of scrap lead aperture plate in a kind of recycling of lead-acid accumulator |
| CN108649290A (en) * | 2018-04-28 | 2018-10-12 | 江苏新春兴再生资源有限责任公司 | A kind of filtering ponds water detaches the separator and method of copper piece terminal in lead ash |
| CN108342581B (en) * | 2018-04-28 | 2023-07-18 | 江苏新春兴再生资源有限责任公司 | System and method for separating and melting waste lead grids in recovery of waste lead acid storage battery |
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Application publication date: 20160921 |
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