CN1808761A - Clean recovery method of lead from waste storage cells by acidic electrolyzing and in-situ deoxidation in solid phase through wet process - Google Patents

Clean recovery method of lead from waste storage cells by acidic electrolyzing and in-situ deoxidation in solid phase through wet process Download PDF

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Publication number
CN1808761A
CN1808761A CNA2006100382980A CN200610038298A CN1808761A CN 1808761 A CN1808761 A CN 1808761A CN A2006100382980 A CNA2006100382980 A CN A2006100382980A CN 200610038298 A CN200610038298 A CN 200610038298A CN 1808761 A CN1808761 A CN 1808761A
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lead
waste
water
slime
acid
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贾雷克
贾立克
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/84Recycling of batteries or fuel cells

Abstract

This invention relates to one complete wet process electrolytic solid phase reduction waste accumulator recycling method, which comprises the following steps: A, dumping acid from the waste accumulator; b, removing the waste shell after the step a; c, taking out inner electrode board from the waste one and digging out lead mud; d, cursing the lead mud in the breaker for wet process and adding one PbO powder and water for mixing up to process mud materials; e, coating the above mud material onto the stainless electrode board for natural drying onto the electrode board; f, putting the dried lead mud onto the electrolytic tank for electrolytic reduction into variable sponge lead; g, creeping out the sponge lead for low temperate casting with 350 to 450 degrees.

Description

Clean recovery method for waste storage battery lead by full-wet-method acid electrolysis solid-phase in-situ reduction
Technical Field
The invention discloses a clean recovery method of lead from a waste storage battery by using a full-wet method acid electrolysis solid-phase in-situ reduction, relates to an environment-friendly method for lead reduction by using full-wet method electrolysis, is suitable for clean recovery of lead from a waste storage battery by using a waste storage battery reduction method, and is an industrialized application technology of a full-wet method electrolysis reduction technology.
Background
At present, lead consumed by lead-acid storage batteries accounts for 82% of the total global lead consumption, and the lead-acid storage batteries cause great harm to the environment and human health. The domestic production of secondary lead from waste lead-acid storage batteries basically adopts pyrometallurgy. In the production process, a large amount of SO2 and lead steam are discharged, the environment is seriously polluted, the health of human beings is harmed, and the product is crude lead, cannot be directly used and needs to be further treated. The lead smelting process is divided into a smelting process section and an electrolysis process section, the electrolysis refining process is the traditional mature process at present, and the development direction of the lead smelting industry in the world mainly refers to the transformation of the smelting process section. The pyrometallurgical process technology of the world lead smelting industry goes through three stages: the first generation is a sintering pot-blast furnace process technology, which is eliminated by various countries due to serious environmental pollution; the second generation is a sintering machine-blast furnace technology, which reduces the pollution to the environment, but is difficult to solve the environmental protection problem fundamentally; the third generation is an oxygen-enriched bottom blowing oxidation-blast furnace reduction smelting process, which consists of two major parts, namely an oxygen-enriched bottom blowing lead concentrate smelting technology and a blast furnace lead oxide slag reducing technology, wherein the core technology is an oxygen-enriched bottom blowing furnace lead smelting technology, and the technology is a novel process independently researched and developed on the basis of a foreign lead smelting method in China and reaches the international advanced level. At present, only a few domestic enterprises adopt the process technology. Because the technology also adopts a high-temperature smelting method, the pollution of lead steam and sulfur dioxide cannot be fundamentally solved, and the extraction rate of lead is less than 90 percent, which cannot meet the national environmental protection requirement.
The research on the wet method regenerated lead of the waste lead storage battery is available in China. The lead recovery of the waste lead-acid storage battery is carried out by adopting a full wet method technology including pretreatment, wet desulphurization, leaching and electrodeposition. The solid-phase electrolytic lead smelting process developed by research is mainly used for treating waste lead storage batteries. The electrolyte is sodium hydroxide solution, and is reduced into metallic lead after electrolysis. However, the electrolyte adopts sodium hydroxide solution, and byproducts are more and difficult to treat, the solid-phase electrolytic lead smelting process is unstable and difficult to operate, and the large-scale production is difficult to carry out. Therefore, the existing technical researches on wet electrolytic reduction of lead in China cannot be applied to industrial production.
Disclosure of Invention
The invention aims to provide a clean recovery method of lead from a waste storage battery by using a full-wet method acid electrolysis solid-phase in-situ reduction method, which is an energy regeneration technology, is an environment-friendly full-wet method lead electrolysis reduction technology, is suitable for the field of waste storage battery reduction, and is a full-wet method lead electrolysis reduction technology applicable to industrial production.
The clean recovery method of the lead from the waste storage battery by the acid electrolysis solid-phase in-situ reduction of the full wet method is realized by adopting the following scheme: the technical method comprises the following steps:
(1) the waste storage battery is subjected to acid pouring treatment, acid in the waste storage battery is poured out, and the acid poured out from the waste storage battery can be reduced for use after being prepared again;
(2) and (4) removing the shells of the waste storage batteries subjected to the acid pouring treatment (without acid). The waste plastics are used as raw materials of the accumulator tank and are made into a plastic shell again after being processed;
(3) taking out the internal polar plate of the waste battery, knocking out (cleaning) lead mud, directly using the remaining grid rib part as lead-antimony alloy, and casting at 350-450 ℃ to obtain a lead-antimony alloy ingot;
(4) the lead slime is placed into a pulverizer to be pulverized and levigated by a wet method, the particle size of the lead slime after being pulverized and levigated is 80-120 meshes, the lead slime is continuously washed by water in the pulverizing and levigating process, the lead slime is taken out through precipitation, lead monoxide PbO powder and water are added to be uniformly mixed and stirred, slurry is prepared, and the weight percentage ratio of the lead slime, the lead monoxide PbO powder and the water in the slurry is as follows: 95-98% of lead mud, 0.5-1% of lead monoxide PbO powder and the balance of water, wherein the precipitated water is recycled and used as washing water for the lead mud in the crushing and grinding process;
(5) coating the prepared slurry on a stainless steel electrode plate for natural drying or drying at the temperature of 30-40 ℃ to enable the slurry to be fixedly bonded on the electrode plate;
(6) putting the dried lead slime coated and fixed on the stainless steel electrode plate into an electrolytic bath for electrolytic reduction to obtain deformed spongy lead, wherein the electrolyte comprises 10-30% of sulfuric acid and the balance of water, and the current density is 400-550A/m2The temperature is 30-60 ℃;
(7) and stripping the sponge lead reduced on the electrode plate, and performing low-temperature casting to obtain a lead ingot, wherein the casting temperature is 350-450 ℃.
The main reactions of several lead compounds occurring at the cathode during electrolysis are:
anode hydroxyl discharge to separate out oxygen:
the preferred electrolysis conditions are: the current density is 500A/m2, and the temperature is 50-60 ℃. The obtained technical indexes are as follows: the power consumption is 550kWh/t&Pb, the lead recovery rate is 95%, the current efficiency is 87.5%, the electrolytically reduced metallic lead is melted and cast into a lead ingot at 400 ℃, and after a small amount of lead is added for removing sulfur, the quality of the electrolytic lead can reach the No. 2 lead standard.
The invention is characterized in that:
1. the full wet method, i.e. no high-temperature smelting operation, SO no SO is generated in the whole process of recovering the lead of the waste storage battery2Lead dust and the like;
2. lead slime (mainly containing PbO) collected from waste storage batteries2、PbO、PbSO4And a small amount of solid-phase substances such as metal Pb) directly slurrying, coating on a metal polar plate, and drying for electrolysis operation;
3. carrying out in-situ reduction on lead slime attached to the polar plate in an acid electrolyte to generate electrolytic lead;
4. carrying out circulating treatment on the electrolyte, and recovering sulfuric acid which can be used for manufacturing a lead-acid storage battery;
5. the process flow is simple, the collected lead slime does not need to be dissolved and desulfurized, and the alkali and Na are not consumed2SO4And the like.
6. The lead recovery rate is more than 95 percent, the current efficiency is more than 95 percent, and the electrolytic lead mass is more than 99.99 percent
7. The positive effects are as follows:
(1) the environmental pollution of lead dust, sulfur dioxide, lead vapor and lead slag caused by the pyrometallurgical high-temperature reduction technology is thoroughly eliminated. Protecting ecological environment, improving human health, and improving human living environment.
(2) The methodavoids huge waste of lead resources, improves the regeneration utilization rate of the lead resources, and relieves the great pressure of the increasing shortage of national mineral resources.
(3) The method provides effective technical guarantee for the lead reduction production technology and development of the waste lead storage battery, and provides a basis for the industrialization development of the lead reduction technology of the waste lead storage battery in the future.
(4) The waste lead storage battery is recycled, good economic benefits can be brought to enterprises, and the social and economic benefits of the technology are very obvious.
Detailed Description
Example 1: the clean recovery method of the lead of the waste storage battery by the full-wet acidic electrolysis solid-phase in-situ reduction comprises the following steps:
(1) acid pouring treatment is carried out on the waste storage battery, acid in the waste storage battery is poured out, and the acid poured out from the waste storage battery can be reduced for use through reconstitution;
(2) and (4) removing the shells of the waste storage batteries subjected to the acid pouring treatment (without acid). The waste plastics are used as raw materials of the accumulator tank and are made into a plastic shell again after being processed;
(3) taking out the internal polar plate of the waste battery, knocking out lead mud, directly using the rib part of the rest grid as lead-antimony alloy, and casting at 350 ℃ to obtain a lead-antimony alloy ingot;
(4) the lead slime is placed into a pulverizer to be pulverized and levigated by a wet method, the particle size of the lead slime is 80 meshes after being pulverized and levigated, the lead slime is continuously washed by water in the pulverizing and levigating process, the lead slime is taken out through precipitation, lead monoxide PbO powder and water are added to be uniformly mixed and stirred, slurry is prepared, and the weight percentage ratio of the lead slime, the lead monoxide PbO powder and the water in the slurry is as follows: 95% of lead mud, 1% of lead monoxide PbO powder and 4% of water, and the precipitated water is recycled and used as washing water for the lead mud in the crushing and grinding process;
(5) coating the prepared slurry on a stainless steel electrode plate for natural drying or drying at the temperature of 40 ℃ to enable the slurry to be fixedly bonded on the electrode plate;
(6) the dried lead slime coated and fixed on the stainless steel electrode plate is put into an electrolytic bath for electrolytic reduction to form deformed spongy lead, and the electrolyte comprises 10 percent of sulfuric acid, 90 percent of water and 400A/m of current density2At a temperature of 60 ℃;
(7) stripping off the sponge lead reduced on the electrode plate, and carrying out low-temperature casting to obtain a lead ingot, wherein the casting temperature is 450 ℃.
Example 2: the clean recovery method of the lead of the waste storage battery by the full-wet acidic electrolysis solid-phase in-situ reduction comprises the following steps:
(1) acid pouring treatment is carried out on the waste storage battery, acid in the waste storage battery is poured out, and the acid poured out from the waste storage battery can be reduced for use through reconstitution;
(2) and (4) removing the shells of the waste storage batteries subjected to the acid pouring treatment (without acid).The waste plastics are used as raw materials of the accumulator tank and are made into a plastic shell again after being processed;
(3) taking out the internal polar plate of the waste battery, knocking out lead mud, directly using the rib part of the rest grid as lead-antimony alloy, and casting at 400 ℃ to obtain a lead-antimony alloy ingot;
(4) the lead slime is placed into a pulverizer to be pulverized and levigated by a wet method, the particle size of the lead slime is 100 meshes after being pulverized and levigated, the lead slime is continuously washed by water in the pulverizing and levigating process, the lead slime is taken out through precipitation, lead monoxide PbO powder and water are added to be uniformly mixed and stirred, slurry is prepared, and the weight percentage ratio of the lead slime, the lead monoxide PbO powder and the water in the slurry is as follows: 96% of lead slime, 0.8% of lead monoxide PbO powder and 3.2% of water, and the precipitated water is recycled and used as washing water for the lead slime in the crushing and grinding processes;
(5) coating the prepared slurry on a stainless steel electrode plate for natural drying or drying at the temperature of 38 ℃ to enable the slurry to be fixedly bonded on the electrode plate;
(6) the dried lead slime coated and fixed on the stainless steel electrode plate is put into an electrolytic bath for electrolytic reduction to form deformed spongy lead, and the proportion of the electrolyte is 20 percent of sulfuric acid, 80 percent of water and 500A/m of current density2Temperature ofThe temperature is 45 ℃;
(7) stripping off the sponge lead reduced on the electrode plate, and carrying out low-temperature casting to obtain a lead ingot, wherein the casting temperature is 400 ℃.
Example 3: the cleanrecovery method of the lead of the waste storage battery by the full-wet acidic electrolysis solid-phase in-situ reduction comprises the following steps:
(1) acid pouring treatment is carried out on the waste storage battery, acid in the waste storage battery is poured out, and the acid poured out from the waste storage battery can be reduced for use through reconstitution;
(2) and (4) removing the shells of the waste storage batteries subjected to the acid pouring treatment (without acid). The waste plastics are used as raw materials of the accumulator tank and are made into a plastic shell again after being processed;
(3) taking out the internal polar plate of the waste battery, knocking out lead mud, directly using the rib part of the rest grid as lead-antimony alloy, and casting at 450 ℃ to obtain a lead-antimony alloy ingot;
(4) the lead slime is placed into a pulverizer to be pulverized and levigated by a wet method, the particle size of the lead slime is 120 meshes after being pulverized and levigated, the lead slime is continuously washed by water in the pulverizing and levigating process, the lead slime is taken out through precipitation, lead monoxide PbO powder and water are added to be uniformly mixed and stirred, slurry is prepared, and the weight percentage ratio of the lead slime, the lead monoxide PbO powder and the water in the slurry is as follows: 98% of lead slime, 0.5% of lead monoxide PbO powder and 1.5% of water, and the precipitated water is recycled and used as washing water for the lead slime in the crushing and grinding processes;
(5) coating the prepared slurry on a stainless steel electrode plate for natural drying or drying at the temperature of 30 ℃ to enable the slurry to be fixedly bonded on the electrode plate;
(6) the dried lead slime coated and fixed on the stainless steelelectrode plate is put into an electrolytic bath for electrolytic reduction to form deformed spongy lead, and the proportion of the electrolyte is 30 percent of sulfuric acid, 70 percent of water and 550A/m of current density2At a temperature of 30 ℃;
(7) and stripping the sponge lead reduced on the electrode plate, and performing low-temperature casting to obtain a lead ingot, wherein the casting temperature is 350 ℃.

Claims (2)

1. A clean recovery method of waste storage battery lead by full-wet acidic electrolysis solid-phase in-situ reduction is characterized by comprising the following steps:
(1) pouring acid from the waste storage battery, and pouring out the acid in the waste storage battery;
(2) removing shells of the waste daily storage batteries subjected to the acid pouring treatment;
(3) taking out the internal polar plate of the waste battery, knocking out lead mud, directly using the remaining grid rib part as lead-antimony alloy, and carrying out fusion casting at 350-450 ℃ to obtain a lead-antimony alloy ingot;
(4) the lead slime is placed into a pulverizer to be pulverized and levigated by a wet method, the particle size of the lead slime after being pulverized and levigated is 80-120 meshes, the lead slime is continuously washed by water in the pulverizing and levigating process, the lead slime is taken out through precipitation, lead monoxide PbO powder and water are added to be uniformly mixed and stirred, slurry is prepared, and the weight percentage ratio of the lead slime, the lead monoxide PbO powder and the water in the slurry is as follows: 95-98% of lead mud, 0.5-1% of lead monoxide PbO powder and the balance of water, wherein the precipitated water is recycled and usedas washing water for the lead mud in the crushing and grinding process;
(5) coating the prepared slurry on a stainless steel electrode plate for natural drying or drying at the temperature of 30-40 ℃ to enable the slurry to be fixedly bonded on the electrode plate;
(6) putting the dried lead slime coated and fixed on the stainless steel electrode plate into an electrolytic bath for electrolytic reduction to obtain deformed spongy lead, wherein the electrolyte comprises 10-30% of sulfuric acid and the balance of water, and the current density is 400-550A/m2The temperature is 30-60 ℃;
(7) and stripping the sponge lead reduced on the electrode plate, and performing low-temperature casting to obtain a lead ingot, wherein the casting temperature is 350-450 ℃.
2. The clean recovery method of lead from waste storage batteries by full-wet acidic electrolysis solid-phase in-situ reduction according to claim 1, characterized in that the stainless steel electrode plate is a cathode.
CNA2006100382980A 2006-02-15 2006-02-15 Clean recovery method of lead from waste storage cells by acidic electrolyzing and in-situ deoxidation in solid phase through wet process Pending CN1808761A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010003382A1 (en) * 2008-07-11 2010-01-14 东莞市松山科技集团有限公司 Method for implementing full cycle regeneration of waste lead acid battery
CN101209496B (en) * 2006-12-27 2010-05-26 于军 Method for using lead flue dust or slag to prepare ultra-fine lead powder
CN102427149A (en) * 2011-12-02 2012-04-25 浙江汇同电源有限公司 Method for recovering lead from storage battery
CN103071668A (en) * 2013-01-29 2013-05-01 江苏超威电源有限公司 Method and system for recycling hazardous lead solid waste
CN103184340A (en) * 2011-12-31 2013-07-03 深圳市雄韬电源科技股份有限公司 Method for recovering lead plaster of negative pole of disused lead acid storage battery and application of recovered lead plaster
CN104131312A (en) * 2014-07-08 2014-11-05 昆明理工大学 Method utilizing eutectic solvent to carry out in-situ reduction on lead oxide to produce lead
CN107204496A (en) * 2017-06-21 2017-09-26 湘潭大学 A kind of method that waste lead acid battery lead plaster prepares pure lead

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101209496B (en) * 2006-12-27 2010-05-26 于军 Method for using lead flue dust or slag to prepare ultra-fine lead powder
WO2010003382A1 (en) * 2008-07-11 2010-01-14 东莞市松山科技集团有限公司 Method for implementing full cycle regeneration of waste lead acid battery
CN102427149A (en) * 2011-12-02 2012-04-25 浙江汇同电源有限公司 Method for recovering lead from storage battery
CN103184340A (en) * 2011-12-31 2013-07-03 深圳市雄韬电源科技股份有限公司 Method for recovering lead plaster of negative pole of disused lead acid storage battery and application of recovered lead plaster
CN103184340B (en) * 2011-12-31 2014-10-29 深圳市雄韬电源科技股份有限公司 Method for recovering lead plaster of negative pole of disused lead acid storage battery and application of recovered lead plaster
CN103071668A (en) * 2013-01-29 2013-05-01 江苏超威电源有限公司 Method and system for recycling hazardous lead solid waste
CN103071668B (en) * 2013-01-29 2015-05-13 江苏超威电源有限公司 Method and system for recycling hazardous lead solid waste
CN104131312A (en) * 2014-07-08 2014-11-05 昆明理工大学 Method utilizing eutectic solvent to carry out in-situ reduction on lead oxide to produce lead
CN107204496A (en) * 2017-06-21 2017-09-26 湘潭大学 A kind of method that waste lead acid battery lead plaster prepares pure lead

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