CN113846223A - Method for desulfurizing, processing and recycling lead slime of waste battery - Google Patents

Method for desulfurizing, processing and recycling lead slime of waste battery Download PDF

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Publication number
CN113846223A
CN113846223A CN202111206305.4A CN202111206305A CN113846223A CN 113846223 A CN113846223 A CN 113846223A CN 202111206305 A CN202111206305 A CN 202111206305A CN 113846223 A CN113846223 A CN 113846223A
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CN
China
Prior art keywords
lead
slime
mud
desulfurized
waste
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Pending
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CN202111206305.4A
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Chinese (zh)
Inventor
应允峰
魏允有
朱庆勇
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ANHUI HUAXIN LEAD INDUSTRY GROUP CO LTD
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ANHUI HUAXIN LEAD INDUSTRY GROUP CO LTD
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Priority to CN202111206305.4A priority Critical patent/CN113846223A/en
Publication of CN113846223A publication Critical patent/CN113846223A/en
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working 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
    • C22B7/006Wet processes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00Preliminary treatment of ores or scrap
    • C22B1/005Preliminary treatment of scrap
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B13/00Obtaining lead
    • C22B13/02Obtaining lead by dry processes
    • C22B13/025Recovery from waste materials
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B13/00Obtaining lead
    • C22B13/04Obtaining lead by wet processes
    • C22B13/045Recovery from waste materials
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working 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
    • C22B7/001Dry processes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/54Reclaiming serviceable parts of waste accumulators
    • 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
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling
    • 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

The invention discloses a method for desulfurizing, processing and recycling lead slime of waste batteries, and relates to the technical field of waste battery recovery. The invention comprises the following steps: step 1: putting the recovered waste lead storage batteries into a crusher for crushing, and crushing the waste lead storage batteries into solid fragments with the size of 100 meshes by the crusher; step 2: pouring the crushed solid fragments into a water separation tank for screening, wherein the plastic and rubber fragments float on the water surface under the action of water power, and the lead plate grid is sunk into the water bottom; step 3: drying and filtering the screened lead plate grids, wherein a vibration screen of 100 meshes is adopted for filtering, Step2 is repeated on lead plate grids with substandard sizes, and the lead plates with substandard sizes are subjected to liquid-solid separation through a filter press to produce lead mud and filtrate; step 4: the method comprises the following steps of conveying lead slime into a desulfurization tank, adding the lead slime into a sodium hydroxide solution, reacting at the temperature of 80 ℃, adding sodium carbonate as a catalyst to accelerate the reaction speed, arranging a stirring device in the desulfurization tank, setting the rotating speed of the stirring device to be 150rad/min, and stirring raw materials for 20min to enable the lead slime to be slurried.

Description

Method for desulfurizing, processing and recycling lead slime of waste battery
Technical Field
The invention relates to the technical field of waste battery recovery, in particular to a method for desulfurizing, processing and recycling lead slime of waste batteries.
Background
With the continuous development of lead-acid storage battery technology, lead-acid storage batteries have made great progress in the aspects of theoretical research, product types, product varieties, product electrical properties and the like, and the lead-acid storage batteries play an indispensable important role in various economic fields of transportation, communication, electric power, military, navigation and aviation, and are roughly divided into four categories according to the structural and application differences of the lead-acid storage batteries: 1. a lead-acid battery for starting; 2. a lead-acid battery for power; 3. a fixed valve-regulated sealed lead-acid battery; 4. other types include small valve-regulated sealed lead-acid batteries, lead-acid batteries for mining lamps, etc., and the nominal voltage of a single-cell lead-acid battery is 2.0V, which can be discharged to 1.5V and charged to 2.4V. In application, 6 single-cell lead-acid batteries are often connected in series to form a lead-acid battery with the nominal value of 12V, and 24V, 36V, 48V and the like;
although lead storage batteries bring great convenience to human life, the lead storage batteries can cause great damage to the environment after being discarded, the lead storage batteries also occupy most of the market share of the world, and with the stricter and stricter stipulation of terms such as environmental protection laws and regulations, the discarded lead-acid batteries are in great quantity every year, so that not only is the soil environment of the world destroyed, but also the resource shortage is highlighted more and more along with the collection of lead ores, the cost of enterprises when processing the discarded lead storage batteries is higher and more, and therefore, the recycling of resources is also paid more and more attention to;
the prior art generally adopts when carrying out lead accumulator's recovery that the mixture is smashed and is retrieved, and the rate of recovery is low and with high costs, and the resource of retrieving is few, can't adapt to present more and more strict recovery requirement, and the usable material cost of retrieving probably exceeds the cost of direct purchase from the market far away to easily illegal environmental protection discharges relevant regulation, causes very big waste at enterprise's production.
Disclosure of Invention
The invention aims to provide a method for desulfurizing, processing and recycling lead slime of waste batteries, which solves the problems of low recovery efficiency and easy waste.
In order to solve the technical problems, the invention is realized by the following technical scheme:
the invention relates to a method for desulfurizing, processing and recycling lead slime of waste batteries, which comprises the following steps:
step 1: putting the recovered waste lead storage batteries into a crusher for crushing, and crushing the waste lead storage batteries into solid fragments with the size of 100 meshes by the crusher;
step 2: pouring the crushed solid fragments into a water separation tank for screening, wherein the plastic and rubber fragments float on the water surface under the action of water power, and the lead plate grid is sunk into the water bottom;
step 3: drying and filtering the screened lead plate grids, wherein a vibration screen of 100 meshes is adopted for filtering, Step2 is repeated on lead plate grids with substandard sizes, and the lead plates with substandard sizes are subjected to liquid-solid separation through a filter press to produce lead mud and filtrate;
step 4: the method comprises the following steps of (1) feeding lead slime into a desulfurization tank, adding the lead slime into a sodium hydroxide solution, reacting at the temperature of 80 ℃, adding sodium carbonate as a catalyst to accelerate the reaction speed, arranging a stirring device in the desulfurization tank, setting the rotating speed of the stirring device to be 150rad/min, and stirring raw materials for 20min to enable the lead slime to be slurried;
step 5: then setting the rotating speed of the stirring device to be 300rad/min to 500rad/min to carry out variable speed stirring on the lead slime, stirring for 30min, standing for 10min, and then repeating Step4 again;
step 6: standing again after the stirring of Step5 is finished, separating solid from liquid in the desulfurization tank, pumping out a liquid product, carrying out filter pressing on the desulfurized lead mud again, and repeating Step4 on the obtained lead mud again;
step 7: sending the desulfurized lead mud produced in Step7 to a washing pool, and continuously washing the desulfurized lead mud by using distilled water until the pH value of the desulfurized lead mud is neutral;
step 8: and smelting the desulfurized lead slime after water washing into lead ingots at the temperature of 400-700 ℃ in a smelting furnace.
Further, in Step1, before the waste lead storage battery is crushed, the external metal and plastic covering parts are firstly removed, the electrolyte of the lead storage battery during crushing is conveyed to an electrolyte recovery device for recovery, the electrolyte recovery device firstly recovers free acid and retains metal salt through a diffusion dialyzer, and the recovered acid is added with the original concentrated acid to increase the concentration to 75%.
Further, the filtrate produced in Step3 is purified and crystallized, so that the lead slime component remained in the filtrate is extracted, and then the lead slime is carried out in Step 4.
Further, the concentration of the sodium hydroxide solution in Step4 is 1.2%, the mass of the sodium hydroxide accounts for 1.2% of the total mass of the lead mud, and the mass of the sodium carbonate in Step4 accounts for 1.2% of the total mass of the lead mud.
Further, the Step4-Step5 procedure took 1 hour.
Further, the specific manner of the water washing operation in Step7 is as follows: placing the desulfurized lead mud produced in Step6 in a washing tank and soaking the desulfurized lead mud into a washing pool, wherein water passing holes are formed in the surface of the washing tank, the diameter of each water passing hole is smaller than that of the desulfurized lead mud, the desulfurized lead mud is soaked for 10min after pure water completely submerges the desulfurized lead mud, and then the washing tank is horizontally shaken to enable the desulfurized lead mud to be fully contacted with the pure water.
The invention has the following beneficial effects:
according to the invention, the lead-containing components of the waste lead storage battery are more finely crushed, the produced lead mud is rapidly desulfurized under the action of the sodium hydroxide solution and the sodium carbonate, a faster reaction speed can be obtained by matching with the stirring of the stirring device, the time of a recovery process is saved, the recovery effect is better, the waste is less, the recovered lead ingots can be directly put into production and use, the production and recovery cost is reduced, and the resource waste is avoided.
The method can effectively recover acid components in the electrolyte by recovering the electrolyte, can be put into acid cleaning production by adding the original concentrated acid proportion, and can recover the residual lead slime components in the filtrate by crystallizing the filtrate in the filter pressing process, thereby effectively improving the recovery rate of various resources in the recovery process of the lead storage battery, having better recovery effect and lower environmental pollution.
Of course, it is not necessary for any product in which the invention is practiced to achieve all of the above-described advantages at the same time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an operation flow chart of the method for desulfurization processing and recycling of lead slime of waste batteries.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Please refer to fig. 1: the invention relates to a method for desulfurizing, processing and recycling lead slime of waste batteries, which comprises the following steps:
step 1: putting the recovered waste lead storage batteries into a crusher for crushing, and crushing the waste lead storage batteries into solid fragments with the size of 100 meshes by the crusher;
step 2: pouring the crushed solid fragments into a water separation tank for screening, wherein the plastic and rubber fragments float on the water surface under the action of water power, and the lead plate grid is sunk into the water bottom;
step 3: drying and filtering the screened lead plate grids, wherein a vibration screen of 100 meshes is adopted for filtering, Step2 is repeated on lead plate grids with substandard sizes, and the lead plates with substandard sizes are subjected to liquid-solid separation through a filter press to produce lead mud and filtrate;
step 4: the method comprises the following steps of (1) feeding lead slime into a desulfurization tank, adding the lead slime into a sodium hydroxide solution, reacting at the temperature of 80 ℃, adding sodium carbonate as a catalyst to accelerate the reaction speed, arranging a stirring device in the desulfurization tank, setting the rotating speed of the stirring device to be 150rad/min, and stirring raw materials for 20min to enable the lead slime to be slurried;
step 5: then setting the rotating speed of the stirring device to be 300rad/min to 500rad/min to carry out variable speed stirring on the lead slime, stirring for 30min, standing for 10min, and then repeating Step4 again;
step 6: standing again after the stirring of Step5 is finished, separating solid from liquid in the desulfurization tank, pumping out a liquid product, carrying out filter pressing on the desulfurized lead mud again, and repeating Step4 on the obtained lead mud again;
step 7: sending the desulfurized lead mud produced in Step7 to a washing pool, and continuously washing the desulfurized lead mud by using distilled water until the pH value of the desulfurized lead mud is neutral;
step 8: and smelting the desulfurized lead slime after water washing into lead ingots at the temperature of 400-700 ℃ in a smelting furnace.
Preferably, the external metal and plastic covering parts are removed before the waste lead storage battery is crushed in Step1, the electrolyte of the lead storage battery during crushing is conveyed to an electrolyte recovery device for recovery, the electrolyte recovery device firstly recovers free acid and retains metal salt through a diffusion dialyzer, and the recovered acid is added with the original concentrated acid to increase the concentration to 75%.
Preferably, the filtrate produced in Step3 is purified and crystallized, so that the lead slime component remained in the filtrate is extracted, and then the lead slime is carried out in Step 4.
Preferably, the concentration of the sodium hydroxide solution in Step4 is 1.2%, the mass of the sodium hydroxide accounts for 1.2% of the total mass of the lead mud, and the mass of the sodium carbonate in Step4 accounts for 1.2% of the total mass of the lead mud.
Preferably, the Step4-Step5 process takes 1 hour.
Preferably, the specific manner of the water washing operation in Step7 is as follows: placing the desulfurized lead mud produced in Step6 in a washing tank and soaking the desulfurized lead mud into a washing pool, wherein water passing holes are formed in the surface of the washing tank, the diameter of each water passing hole is smaller than that of the desulfurized lead mud, the desulfurized lead mud is soaked for 10min after pure water completely submerges the desulfurized lead mud, and then the washing tank is horizontally shaken to enable the desulfurized lead mud to be fully contacted with the pure water.
In this scheme, through the lead-containing composition to old and useless lead accumulator carry out more careful breakage, the lead slime of production is desulfurization rapidly under the effect of sodium hydroxide solution and sodium carbonate, and the stirring of cooperation agitating unit can obtain faster reaction rate, saves the time of retrieving the process, carries out chemical desulfurization through the repetition, and it is better to retrieve the effect, and extravagant few, the lead ingot of recovery can directly put into production and use, reduction in production and recovery cost avoid the wasting of resources.
In this scheme, through retrieving electrolyte, can effectively retrieve the acid composition in the electrolyte, add former concentrated acid ratio again and can drop into the pickling production, crystallize through the filtrate to the filter-pressing in-process to retrieve the surplus lead slime composition in the filtrate, effectively promote the rate of recovery to various resources in the lead accumulator recovery process, it is better to retrieve the effect, and environmental pollution is lower.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims (6)

1. A method for desulfurizing, processing and recycling lead slime of waste batteries is characterized by comprising the following steps:
step 1: putting the recovered waste lead storage batteries into a crusher for crushing, and crushing the waste lead storage batteries into solid fragments with the size of 100 meshes by the crusher;
step 2: pouring the crushed solid fragments into a water separation tank for screening, wherein the plastic and rubber fragments float on the water surface under the action of water power, and the lead plate grid is sunk into the water bottom;
step 3: drying and filtering the screened lead plate grids, wherein a vibration screen of 100 meshes is adopted for filtering, Step2 is repeated on lead plate grids with substandard sizes, and the lead plates with substandard sizes are subjected to liquid-solid separation through a filter press to produce lead mud and filtrate;
step 4: the method comprises the following steps of (1) feeding lead slime into a desulfurization tank, adding the lead slime into a sodium hydroxide solution, reacting at the temperature of 80 ℃, adding sodium carbonate as a catalyst to accelerate the reaction speed, arranging a stirring device in the desulfurization tank, setting the rotating speed of the stirring device to be 150rad/min, and stirring raw materials for 20min to enable the lead slime to be slurried;
step 5: then setting the rotating speed of the stirring device to be 300rad/min to 500rad/min to carry out variable speed stirring on the lead slime, stirring for 30min, standing for 10min, and then repeating Step4 again;
step 6: standing again after the stirring of Step5 is finished, separating solid from liquid in the desulfurization tank, pumping out a liquid product, carrying out filter pressing on the desulfurized lead mud again, and repeating Step4 on the obtained lead mud again;
step 7: sending the desulfurized lead mud produced in Step7 to a washing pool, and continuously washing the desulfurized lead mud by using distilled water until the pH value of the desulfurized lead mud is neutral;
step 8: and smelting the desulfurized lead slime after water washing into lead ingots at the temperature of 400-700 ℃ in a smelting furnace.
2. The method as claimed in claim 1, wherein Step1, the external metal and plastic covering parts are removed before the waste lead storage battery is crushed, the electrolyte of the crushed lead storage battery is sent to an electrolyte recovery device for recovery, the electrolyte recovery device first recovers free acid and retains metal salt through a diffusion dialyzer, and the recovered acid is added with original concentrated acid to raise the concentration to 75%.
3. The method for recycling the grids from disassembled waste batteries as claimed in claim 1, wherein the filtrate produced in the Step3 is purified and crystallized, so that the lead slime component remained in the filtrate is mixed in the lead slime and the Step4 is performed.
4. The method for desulfurizing, processing and recycling lead slime of waste batteries according to claim 1, wherein the concentration of the sodium hydroxide solution in Step4 is 1.2%, the mass of the sodium hydroxide accounts for 1.2% of the total mass of the lead slime, and the mass of the sodium carbonate in Step4 accounts for 1.2% of the total mass of the lead slime.
5. The method for desulfurizing, processing and recycling lead slime from waste batteries according to claim 1, wherein the time of one process of Step4-Step5 is 1 hour.
6. The method for the desulfurization processing and recycling of the lead slime of the waste batteries as claimed in claim 1, wherein the water washing operation in Step7 is implemented by the following specific method: placing the desulfurized lead mud produced in Step6 in a washing tank and soaking the desulfurized lead mud into a washing pool, wherein water passing holes are formed in the surface of the washing tank, the diameter of each water passing hole is smaller than that of the desulfurized lead mud, the desulfurized lead mud is soaked for 10min after pure water completely submerges the desulfurized lead mud, and then the washing tank is horizontally shaken to enable the desulfurized lead mud to be fully contacted with the pure water.
CN202111206305.4A 2021-10-16 2021-10-16 Method for desulfurizing, processing and recycling lead slime of waste battery Pending CN113846223A (en)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101205080A (en) * 2006-12-18 2008-06-25 湖南大学 Method for preparing high-quality red lead by lead slime of lead-acid batteries
CN101318692A (en) * 2007-06-04 2008-12-10 湖南大学 Method for preparing high quality lead dioxide with plumbum mud in waste lead acid accumulator
CN102351217A (en) * 2011-06-21 2012-02-15 南京大学 Method of removing lead in by-product sodium sulfate of recovery and processing of waste lead storage batteries
CN104975168A (en) * 2014-04-01 2015-10-14 北京化工大学 Method for rapidly desulfurizing lead-sulfate-containing substances
CN105420489A (en) * 2015-11-28 2016-03-23 湘潭大学 Diachylon desulphurization method based on throttling self-collision
CN105925807A (en) * 2016-05-26 2016-09-07 广东新生环保科技股份有限公司 Recycling process of waste battery lead
CN108511836A (en) * 2018-03-23 2018-09-07 天能电池集团(安徽)有限公司 A kind of lead mud recovery process of lead-acid accumulator
CN110468279A (en) * 2019-09-09 2019-11-19 赵坤 A method of recycling lead from the lead plaster material of waste lead storage battery

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101205080A (en) * 2006-12-18 2008-06-25 湖南大学 Method for preparing high-quality red lead by lead slime of lead-acid batteries
CN101318692A (en) * 2007-06-04 2008-12-10 湖南大学 Method for preparing high quality lead dioxide with plumbum mud in waste lead acid accumulator
CN102351217A (en) * 2011-06-21 2012-02-15 南京大学 Method of removing lead in by-product sodium sulfate of recovery and processing of waste lead storage batteries
CN104975168A (en) * 2014-04-01 2015-10-14 北京化工大学 Method for rapidly desulfurizing lead-sulfate-containing substances
CN105420489A (en) * 2015-11-28 2016-03-23 湘潭大学 Diachylon desulphurization method based on throttling self-collision
CN105925807A (en) * 2016-05-26 2016-09-07 广东新生环保科技股份有限公司 Recycling process of waste battery lead
CN108511836A (en) * 2018-03-23 2018-09-07 天能电池集团(安徽)有限公司 A kind of lead mud recovery process of lead-acid accumulator
CN110468279A (en) * 2019-09-09 2019-11-19 赵坤 A method of recycling lead from the lead plaster material of waste lead storage battery

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Application publication date: 20211228