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WO2016049994A1 - Procédé de désulfuration de pâte de plomb en fonction d'un mécanisme de broyage - Google Patents

Procédé de désulfuration de pâte de plomb en fonction d'un mécanisme de broyage Download PDF

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Publication number
WO2016049994A1
WO2016049994A1 PCT/CN2014/095940 CN2014095940W WO2016049994A1 WO 2016049994 A1 WO2016049994 A1 WO 2016049994A1 CN 2014095940 W CN2014095940 W CN 2014095940W WO 2016049994 A1 WO2016049994 A1 WO 2016049994A1
Authority
WO
WIPO (PCT)
Prior art keywords
desulfurization
slurry
lead
lead paste
grinding
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.)
Ceased
Application number
PCT/CN2014/095940
Other languages
English (en)
Chinese (zh)
Inventor
吴光辉
王振云
范伟
彭德其
张俊丰
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.)
Hunan Jiang Ye Mechanical And Electrical Technology Co Ltd
Original Assignee
Hunan Jiang Ye Mechanical And Electrical Technology Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hunan Jiang Ye Mechanical And Electrical Technology Co Ltd filed Critical Hunan Jiang Ye Mechanical And Electrical Technology Co Ltd
Publication of WO2016049994A1 publication Critical patent/WO2016049994A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • 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
    • 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

Definitions

  • the invention belongs to the field of waste lead-acid battery regeneration, and particularly relates to a lead paste desulfurization method based on a grinding mechanism.
  • the main components of the lead-acid battery include: anode plate (lead peroxide PbO 2 ), cathode plate (sponge lead Pb), and electrolyte (dilute sulfuric acid). It is a kind of chemical power source widely used in the world. It has the advantages of stable voltage, safe and reliable, low price, wide application range and abundant raw materials. It is the largest and most versatile battery in all kinds of batteries in the world.
  • the main components in the lead-acid battery after reaching the end of life are converted into: PbSO 4 (50-60%), PbO 2 (30-35%), PbO (10-15%) and Sb (0.2-0.7%).
  • the lead paste (or sulfuric acid) containing sulfuric acid compounds and heavy metal substances such as lead, antimony, arsenic and zinc may adversely affect the environment and human health. Therefore, it is of great significance to carry out the recycling of waste lead-acid batteries.
  • the traditional lead-acid lead-acid battery recycling process is to mix the battery plate and coke, and then directly roast at a high temperature above 1350 ° C to reduce lead sulfate to metal lead.
  • toxic and harmful fumes such as SO 2 and lead dust generated during the whole process will cause serious damage to the ecological environment.
  • Han Zhao et al. proposed in the patent “a method for desulfurization of lead-acid battery lead paste” that the lead-acid battery lead paste and desulfurizer and co-solvent are mixed in a certain ratio, and then fired at a high temperature of 100-1000 ° C for 5-240 min. Desulfurization is carried out.
  • the disadvantage of this method is that the reaction requires a higher temperature, and the reaction time is longer, and the subsequent treatment is more complicated.
  • the clean production standard (HJ510-2009) of China's lead-acid battery lead recycling industry recommends a clean production process.
  • the core of the process is to convert lead sulfate in lead paste into lead carbonate and sodium sulfate under the action of sodium carbonate.
  • the solid After the mixture obtained by the reaction is filtered, the solid enters the smelting process to recover lead, and the sodium sulfate solution is purified and crystallized to obtain a sodium sulfate product, which transfers the sulfur-containing solid from the solid to the liquid before entering the thermal decomposition, so Also known as lead paste pre-desulfurization.
  • the decomposition temperature of lead carbonate obtained by the method is very low, which can greatly save the energy consumption of the subsequent decomposition furnace, and at the same time, enter the melting
  • the solid material of the furnace contains no sulfur, and the produced flue gas also contains no or little sulfur dioxide.
  • the process has good energy saving benefits and economic benefits.
  • the desulfurization reaction is as follows:
  • the PbCO 4 particles and the Na 2 CO 3 solution are reacted, and the formed PbCO 3 is coated on the surface of the PbSO 4 particles.
  • the PbCO 3 outer shell covering the outer surface of the PbSO 4 must be stripped in time to expose the PbSO 4 to the PbSO 4 .
  • a pre-desulfurization reaction can occur in order to increase the efficiency of the reaction.
  • both domestic and foreign adopting a tank reactor with stirring function the equipment achieves the renewal of the surface of lead sulfate particles by the hydraulic shearing action by stirring, the capacity is limited, the reaction is slow, and the desulfurization effect is unstable.
  • the method is to grind the lead paste raw material before the desulfurization reaction to reduce the particle size of the solid matter in the lead paste, the essence of which is to increase the contact area, in fact, the performance update during the pre-desulfurization reaction process It is the key to the process. Reducing the particle size of the raw material of the lead paste has limited promotion of the progress of the desulfurization reaction. Yang Zhengqun et al.
  • the existing methods have problems such as high reaction temperature, long cycle, complicated subsequent processing, or environmental pollution.
  • the present invention provides an energy-efficient, desulfurization-based effect based on The lead paste desulfurization method of the grinding mechanism.
  • a desulfurizing agent one or several desulfurizing agents in soda ash, caustic soda, sodium oxalate, ammonium carbonate or ammonium hydrogencarbonate are added to the stirred tank as a powder or a solution, and the desulfurizing agent and the PbSO 4 in the lead paste slurry are The ratio of the amount of the substance is 1-1.5:1;
  • the desulfurizing agent may be another chemical substance capable of undergoing precipitation displacement reaction with PbSO 4 .
  • the invention not only stirs the lead paste slurry and the desulfurizing agent, but also performs the desulfurization reaction under the action of the grinding desulfurization device, and the stirring action can make the two fully contact, and the grinding action can make the surface of the lead sulfate be updated in time, so that the lead paste
  • the lead sulfate in the timely action with the desulfurizer, the reaction is rapid, the sulfur content of the end material is low, the desulfurization efficiency is obviously improved, the desulfurization rate is over 90%, and the production capacity of the system is also improved;
  • the invention has simple operation, stable process, low energy consumption and cost, no high temperature, no secondary pollution, and belongs to an environmentally friendly process, and has broad application prospects.
  • the lead paste slurry obtained by crushing and separating the lead-acid battery is pumped into the desulfurization stirred tank.
  • the initial sulfur content of the lead paste is 5.4%
  • the specific gravity of the control slurry is 1.8t/m 3
  • the pumping amount is 15m 3
  • the Na 2 CO is pressed.
  • the molar ratio of PbSO 4 to 1.2:1 is added with Na 2 CO 3 solution, and the temperature of the slurry in the stirred tank is controlled to 70 ° C.
  • the slurry in the desulfurization stirred tank is pumped out through the grinding desulfurization device, and the slurry is in the slurry.
  • the tank is circulated between the stirred tank and the grinding desulfurization unit.
  • the lead paste slurry obtained by crushing and separating the lead-acid battery is pumped into the desulfurization stirred tank.
  • the initial sulfur content of the lead paste is 5.6%
  • the specific gravity of the control slurry is 1.8t/m 3
  • the pumping amount is 15m 3
  • the Na 2 CO is pressed.
  • the molar ratio of PbSO 4 is 1.1:1
  • the Na 2 CO 3 powder is added
  • the temperature of the slurry in the stirred tank is controlled to 50 ° C
  • the slurry in the desulfurization stirred tank is pumped out through the grinding desulfurization device while stirring, and the slurry is The tank is circulated between the stirred tank and the grinding desulfurization unit.
  • the sulfur content of the lead paste after desulfurization is 0.23%, and the desulfurization rate is 95.9%.
  • the lead paste slurry obtained by crushing and separating the lead-acid battery is pumped into the desulfurization stirring tank.
  • the initial sulfur content of the lead paste is 5.2%
  • the specific gravity of the control slurry is 1.6t/m 3
  • the pumping amount is 15m 3
  • the Na 2 CO is pressed.
  • the molar ratio of PbSO 4 is 1.1:1, adding Na 2 CO 3 powder, controlling the temperature of the slurry in the stirred tank to 60 ° C, while stirring, the slurry in the desulfurization stirred tank is pumped out through the grinding desulfurization device, and the slurry is The tank is circulated between the stirred tank and the grinding desulfurization unit.
  • the lead paste slurry obtained by crushing and separating the lead-acid battery is pumped into the desulfurization stirring tank.
  • the initial sulfur content of the lead paste is 5.1%
  • the specific gravity of the control slurry is 1.6t/m 3
  • the pumping amount is 15m 3
  • the Na 2 CO is pressed.
  • the molar ratio of PbSO 4 is 1:1 to the Na 2 CO 3 solution
  • the temperature of the slurry in the stirred tank is controlled to 70 ° C.
  • the slurry in the desulfurization stirred tank is pumped out through the grinding desulfurization device, and the slurry is in the slurry.
  • the tank is circulated between the stirred tank and the grinding desulfurization unit.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Secondary Cells (AREA)

Abstract

L'invention concerne un procédé de désulfuration de pâte de plomb en fonction d'un mécanisme de broyage, ledit procédé comprenant : la bonne agitation d'une suspension épaisse de pâte de plomb et d'un agent de désulfuration dans une cuve d'agitation, le pompage de la suspension épaisse présente dans la cuve d'agitation et l'opération consistant à amener la suspension épaisse à s'écouler dans un appareil de désulfuration et de broyage pour une réaction de désulfuration, l'opération consistant à amener la suspension épaisse à circuler entre la cuve d'agitation et de broyage et l'appareil de désulfuration ; l'exécution d'une filtration sous pression de la suspension épaisse désulfurée, à l'aide d'un filtre sous pression de manière à obtenir un gâteau de filtration, l'opération consistant à amener le gâteau de filtration à entrer dans un étage de fusion, la purification, puis la cristallisation d'une solution de sulfate de sodium obtenue et d'une solution de sulfate d'ammonium obtenue, de manière à obtenir une production de sulfate de sodium et un produit sulfate d'ammonium. Le procédé présente une vitesse de désulfuration élevée, un bon effet de désulfuration et un fonctionnement stable.
PCT/CN2014/095940 2014-09-29 2014-12-31 Procédé de désulfuration de pâte de plomb en fonction d'un mécanisme de broyage Ceased WO2016049994A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201410513101.9A CN104263944A (zh) 2014-09-29 2014-09-29 一种基于研磨机制的铅膏脱硫方法
CN201410513101.9 2014-09-29

Publications (1)

Publication Number Publication Date
WO2016049994A1 true WO2016049994A1 (fr) 2016-04-07

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CN (1) CN104263944A (fr)
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Cited By (1)

* Cited by examiner, † Cited by third party
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CN113957258A (zh) * 2021-10-23 2022-01-21 安徽省华鑫铅业集团有限公司 一种基于富氧侧吹的铅膏冶炼工艺

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CN105420489B (zh) * 2015-11-28 2018-05-08 湘潭大学 一种基于节流自碰撞的铅膏脱硫方法
CN106367594A (zh) * 2016-08-25 2017-02-01 安徽华铂再生资源科技有限公司 一种低能耗、快速、可循环铅膏脱硫母液脱盐工艺
CN106337112A (zh) * 2016-08-25 2017-01-18 安徽华铂再生资源科技有限公司 一种湿法、低液固比废铅酸蓄电池铅膏脱硫工艺
CN106367593B (zh) * 2016-08-25 2018-05-01 安徽华铂再生资源科技有限公司 一种利用高锡再生铅生产铅锡合金的工艺
CN106282540A (zh) * 2016-08-25 2017-01-04 安徽华铂再生资源科技有限公司 铅膏中铅金属低能耗高效回收工艺
CN106222425A (zh) * 2016-08-31 2016-12-14 株洲鼎端装备股份有限公司 一种废旧铅酸蓄电池中铅膏的脱硫方法
CN106435194A (zh) * 2016-09-30 2017-02-22 刘振 废旧铅酸电池铅膏高效脱硫工艺
CN106521180A (zh) * 2016-10-31 2017-03-22 湘潭大学 一种以碳酸氢铵为脱硫剂的铅膏脱硫方法
CN106834734A (zh) * 2017-03-18 2017-06-13 江西理工大学 一种搅拌球磨机高效脱硫方法
CN107394300A (zh) * 2017-06-30 2017-11-24 湖北楚凯冶金有限公司 一种废铅酸蓄电池铅膏的脱硫方法
IT201800005267A1 (it) * 2018-05-11 2019-11-11 Procedimento per la desolforazione di materiali e/o residui contenenti solfato di piombo mediante un composto amminico
CN112430744A (zh) * 2020-10-09 2021-03-02 超威电源集团有限公司 一种废旧铅膏回收方法
CN112442588A (zh) * 2020-10-09 2021-03-05 超威电源集团有限公司 一种脱硫剂再生的方法
CN113943866A (zh) * 2021-10-16 2022-01-18 安徽省华鑫铅业集团有限公司 一种废旧电池的铅泥脱硫回收工艺

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4927510A (en) * 1987-10-20 1990-05-22 Engitec Impianti S.P.A. Hydrometallurgical process for recovering in pure metal form all the lead contained in the active mass of exhausted batteries
JPH05311259A (ja) * 1992-04-13 1993-11-22 Nikko Kinzoku Kk 鉛電解アノードスライムの湿式処理方法
CN103000968A (zh) * 2012-10-31 2013-03-27 高金菊 一种废铅酸蓄电池铅膏脱硫转化方法
CN103468970A (zh) * 2013-09-03 2013-12-25 四川景星环境科技有限公司 一种用于再生铅行业铅膏脱硫剂及其脱硫方法
CN103540741A (zh) * 2013-11-05 2014-01-29 湖南江冶机电科技股份有限公司 一种铅膏湿法强制脱硫工艺
CN103633394A (zh) * 2013-12-13 2014-03-12 华南师范大学 一种废旧铅膏脱硫方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1191650B (it) * 1986-01-09 1988-03-23 Tecneco Spa Processo idrometallurgico per un recupero complessivo dei componenti delle batterie acide al piombo esauste
CN102534220B (zh) * 2011-12-22 2013-07-03 阳煤集团山西吉天利科技有限公司 废旧铅酸蓄电池闭合循环回收利用方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4927510A (en) * 1987-10-20 1990-05-22 Engitec Impianti S.P.A. Hydrometallurgical process for recovering in pure metal form all the lead contained in the active mass of exhausted batteries
JPH05311259A (ja) * 1992-04-13 1993-11-22 Nikko Kinzoku Kk 鉛電解アノードスライムの湿式処理方法
CN103000968A (zh) * 2012-10-31 2013-03-27 高金菊 一种废铅酸蓄电池铅膏脱硫转化方法
CN103468970A (zh) * 2013-09-03 2013-12-25 四川景星环境科技有限公司 一种用于再生铅行业铅膏脱硫剂及其脱硫方法
CN103540741A (zh) * 2013-11-05 2014-01-29 湖南江冶机电科技股份有限公司 一种铅膏湿法强制脱硫工艺
CN103633394A (zh) * 2013-12-13 2014-03-12 华南师范大学 一种废旧铅膏脱硫方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113957258A (zh) * 2021-10-23 2022-01-21 安徽省华鑫铅业集团有限公司 一种基于富氧侧吹的铅膏冶炼工艺

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