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WO2016049994A1 - Lead paste desulfurization method based on grinding mechanism - Google Patents

Lead paste desulfurization method based on grinding mechanism 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
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Prior art keywords
desulfurization
slurry
lead
lead paste
grinding
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Chinese (zh)
Inventor
吴光辉
王振云
范伟
彭德其
张俊丰
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Hunan Jiang Ye Mechanical And Electrical Technology Co Ltd
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Hunan Jiang Ye Mechanical And Electrical Technology Co Ltd
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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
    • 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

A lead paste desulfurization method based on a grinding mechanism comprises: fully stirring lead paste slurry and a desulfurization agent in a stirring tank, pumping the slurry in the stirring tank and enabling the slurry to flow through a grinding and desulfurization apparatus for a desulfurization reaction, and enabling the slurry to be circulated between the stirring tank and the grinding and desulfurization apparatus; and carrying out pressure filtering of the desulfurized slurry by using a pressure filter so as to obtain a filter cake, and enabling the filter cake to enter a smelting stage, and purifying and then crystallizing an obtained sodium sulfate solution and an obtained ammonium sulfate solution, so as to obtain a sodium sulfate production and an ammonium sulfate product. The method has a fast desulfurization speed, a good desulfurization effect and stable operation.

Description

一种基于研磨机制的铅膏脱硫方法Lead paste desulfurization method based on grinding mechanism 技术领域Technical field

本发明属于废旧铅酸蓄电池再生领域，具体涉及一种基于研磨机制的铅膏脱硫方法。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.

背景技术Background technique

铅酸蓄电池内部主要组成成分包括：阳极板(过氧化铅PbO2)、阴极板(海绵状铅Pb)、电解液(稀硫酸)。它是目前世界上广泛使用的一种化学电源，具有电压平稳、安全可靠、价格低廉、适用范围广、原材料丰富等优点，是世界上各类电池中产量最大、用途最广的一种电池。达到使用寿命后的铅酸蓄电池中主要成分会转化为：PbSO4(50-60％)、PbO2(30-35％)、PbO(10-15％)和Sb(0.2-0.7％)。其中含硫酸化合物的铅膏(或硫酸)及铅、锑、砷、锌等重金属物质会对环境和人体健康造成不利的影响。所以开展废铅酸电池的再生利用意义重大。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.

传统火法废铅酸电池回收铅工艺是将电池极板破碎与焦炭混合，然后直接在1350℃以上的高温下焙烧，将硫酸铅还原为金属铅。但是在整个过程中会产生的SO2、铅尘等有毒有害烟气，对生态环境造成严重的破环。韩召等在专利“一种废铅酸蓄电池铅膏脱硫方法”中提出将废铅酸蓄电池铅膏和脱硫剂、助溶剂按一定比例混合，然后在100-1000℃的高温中焙烧5-240min进行脱硫。该方法的不足之处在于反应需要较高的温度，并且反应时间较长，后续处理也较为复杂。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. However, 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.

我国废铅酸蓄电池铅回收业的清洁生产标准(HJ510-2009)推荐采用清洁的生产工艺，该工艺的核心内容为：在碳酸钠作用下将铅膏中硫酸铅转化为碳酸铅和硫酸钠，反应得到的混合物过滤后，固体进入冶炼环节回收铅，硫酸钠溶液进入净化、结晶后得到硫酸钠产品，该过程将含硫固体在进入热分解前即将硫从固体中转移到液体中去，所以也称为铅膏预脱硫。该法得到的碳酸铅分解温度很低，可以大大节省后续分解炉的能耗，同时，进入熔炼 炉的固体物料不含硫，产出的烟气中也不含或含有很少的二氧化硫，该工艺有很好的节能效益和经济效益。脱硫反应如下：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. 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:

PbSO4+Na2CO3→PbCO3+Na2SO4 PbSO 4 +Na 2 CO 3 →PbCO 3 +Na 2 SO 4

该反应中KspPbSO4＝1.6*10-8、KspPbCO3＝7.4*10-14，两者相差6个数量级，热力学上很容易进行。In this reaction, K sp PbSO 4 =1.6*10 -8 and K sp PbCO 3 =7.4*10 -14 , which differ by 6 orders of magnitude and are thermodynamically easy to carry out.

在上述预脱硫过程中PbSO4颗粒和Na2CO3溶液的反应，生成的PbCO3包裹在PbSO4颗粒表面，必须及时将包裹PbSO4外表面的PbCO3外壳剥除，才能使PbSO4暴露在Na2CO3溶液中，才能发生预脱硫反应，为提高该反应的效率。国内外目前采用的均是带搅拌功能的釜式反应器，该设备通过搅拌产生的水力剪切作用实现硫酸铅颗粒表面的更新，能力有限，反应慢，脱硫效果不稳定。高金菊在专利“一种废铅酸蓄电池铅膏脱硫转化方法”中提到将电池破碎后产生的铅膏浆液烘干，然后在研磨机内研磨10-30min，将铅膏颗粒研磨至50-300μm后再进行后续脱硫，该方法是对脱硫反应前的铅膏原料进行研磨以减小铅膏内固体物质的粒径，其本质是增大接触面积，实际上，预脱硫反应过程中的表现更新才是过程的关键，减小铅膏原始物料的粒径对脱硫反应进程促进有限。杨正群等在专利“一种废铅酸蓄电池铅膏脱硫方法”中提出用氨水或含氨基物质的溶液在连续搅拌作用下，经固液分离进行铅膏脱硫。该方法并未对反应过程进行有效的强化，同时采用了容易挥发的氨水，在使用过程中会对生产和环境造成一定二次污染。In the above pre-desulfurization process, 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 . In the Na 2 CO 3 solution, a pre-desulfurization reaction can occur in order to increase the efficiency of the reaction. At present, 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. Gao Jinju mentioned in the patent “A method for desulfurization of lead-acid battery lead paste desulfurization” that the lead paste slurry produced by crushing the battery is dried, and then ground in a grinder for 10-30 min to grind the lead paste particles to 50-300 μm. After the subsequent desulfurization, 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. proposed in the patent “a method for desulfurization of lead-acid battery lead paste desulfurization” that the solution of ammonia or water-containing substance is subjected to solid-liquid separation for desulfurization of lead paste under continuous stirring. The method does not effectively strengthen the reaction process, and at the same time uses a volatile ammonia water, which causes a certain secondary pollution to the production and environment during use.

技术问题technical problem

现有的方法存在反应温度高、周期长、后续处理复杂或会造成环境污染等问题。The existing methods have problems such as high reaction temperature, long cycle, complicated subsequent processing, or environmental pollution.

技术解决方案Technical solution

为了解决上述技术问题，本发明提供一种高效节能、脱硫效果好的基于 研磨机制的铅膏脱硫方法。In order to solve the above technical problems, the present invention provides an energy-efficient, desulfurization-based effect based on The lead paste desulfurization method of the grinding mechanism.

本发明解决上述技术问题的技术方案包括以下步骤：The technical solution of the present invention to solve the above technical problem includes the following steps:

(1)制备铅膏浆液：铅酸废电池经破碎之后分离出其中的铅栅和塑料片，将产生的铅泥引入搅拌罐中，将铅膏浆液的浓度调配至铅膏的质量分数为10-90％；(1) Preparation of lead paste slurry: After the lead-acid waste battery is crushed, the lead grid and the plastic piece are separated, and the produced lead mud is introduced into the stirring tank, and the concentration of the lead paste slurry is adjusted to a mass fraction of the lead paste of 10 -90%;

(2)加入脱硫剂：将纯碱、烧碱、草酸钠、碳酸铵或碳酸氢铵中的一种或几种脱硫剂以粉末或者溶液形式加入搅拌罐，脱硫剂与铅膏浆液中的PbSO4的物质的量之比为1-1.5：1；(2) adding 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;

(3)研磨脱硫：将铅膏浆液与脱硫剂在搅拌罐中充分搅拌，同时将搅拌罐内的浆液泵出流经研磨脱硫装置进行脱硫反应，浆液在搅拌罐与研磨脱硫装置之间循环，脱硫反应10-60min，温度控制在20-80℃；(3) Grinding desulfurization: the lead paste slurry and the desulfurizing agent are thoroughly stirred in the stirring tank, and the slurry in the stirring tank is pumped out through the grinding desulfurization device for desulfurization reaction, and the slurry is circulated between the stirring tank and the grinding desulfurization device. Desulfurization reaction 10-60min, temperature control at 20-80 ° C;

(4)后续处理：脱硫后的浆液经压滤机压滤得到的滤饼进入熔炼环节，得到的硫酸钠、硫酸铵溶液净化后结晶得到硫酸钠、硫酸铵产品。(4) Subsequent treatment: the filter cake obtained by pressure filtration of the slurry after desulfurization enters the melting step, and the obtained sodium sulfate and ammonium sulfate solution are purified and crystallized to obtain sodium sulfate and ammonium sulfate products.

上述的基于研磨机制的铅膏脱硫方法，所述的脱硫剂还可为其它能够与PbSO4发生沉淀置换反应的化学物质。In the above-mentioned polishing mechanism-based lead paste desulfurization method, the desulfurizing agent may be another chemical substance capable of undergoing precipitation displacement reaction with PbSO 4 .

有益效果Beneficial effect

本发明的有益效果在于：The beneficial effects of the invention are:

(1)本发明不但对铅膏浆液与脱硫剂进行搅拌，同时在研磨脱硫装置作用下进行脱硫反应，搅拌作用可以使二者充分接触，研磨作用能够使得硫酸铅表面及时得到更新，使铅膏中的硫酸铅及时与脱硫剂作用，反应迅速、终点物料含硫率低，明显提高了脱硫效率，脱硫率达到90％以上，同时也提高了系统的生产能力；(1) 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;

(2)本发明的操作简单，工艺稳定，能耗和成本都较低，不需要高温，不会产生二次污染，属于环保型工艺，有广阔的应用前景。(2) 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.

本发明的最佳实施方式 BEST MODE FOR CARRYING OUT THE INVENTION

首先将铅酸蓄电池破碎分离后所得的铅膏浆液泵入脱硫搅拌罐，铅膏初始含硫量为5.4％，控制浆液比重1.8t/m3，泵入量为15m3，然后按Na2CO3与PbSO4的摩尔比为1.2：1添加Na2CO3溶液，控制搅拌罐中浆液温度为70℃，在搅拌的同时，将脱硫搅拌罐内的浆液泵出流经研磨脱硫装置，浆液在搅拌罐与研磨脱硫装置之间循环。Firstly, 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 , and then the Na 2 CO is pressed. 3 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. While stirring, 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.

经此脱硫工艺脱硫40min，脱硫后铅膏含硫率为0.12％，脱硫率为97.8％。After desulfurization for 40 min by this desulfurization process, the sulfur content of the lead paste after desulfurization was 0.12%, and the desulfurization rate was 97.8%.

本发明的实施方式Embodiments of the invention

实施例1Example 1

首先将铅酸蓄电池破碎分离后所得的铅膏浆液泵入脱硫搅拌罐，铅膏初始含硫量为5.6％，控制浆液比重1.8t/m3，泵入量为15m3，然后按Na2CO3与PbSO4的摩尔比为1.1：1添加Na2CO3粉末，控制搅拌罐中浆液温度为50℃，在搅拌的同时，将脱硫搅拌罐内的浆液泵出流经研磨脱硫装置，浆液在搅拌罐与研磨脱硫装置之间循环。Firstly, 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 , and then the Na 2 CO is pressed. 3 , 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, and 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.

经此脱硫工艺脱硫40min，脱硫后铅膏含硫率为0.23％，脱硫率为95.9％。After desulfurization for 40 minutes by this desulfurization process, the sulfur content of the lead paste after desulfurization is 0.23%, and the desulfurization rate is 95.9%.

实施例2Example 2

首先将铅酸蓄电池破碎分离后所得的铅膏浆液泵入脱硫搅拌罐，铅膏初始含硫量为5.2％，控制浆液比重1.6t/m3，泵入量为15m3，然后按Na2CO3与PbSO4的摩尔比为1.1：1添加Na2CO3粉末，控制搅拌罐中浆液温度为60℃，在搅拌的同时，将脱硫搅拌罐内的浆液泵出流经研磨脱硫装置，浆液在搅拌罐与研磨脱硫装置之间循环。Firstly, 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 , and then the Na 2 CO is pressed. 3 , 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.

经此脱硫工艺脱硫40min，脱硫后铅膏含硫率为0.28％，脱硫率为94.6％。After desulfurization for 40 min by this desulfurization process, the sulfur content of the lead paste after desulfurization was 0.28%, and the desulfurization rate was 94.6%.

实施例3Example 3

首先将铅酸蓄电池破碎分离后所得的铅膏浆液泵入脱硫搅拌罐，铅膏初始含硫量为5.1％，控制浆液比重1.6t/m3，泵入量为15m3，然后按Na2CO3与PbSO4的摩尔比为1：1添加Na2CO3溶液，控制搅拌罐中浆液温度为70℃，在搅拌的同时，将脱硫搅拌罐内的浆液泵出流经研磨脱硫装置，浆液在搅拌 罐与研磨脱硫装置之间循环。Firstly, 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 , and then the Na 2 CO is pressed. 3 The molar ratio of PbSO 4 is 1:1 to the Na 2 CO 3 solution, and the temperature of the slurry in the stirred tank is controlled to 70 ° C. While stirring, 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.

经此脱硫工艺脱硫40min，脱硫后铅膏含硫率为0.32％，脱硫率为93.7％。 After desulfurization for 40 min by this desulfurization process, the sulfur content of the lead paste after desulfurization was 0.32%, and the desulfurization rate was 93.7%.

Claims (5)

一种基于研磨机制的铅膏脱硫方法，其特征在于，包括如下步骤：A method for desulfurization of a lead paste based on a grinding mechanism, comprising the steps of: (1)制备铅膏浆液：铅酸废电池经破碎之后分离出其中的铅栅和塑料片，将产生的铅泥引入搅拌罐中，制成铅膏浆液；(1) preparing a lead paste slurry: the lead acid waste battery is separated, and the lead grid and the plastic piece are separated, and the produced lead mud is introduced into the stirring tank to prepare a lead paste slurry; (2)加入脱硫剂：将脱硫剂加入步骤(1)制得的铅膏浆液中；(2) adding a desulfurizing agent: adding the desulfurizing agent to the lead paste slurry prepared in the step (1); (3)研磨脱硫：将铅膏浆液与脱硫剂在搅拌罐中充分搅拌，同时将搅拌罐内的浆液泵出流经研磨脱硫装置进行脱硫反应，浆液在搅拌罐与研磨脱硫装置之间循环；(3) Grinding desulfurization: the lead paste slurry and the desulfurizing agent are thoroughly stirred in the stirring tank, and the slurry in the stirring tank is pumped out through the grinding desulfurization device for desulfurization reaction, and the slurry is circulated between the stirring tank and the grinding desulfurization device; (4)后续处理：脱硫后的浆液经压滤机压滤得到的滤饼进入熔炼环节，得到的硫酸钠、硫酸铵溶液净化后结晶得到硫酸钠、硫酸铵产品。(4) Subsequent treatment: the filter cake obtained by pressure filtration of the slurry after desulfurization enters the melting step, and the obtained sodium sulfate and ammonium sulfate solution are purified and crystallized to obtain sodium sulfate and ammonium sulfate products. 根据权利要求1所述的基于研磨机制的铅膏脱硫方法，所述的铅膏浆液的质量分数为10％-90％。The method according to claim 1, wherein the lead paste slurry has a mass fraction of 10% to 90%. 根据权利要求1所述的基于研磨机制的铅膏脱硫方法，所述的脱硫反应的反应时间为10-60min，反应温度为20-80℃。The polishing mechanism-based lead paste desulfurization method according to claim 1, wherein the desulfurization reaction has a reaction time of 10 to 60 minutes and a reaction temperature of 20 to 80 °C. 根据权利要求1所述的基于研磨机制的铅膏脱硫方法，所述脱硫剂为纯碱、烧碱、草酸钠、碳酸铵或碳酸氢铵中的一种或几种。The polishing mechanism-based lead paste desulfurization method according to claim 1, wherein the desulfurizing agent is one or more of soda ash, caustic soda, sodium oxalate, ammonium carbonate or ammonium hydrogencarbonate. 根据权利要求1或4所述的基于研磨机制的铅膏脱硫方法，所述脱硫剂与铅膏浆液中的PbSO4的物质的量之比为1-1.5：1。 The polishing mechanism-based lead paste desulfurization method according to claim 1 or 4, wherein a ratio of the amount of the PbSO 4 substance in the desulfurizing agent to the lead paste slurry is from 1 to 1.5:1.
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