CN105950870B - 一种废铅酸蓄电池铅膏水热深度转化脱硫的方法 - Google Patents
一种废铅酸蓄电池铅膏水热深度转化脱硫的方法 Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
一种废铅酸蓄电池铅膏水热深度转化脱硫的方法,废铅膏与碱溶液混合后加入到高压反应釜中,在要求温度和氮气分压下进行反应,使硫酸铅与碱完全反应脱除硫酸根,达到反应时间后固液分离,脱硫转化液回收硫酸钠,脱硫转化渣进一步提取铅。本发明采用水热方式强化了废铅膏碱性转化脱硫过程,实现废铅膏中硫酸根的完全脱除,碱的消耗量仅为理论用量的1.0~1.05倍,脱硫率达到99.0%以上,为转化渣后续提取铅创造了有利条件。
Description
技术领域
本发明涉及有色冶金领域中湿法冶金过程,特别是废铅酸蓄电池铅膏水热深度转化脱硫的湿法冶金方法。
背景技术
铅是银白色重有色金属,基于其特殊的物理化学性质主要被用于制造合金,其中铅酸蓄电池是最主要的消费领域,其占全球总铅消耗量的80.0%以上。虽然铅酸蓄电池重量能量比低于MH-Ni电池和Li-ion电池,但由于其性价比高、技术成熟和安全性能好等优点,广泛应用于国民经济的各个领域,铅酸蓄电池使用量占全球二次电池市场份额的70.0%以上。近些年我国汽车工业的快速发展刺激了铅酸蓄电池工业的飞速发展,我国已经成为世界上最大的铅酸蓄电池制造国、消费国和出口国,铅酸蓄电池的大量使用势必会产生相当数量的废铅酸蓄电池,使得废旧铅酸蓄电池已经变成最重要的铅再生资源(代少振等.废铅酸蓄电池回收技术现状[J].世界有色金属, 2015, 9, 15-17.)。根据国家***和中国有色金属工业协会数据,2014年中国精炼铅产量达到421.8万吨,其中再生铅产量为160.0万吨,占全年铅产量的37.9%,并有进一步增加的趋势。
废铅酸蓄电池的回收利用过程通常是先拆解后再分别回收(高倩等.废旧铅酸蓄电池破碎分选***研究与探讨[J]. 蓄电池, 2013, 50(1), 3-7),拆解产物有四种,一是废电解液,成分为硫酸溶液,通常送废水处理;二是板栅,主要成分为铅锑合金,通常重新熔铸成合金;三是塑料,通常返回塑料厂家重新利用;四是废铅膏,主要成分为硫酸铅和铅氧化物,通常用于炼铅原料,这四种产物的重量分别占蓄电池总重量的10-20%、20-30%、10-15%和35-50%。废铅膏的成分由于电池生产厂家不同和报废程度差异,各组分含量有所波动,分别为PbSO4(40-60%)、PbO2(25-35%)、PbO(5-10%)和Pb(1-5%)及少量Sb(0.5%)。
由于废铅膏中含有大量的硫酸铅和铅多种价态氧化物,处理难度大,使其成为废铅酸蓄电池回收利用的瓶颈。废铅膏处理分为火法工艺和湿法工艺,这两种工艺通常都是以阴极铅为目标产物,各有利弊,其中火法工艺获得了广泛应用。
火法工艺是废铅膏经过还原熔炼得到粗铅,然后电解精炼产出阴极铅,有单独熔炼和混合熔炼两类。单独熔炼方法包括直接和间接两种方式(李卫锋等.废铅酸蓄电池前再生技术现状及进展[J].中国有色冶金, 2011, (6): 53-57.),直接单独熔炼法是指废铅膏直接在反射炉、鼓风炉、短窑、底吹炉和侧吹炉等熔炼炉中还原熔炼,熔炼烟气经过淋洗后排放,具有流程短的优点并获得广泛应用,但存在熔炼能耗高、高温铅粉尘危害和烟气污染治理难度大等缺点,普遍认为这是由于废铅膏中硫酸铅的存在引起的。为了克服此缺点,研究人员提出间接单独熔炼方法(吴广龙等.废铅膏冶炼工艺比较分析研究[J].蓄电池,2015,152(5): 209-211.),即废铅膏在熔炼前采用预处理方法脱除硫酸根,中间产物再单独还原熔炼产出粗铅,该方法似乎克服了直接单独熔炼方法的缺点,但是预处理过程往往存在脱硫不彻底的问题。混合熔炼方法是将废铅膏与铅精矿搭配后熔炼,利用铅精矿的化学反应热,使两者同步熔炼产出粗铅。该方法在原生铅冶炼厂获得了广泛应用,表面上解决了废铅膏熔炼过程对温度和尾气治理的要求,但是将杂质含量低的高品位铅膏与铅精矿混合熔炼,产出的粗铅质量差,增加了提纯的难度,此外,铅膏的配入导致原生铅冶炼***炉况恶化和污酸产量增加。
为了克服火法工艺处理的缺点,研究人员开发了废铅膏的湿法处理工艺,即废铅膏通过固相电解或湿法溶解后电积产出阴极铅,主要包括固相电解工艺、浸出-电积工艺和转化-浸出-电积工艺三类( 杨家宽等.废铅酸电池铅膏回收技术的研究进展[J]. 现代化工, 2009, 29(3): 32-37.)。固相电解工艺是将废铅膏涂布于阴极板上并在碱性体系隔膜电解产出阴极铅。浸出-电积工艺是将废铅膏浸出并电积产出阴极铅,废铅膏直接浸出过程通常使用能与铅形成配合物的醋酸、氢氧化钠、铵盐、氯化物和碱性有机物等试剂。转化-浸出-电积工艺则是废铅膏转化脱硫后再经过浸出并电积产出阴极铅,该工艺注重废铅膏中铅的提取效率和溶液再生等方面,所以浸出和电积通常在HBF4或H2SiF6体系进行,但不同工艺对转化脱硫过程略有不同。经典的RSR工艺则是用碳酸铵脱除废铅膏中的硫酸根并使其转化为碳酸铅,然后用亚硫酸钠和二氧化硫还原铅膏中的二氧化铅,转化渣用HBF4或H2SiF6浸出,含铅溶液最后电积产出阴极铅。USBM工艺略有区别的是采用铅粉作为还原剂,而CX-EW工艺则采用碳酸钠作为脱硫剂和双氧水作为还原剂。EX-EWS工艺则用细菌将铅膏中的铅化合物转化为PbS,PbS用氟硼酸高铁溶液氧化浸出,浸出液在阴极室电积阴极铅,阳极室实现氟硼酸高铁溶液的再生。湿法工艺很好的解决了火法工艺存在的问题,但是仍然存在试剂消耗大和能耗高的缺点,尤其是电积过程难以抑制阳极PbO2的析出,使得铅回收率低。
详细对比废铅膏处理工艺可以看出,火法工艺的难点是在熔炼过程如何对待PbSO4的分解问题,湿法工艺的难点则是如何使PbSO4完全转化脱硫,这两个问题的解决都是通过转化脱硫的预处理过程。废铅膏转化脱硫过程目的是脱除废铅膏PbSO4的硫酸根并使其转化为碳酸铅或氢氧化铅,脱硫转化过程使用的转化剂主要有Na2CO3、K2CO3、(NH4)2CO3、NH4HCO3、NaOH和KOH等,通常实际操作中硫酸根的脱除率仅85-95%,脱硫不彻底和还原效率低严重影响了该方法的应用效果,研究人员提出采用超重力、球磨和超声波等手段强化转化脱硫过程(潘军青等.铅酸蓄电池回收铅技术的发展现状[J].北京化工大学学报, 2014,41(3): 1-14.),但仍然达不到期望的效果,主要原因可能是废铅酸蓄电池在放电过程板栅上析出的非导电硫酸铅晶体,在常规转化脱硫过程很难与试剂反应。所以,采用何种方法能实现完全转化脱硫则是废铅膏处理的关键。
近些年国家为了进一步规范废铅酸蓄电池的回收体系和处理技术,相继出台了多个文件以保证铅酸蓄电池回收的正常发展,尤其是2012年工信部与环保部联合制定的《再生铅行业准入条件》,对生产规模、工艺和装备等提出了明确要求,“对分选出的铅膏必须进行脱硫预处理或送硫化铅精矿冶炼厂合并处理,脱硫母液必须进行处理并回收副产品……,再生铅企业不得直接熔炼带壳废铅蓄电池,不得利用坩埚炉熔炼再生铅,应采用密闭熔炼、低温连续熔炼、新型节能环保熔炼炉等先进工艺及设备,并在负压条件下生产,防止废气逸出。”这些文件的制定,有力地推进了再生铅行业规范健康的发展,提高资源利用率和节能环保水平。
发明内容
为了克服传统废铅膏转化脱硫方法的不足,本发明提供一种采用水热强化方式深度转化脱除废铅膏中硫酸根,且碱耗量低和环境污染小的湿法冶金方法。
为达到上述目的本发明采用的技术方案是:废铅膏与碱溶液混合后加入到高压反应釜中,在要求温度和氮气分压下进行反应,使硫酸铅与碱完全反应脱除硫酸根,达到反应时间后固液分离,脱硫转化液回收硫酸钠,脱硫转化渣进一步提取铅。本技术方案的实质是采用水热方式强化了废铅膏碱性转化脱硫过程,实现废铅膏中硫酸根的完全脱除,为转化渣后续提取铅创造了有利条件。
具体的工艺过程和参数如下:
废铅膏按液固比(液体体积与固体重量之比,L/Kg)1~3∶1加水浆化,同时加入废铅膏重量比0.15~0.40倍的固体碱,将混合浆液加入到不锈钢高压反应釜中,启动搅拌并控制转速为100~200r/min,向反应釜内通入氮气,控制氮气分压0.2~0.5MPa通气1~5min,然后升高温度至100~200℃,控制氮气分压0.5~1.0MPa反应1~5h,反应完成冷却降低温度至60~80℃时,采用真空抽滤方式实现液固分离,脱硫转化液回收硫酸钠,脱硫转化渣进一步提取铅。水热深度转化脱硫过程发生的主要化学反应如下:
(1)
(2)
本发明使用的碱为碳酸钠和氢氧化钠中的一种或两种。
本发明适用于处理废铅酸蓄电池拆解产物中的废铅膏,其主要成分以重量百分比计为(%):Pb50.0~75.0%、S4.0~6.5%、Sb0.1~0.5% 和H2O5.0~10.0%。也适合处理含硫酸铅的固体物料。
本发明与传统的废铅膏转化脱硫处理方法比较,有以下优点:1、本发明采用水热方式强化了废铅膏碱性转化脱硫过程,实现废铅膏中硫酸根的完全脱除,脱硫率达到99.0%以上;2、本发明采用水热强化方式,不仅提高了脱硫率,而且降低了碱的消耗,碱的消耗量仅为理论用量的1.0~1.05倍;3、本发明具有工艺过程操作简单、技术指标稳定、劳动强度小和生产成本低等优点。
附图说明
图1:本发明工艺流程示意图。
具体实施方式
实施例1:
废铅酸蓄电池拆解产物中的废铅膏,其主要成分以重量百分比计为(%):Pb73.80%、S5.25%和Sb0.15%,碳酸钠为分析纯试剂。将2000g废铅膏与356g碳酸钠同时加入到4000ml水中浆化,然后混合浆液加入到不锈钢高压反应釜中,使搅拌速度保持在120r/min,控制氮气分压0.3MPa通气2min,然后升高温度至160℃,控制氮气分压0.8MPa反应3h,反应完成冷却降低温度至65℃时,采用真空抽滤方式实现液固分离,脱硫转化渣中硫含量降低至0.02%,脱硫率达到99.40%。
实施例2:
废铅酸蓄电池拆解产物中的废铅膏,其主要成分范围以重量百分比计为(%):Pb73.80%、S5.25%和Sb0.15%,氢氧化钠为分析纯试剂。将2000g废铅膏与268g氢氧化钠同时加入到4000ml水中浆化,然后混合浆液加入到不锈钢高压反应釜中,使搅拌速度保持在120r/min,控制氮气分压0.3MPa通气2min,然后升高温度至180℃,控制氮气分压0.8MPa反应3h,反应完成冷却降低温度至70℃时,采用真空抽滤方式实现液固分离,脱硫转化渣中硫含量降低至0.01%,脱硫率达到99.38%。
Claims (3)
1.一种废铅酸蓄电池铅膏水热深度转化脱硫的方法,其特征在于:废铅膏加水浆化,按水体积L与废铅膏重量kg的液固比为1~3∶1,同时加入废铅膏重量比0.15~0.40倍的固体碱,将混合浆液加入到高压反应釜中,启动搅拌并控制转速为100~200r/min,向反应釜内通入氮气,控制氮气分压0.2~0.5MPa通气1~5min,然后升高温度至150~200℃,控制氮气分压0.5~1.0MPa反应1~5h,反应完成冷却降低温度至60~80℃,再采用真空抽滤方式实现液固分离,脱硫转化液回收硫酸钠,脱硫转化渣进一步提取铅。
2.如权利要求1所述的废铅酸蓄电池铅膏水热深度转化脱硫的方法,其特征在于所述的固体碱为碳酸钠和氢氧化钠中的一种或两种。
3.如权利要求1所述的废铅酸蓄电池铅膏水热深度转化脱硫的方法,其特征在于:所述的废铅膏的主要成分以重量百分比计为:Pb50.0~75.0%、S4.0~6.5%、Sb0.1~0.5%和H2O5.0~10.0%。
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