WO2018014748A9 - 氯化铵氨电还原制取铅工艺 - Google Patents

氯化铵氨电还原制取铅工艺 Download PDF

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WO2018014748A9
WO2018014748A9 PCT/CN2017/092333 CN2017092333W WO2018014748A9 WO 2018014748 A9 WO2018014748 A9 WO 2018014748A9 CN 2017092333 W CN2017092333 W CN 2017092333W WO 2018014748 A9 WO2018014748 A9 WO 2018014748A9
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lead
ammonium chloride
ammonia
reduction
cathode
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WO2018014748A1 (zh
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舒毓璋
杨龙
刘荣祥
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云南祥云飞龙再生科技股份有限公司
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Priority to US16/318,715 priority Critical patent/US10563315B2/en
Publication of WO2018014748A1 publication Critical patent/WO2018014748A1/zh
Publication of WO2018014748A9 publication Critical patent/WO2018014748A9/zh

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/18—Electrolytic production, recovery or refining of metals by electrolysis of solutions of lead
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
    • C25C5/02—Electrolytic production, recovery or refining of metal powders or porous metal masses from solutions
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/02—Electrodes; Connections thereof

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  • the invention belongs to the hydrometallurgical process technology, and particularly relates to a process for preparing lead by ammonium chloride ammonia electroreduction.
  • lead-acid batteries At present, more than 80% of the use of lead is used in lead-acid batteries. With the popularization of automobiles and the development of new energy industries, the use of lead-acid batteries is increasing, and more and more lead-acid batteries are being scrapped. How to be simple and economical Scientific and environmentally friendly disposal of used batteries, metallurgical researchers and environmental protection workers have carried out a lot of research, especially in the face of the increasingly stringent environmental requirements, the wet smelting of lead is imperative. The dismantling technology of used batteries has developed rapidly. The battery is broken and disassembled to achieve large-scale modern production. The plastic boxes and conductive grid materials are effectively recycled, but the battery paste treatment is still used. Fire smelting for processing.
  • Lead pastel mud mainly PbSO 4, PbO 2, PbO, and a small amount of metallic lead, as well as other required additives such as barium sulfate, carbon, and organic nucleating additive, lead inevitably produce dust when handling the battery manufacturing fire, sulfur dioxide, Harmful substances such as dioxins cause serious pollution to the environment.
  • the clean and environmentally friendly treatment of lead paste mud is still an urgent issue to be solved.
  • the first method is the solid phase reduction method. This method is represented by the study of solid phase electrolysis by Lu Keyuan, former Institute of Chemical Metallurgy, Chinese Academy of Sciences. Electrolysis is carried out in a NaOH solution. First, the paste is converted with NaOH (electrolytic residual liquid), PbSO 4 is converted into Pb(OH) 2 and sodium sulfate, and after transformation, dehydrated, and then the converted lead mud is coated on a special one.
  • NaOH electrolytic residual liquid
  • PbSO 4 is converted into Pb(OH) 2 and sodium sulfate
  • the second way is the electrowinning method.
  • the main feature is to dissolve lead into a soluble lead salt solution, direct current in the electrolytic cell, lead in the solution at the cathode, oxygen and PbO 2 in the anode, and the electrolyte solution used.
  • the third way is to make lead paste mud into lead compounds such as lead oxide, lead chloride and the like.
  • lead is contained in the wet zinc smelting raw material and the secondary zinc resource, and these lead are finally left in the zinc leaching slag in the form of lead sulfate.
  • lead smelting raw material and the secondary zinc resource, and these lead are finally left in the zinc leaching slag in the form of lead sulfate.
  • lead smelting raw material and the secondary zinc resource, and these lead are finally left in the zinc leaching slag in the form of lead sulfate.
  • lead smelted and recovered by fire method which not only consumes high energy, but also causes harmful pollution to the environment due to harmful substances such as lead dust, sulfur dioxide and dioxins generated during the smelting process.
  • the invention belongs to the hydrometallurgical process technology and relates to a process for reducing lead compounds to metal lead in an aqueous solution of ammonium chloride.
  • an aqueous solution of ammonium chloride is used as an electrolyte
  • a lead compound is used as a raw material
  • titanium is used as an anode
  • stainless steel or lead is used as a cathode
  • a direct current electric field is applied in the electrolytic bath
  • the lead compound is electronically reduced to metallic lead at the cathode.
  • Ammonia is oxidized to nitrogen at the anode and simultaneously generates H + ions.
  • Sulfate and chloride ions in the compound enter the solution and the added ammonia water to form ammonium sulfate, ammonium chloride, lead oxide in the lead compound, and lead dioxide reduction. It is a metal lead, and simultaneously releases OH - combined with hydrogen ions generated by the anode to form water.
  • Lead compounds include lead chloride, lead sulfate, lead monoxide, lead dioxide and mixtures thereof such as waste lead battery paste. This process is different from the existing electrolysis process and electrowinning process. The electrolyte does not contain lead, and the lead compound is directly reduced to metal lead at the cathode.
  • the process includes the following steps:
  • causticization of electrolytic waste liquid the electrolytic waste liquid is subjected to caustic demineralization with lime milk, and ammonia gas is returned to electrolysis.
  • the sulfate in the lead compound enters the lime causticized slag in the form of calcium sulfate, and the chlorine in the lead compound is The calcium chloride form is recycled.
  • the material includes lead chloride, lead sulfate, lead monoxide, and dioxide.
  • the electrolyte is ammonium chloride.
  • the anode plate comprises a titanium mesh
  • the cathode plate comprises a stainless steel plate or a lead plate.
  • the titanium mesh is a titanium mesh coated with a ruthenium coating.
  • the ammonium chloride concentration is from 0.5 to 4 mol/L.
  • the reduction voltage in the step (3) is 2.0-2.7 v
  • the current density is 100-500 A/m 2
  • the pH 6-9 is controlled by adding ammonia water.
  • the reduced solution in the step (7) includes an ammonium chloride solution.
  • the production process is free of smelting lead dust, lead fumes, sulfur dioxide fumes, dioxins and other harmful gases.
  • no chlorine gas is produced, only nitrogen, friendly to the environment, no environment. pollution problem.
  • the pH value of the solution in the whole process of ammonium reduction is neutral or weakly alkaline, and the corrosion of the equipment is small.
  • the electrolyte does not contain lead, and the electrolytic waste liquid is easy to handle.
  • raw material is divalent lead (lead chloride, lead sulfate, lead monoxide) tons of lead
  • the power consumption is 520-650 degrees
  • the raw material is lead-acid battery paste mud.
  • the lead consumption is 800-1100 degrees.
  • Lead recovery rate is over 99%, which can be used for large-scale production.
  • 1 is a process flow diagram of an embodiment of a process for preparing lead by ammonium chloride ammonia reduction.
  • a method for preparing lead by electrochemical reduction of ammonium chloride, wherein the lead compound is reduced to obtain metal lead and specifically a method for directly reducing lead compound to obtain metal lead by using an ammonium chloride electrolyte at the cathode of the electrolytic cell, wherein
  • the lead compounds include lead-containing lead chloride, lead sulfate, lead oxide, lead dioxide and mixtures thereof such as waste lead battery paste, wherein the electrolytic bath comprises an anode plate, a cathode plate and a material layer.
  • the process includes the following steps:
  • causticization of electrolytic waste liquid the electrolytic waste liquid is fermented by lime milk to obtain ammonium gas, and the ammonia gas is returned to the electrolysis.
  • the sulfate acid released by the lead compound at the cathode enters the caustic slag in the form of calcium sulfate, and is in the lead compound.
  • Chloride ions are recycled in the form of calcium chloride.
  • the lead compounds include lead chloride, lead sulfate, lead oxide, lead dioxide, and mixtures thereof such as waste lead battery paste.
  • the electrolyte is ammonium chloride.
  • the anode plate includes a titanium mesh
  • the cathode plate includes a stainless steel plate or a lead plate.
  • the titanium mesh is a titanium mesh coated with a ruthenium coating.
  • the ammonium chloride concentration is from 0.5 to 4 mol/L.
  • the reduction voltage in the step (3) is 2.0-2.7 v
  • the current density is 100-500 A/m 2
  • the pH 6-9 is controlled with ammonia water.
  • the reduced solution in the step (7) includes an ammonia sulfate solution.
  • the anode Using a titanium mesh coated with a ruthenium coating as an anode, the anode has a width of 10 cm and a height of 20 cm;
  • the cathode is 10 cm wide and 20 cm high;
  • Electrolyte preparation take 5L of 2mol/L ammonium chloride solution and add 200ml of ammonia water;
  • the reduced lead was 656.2 g after being pressed into a pellet, and the sample analysis result was Pb 98.3%;
  • initial current 10A peak current 20.8A
  • reduction power consumption 339wh ton lead power consumption 525kwh
  • anode current density 250-545A/m 2 lead recovery rate 99.8%
  • ammonia consumption 890ml including NH 3 25- 28%).
  • the anode Using a titanium mesh coated with a ruthenium coating as an anode, the anode has a width of 10 cm and a height of 20 cm;
  • the cathode is 10 cm wide and 20 cm high;
  • Electrolyte preparation take 5L of 2mol/L ammonium chloride solution and add 200ml of ammonia water;
  • the reduced lead was 656.2 g after being pressed into a pellet, and the sample analysis result was Pb 98.8%;
  • initial current 12A peak current 23A
  • reduction power consumption 370wh ton lead power consumption 575kwh
  • anode current density 300-575A/m 2 lead recovery rate 99.8%
  • ammonia consumption 850ml including NH 3 25-28 %).
  • Two blocks of titanium mesh coated with ruthenium are used as anodes, the anode width is 10 cm and the height is 20 cm;
  • the cathode is 10 cm wide and 20 cm high;
  • Pre-electrolysis liquid preparation prepare 2L / L ammonium chloride solution 5L, add ammonia water 200ml;
  • the lead reduced by weight was 380.0 g, and the sample analysis result was Pb 98.1%.
  • initial current 12A peak current 23A
  • reduction power consumption 411wh ton lead power consumption 1094kwh
  • lead recovery rate 99.9% ammonia water consumption 300ml (including NH325-28%).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)

Abstract

氯化铵氨电还原制取铅工艺，属于湿法冶金工艺技术，具体为一种使用氯化铵水溶液为电解质，以铅化合物为原料，用钛做阳极，用不锈钢或铅做阴极，在电解槽内施加直流电场，铅化合物在阴极获得电子还原为金属铅，氨在阳极被氧化成氮气逸出，同时生成H +离子，化合物中的硫酸根、氯离子进入溶液生成硫酸铵、氯化铵，铅化合物中的一氧化铅、二氧化铅还原为金属铅同时释放出OH -与阳极生成的H +离子结合生成水。其中铅化合物包括硫酸铅、一氧化铅、二氧化铅、氯化铅及其混合物如废旧铅蓄电池膏泥等物料。本工艺与现有的电解工艺、电积工艺不同，电解液中不含铅化合物在阴极直接还原为金属铅。

Description

一种氯化铵氨电还原制取铅工艺 技术领域
本发明属于湿法冶金工艺技术，具体涉及一种氯化铵氨电还原制取铅工艺。
背景技术
目前铅的用途80％以上用于铅酸蓄电池，随着汽车的普及，新能源产业的发展，铅酸蓄电池的用量越来越大，报废的铅酸蓄电池也越来越多，如何既简单经济又科学环保的处理废旧蓄电池，冶金科研人员和环保工作者进行了大量研究，特别是面对目前日益严苛的环保要求，铅的湿法冶炼势在必行。废旧蓄电池的拆解技术已有飞跃的发展，蓄电池的破碎、拆解都实现了大规模现代化生产，其中的塑料盒、导电板栅材料得到有效的回收利用，但蓄电池的膏泥处理铅仍然沿用火法熔炼进行处理。铅膏泥中的铅主要有PbSO4、PbO2、PbO和少量金属铅，其它还有制造蓄电池时需添加物如硫酸钡、炭核和有机添加剂，火法处理时必然产生铅烟尘、二氧化硫、二噁英等有害物质对环境产生严重污染。铅膏泥的清洁环保处理仍然是急待研究解决的课题。
为此，人们进行了大量的研究，试图用环保经济的湿法冶金方法，取代火法处理方法。但由于膏泥的物相组成复杂，目前无一种湿法处理方法在经济、成本、能源消耗和环境保护方面与火法相竞争，因此，铅膏泥处理仍然用火法熔炼工艺。有的在火法熔炼前采用碳铵或钠碱脱硫，再进行火法还原熔炼。
人们对铅膏泥的湿法处理进行了大量的研究，主要有三种途径，第一种途径是固相还原法，该方法以中科院原化工冶金研究所陆克源等研究固相电解为代表，其特征是在NaOH溶液中进行电解，首先将膏泥用NaOH(电解残液)转化，将PbSO4转化为Pb(OH)2和硫酸钠，转化后经脱水，再把转化后的铅泥凃在特制的阴极板上，PbO2、Pb(OH)2、PbO在阴极被还原成金属铅，阳极析出O2，含硫酸钠的溶液经处理后排放。第二种途径是电积法，主要特征是将铅溶解为可溶的铅盐溶液，在电解槽中通以直流电，溶液中的铅在阴极析出，阳极析出氧气和PbO2，采用的电解质溶液有硅氟酸、硼氟酸、氢氧化钠溶液、高氯酸溶液等。第三种途径是将铅膏泥制成铅的化合物，如氧化铅、氯化铅等。
以上多种湿法处理废铅蓄电池膏泥的方法，在经济上都不可能与当前的火法熔炼工艺相竞争，所以目前国内外对铅膏泥的处理仍然采用火法熔炼。
另外，湿法炼锌原料和锌二次资源中含有铅，这些铅最终都以硫酸铅的形态留存在锌浸出渣中。目前，这类物料都采用火法熔炼回收其中的铅，不仅能耗高，冶炼过程中产生的铅烟尘、二氧化硫、二噁英等有害物质对环境产生严重污染。
发明内容
本发明属于湿法冶金工艺技术，涉及在氯化铵水溶液中将铅化合物还原为金属铅的工艺。具体为一种使用氯化铵水溶液为电解液，以铅化合物为原料，用钛作阳极，用不锈钢或铅作阴极，在电解槽内施加直流电场，铅化合物在阴极获得电子还原为金属铅，氨在阳极被氧化成氮气逸出，同时生成H+离子，化合物中的硫酸根、氯离子进入溶液与加入的氨水生成硫酸铵、氯化铵，铅化合物中的一氧化铅、二氧化铅还原为金属铅，同时释放出OH-与阳极生成的氢离子结合生成水。其中铅化合物包括氯化铅、硫酸铅、一氧化铅、二氧化铅及其混合物如废旧铅蓄电池膏泥等物料。本工艺与现有的电解工艺、电积工艺不同，电解液中不含铅，铅化合物在阴极直接还原为金属铅。
作为优选的技术方案，所述工艺包括以下步骤：
(1)装料：将铅物料装在阴极框架上；
(2)配制电解液：调配电解质的浓度；
(3)还原：在电解槽内施加直流电场，铅化合物在阴极获得电子直接还原为金属铅，在铅还原过程中阳极产生H+离子，使溶液PH值下降，加氨水控制PH值；
(4)出槽：还原结束，将阴极提起，取出还原铅；
(5)压团：将还原铅压团脱去铅中水分；
(6)熔铸铸锭：将铅团熔铸铸锭成产品；
(7)电解废液苛化：将电解废液用石灰乳苛化脱铵，得到氨气返回电解，铅化合物中的硫酸根以硫酸钙形态进入石灰苛化渣带走，铅化合物中氯以氯化钙形态回收利用。
作为优选的技术方案，所述物料包括氯化铅、硫酸铅、一氧化铅、二氧化 铅及其混合物，如废旧铅蓄电池膏泥，所述废旧铅蓄电池膏泥为金属铅、一氧化铅、二氧化铅、硫酸铅的混合物。
作为优选的技术方案，所述电解质为氯化铵。
作为优选的技术方案，所述阳极板包括钛网，阴极板包括不锈钢板或铅板。
作为优选的技术方案，所述的钛网为涂有铱钌涂层的钛网。
作为优选的技术方案，所述氯化铵浓度为0.5-4mol/L。
作为优选的技术方案，所述的步骤(3)中的还原电压2.0-2.7v，电流密度100-500A/m2，用加氨水控制PH 6-9。
作为优选的技术方案，所述的步骤(7)中的还原后的的溶液包括氯化铵溶液。
其中，还原化学反应式：
阳极反应：
2NH3 +-6e＝N2↑+6H+
阴极主要反应：
PbSO4+2e＝Pb+SO4 2-
PbO+H2O+2e＝Pb+2OH-
PbO2+2H2O+4e＝Pb+4OH-
PbCl2+2e＝Pb+2Cl-
本发明优点:
1.采用全湿法工艺，生产过程无火法熔炼的铅尘、铅烟气、二氧化硫烟气、二噁英等有害气体产生，还原过程中没有氯气产生只有氮气，对环境比较友好，无环境污染问题。
2.采用固体直接还原，不需要脱硫、转化等工序，缩短工艺流程，大幅降低投资和生产成本。
3.氨电还原过程中不需要添加剂。
4.铵电还原整个过程在常温下进行，能源消耗低，操作环境好。
5.铵电还原整个过程溶液PH值呈中性或弱碱性，对设备腐蚀小。
6.电解液中不含铅，电解废液容易处理。
7.采用氨电固体直接还原，还原电压低，电流密度大，阳极电流密度可达400A/m2，电能消耗低，原料为二价铅(氯化铅、硫酸铅、一氧化铅)吨铅电耗 在520-650度，原料为铅酸蓄电池膏泥吨铅电耗在800-1100度。
8.铅回收率高达99％以上，可进行规模化生产应用。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需使用的附图作简单的介绍，显而易见，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，可以根据这些附图获得其他的附图。
图1为发明一种氯化铵氨电还原制取铅工艺实施例的工艺流程图。
具体实施方式
为了进一步说明本发明，下面结合附图进行说明：
一种氯化铵氨电还原制取铅工艺，所述工艺为铅化合物在还原得到金属铅，具体为一种使用氯化铵电解质在电解槽阴极将铅化合物直接还原得到金属铅方法，其中所述铅化合物包括含铅的氯化铅、硫酸铅、氧化铅、二氧化铅及其混合物如废旧铅蓄电池膏泥，其中电解槽包括阳极板、阴极板和物料层。
所述工艺包括以下步骤：
(1)装料：将铅物料装在阴极框架上；
(2)配制电解液：调配电解质的浓度；
(3)还原：在电解槽内施加直流电场，铅化合物在阴极获得电子直接还原为金属铅，在铅还原过程中阳极产生H+离子，使溶液PH值下降，加入氨水控制PH值；
(4)出槽：还原结束，将阴极提起，取出还原铅；
(5)压团：将还原铅压团脱去铅中水分；
(6)熔铸铸锭：将铅团熔铸铸锭成产品；
(7)电解废液苛化：将电解废液用石灰乳苛化脱铵，得到氨气返回电解，铅化合物在阴极放出的硫酸根以硫酸钙形态进入苛化渣带走，铅化合物中的氯离子以氯化钙形态回收利用。
所述铅化合物包括氯化铅、硫酸铅、氧化铅、二氧化铅及其混合物如废旧铅蓄电池膏泥等。
所述电解质为氯化铵。
所述阳极板包括钛网，阴极板包括不锈钢板或铅板。
所述的钛网为涂有铱钌涂层的钛网。
所述氯化铵浓度为0.5-4mol/L。
所述的步骤(3)中的还原电压2.0-2.7v，电流密度100-500A/m2，用氨水控制PH 6-9。
所述的步骤(7)中的还原后的溶液包括硫酸氨溶液。
实施例1：
用凃有铱钌涂层的钛网两块作阳极，阳极宽为10cm，高为20cm；
用不锈钢一块作阴极，阴极宽为10cm，高为20cm；
投料：氯化铅1000g，其中Pb64.3％、Cl 22.4％；
电解液配制：取2mol/L氯化铵溶液5L，加氨水200ml；
还原：恒压模式2.0v电压，进行还原20小时，用氨水控制PH 8-9，还原结束，出槽；
还原铅经压团后重656.2g，取样分析结果Pb98.3％；
主要技术指标：起始电流10A，峰值电流20.8A，还原耗电339wh，吨铅电耗525kwh，阳极电流密度250-545A/m2，铅回收率99.8％，氨水消耗890ml(含NH325-28％)。
实施例2：
用凃有铱钌涂层的钛网两块作阳极，阳极宽为10cm，高为20cm；
用不锈钢一块作阴极，阴极宽为10cm，高为20cm；
投料：氯化铅1000g，其中Pb64.3％、Cl 22.4％；
电解液配制：取2mol/L氯化铵溶液5L，加氨水200ml；
还原：恒压模式2.2v电压，进行还原20小时，用氨水控制PH 8-9，还原结束，出槽；
还原铅经压团后重656.2g，取样分析结果Pb98.8％；
主要技术指标：起始电流12A，峰值电流23A，还原耗电370wh，吨铅电耗575kwh，阳极电流密度300-575A/m2，铅回收率99.8％，氨水消耗850ml(含NH325-28％)。
实施例3：
取废铅酸蓄电池料500g，含Pb75.04％(其中Pb5.2％、PbSO441.06％、PbO244.32％、PbO3.65％)；
用凃有铱钌涂层的钛网两块作阳极，阳极宽为10cm、高为20cm；
用不锈钢一块作阴极，阴极宽为10cm，高为20cm；
电解前液配制：配制2mol/L氯化铵溶液5L，加氨水200ml；
还原：恒压模式2.5v电压，进行还原20小时，用氨水控制PH 8-9，还原结束，出槽；
还原铅经压团后重380.0g，取样分析结果Pb98.1％。
主要技术指标：起始电流12A，峰值电流23A，还原耗电411wh，吨铅电耗1094kwh，铅回收率99.9％，氨水消耗300ml(含NH325-28％)。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (9)

  1. 一种氯化铵氨电还原制取铅工艺，其特征是：所述工艺使用氯化铵水溶液为电解质，以铅化合物为原料，用钛做阳极，用不锈钢或铅做阴极，在电解槽内施加直流电场，铅化合物在阴极获得电子还原为金属铅，氨在阳极被氧化成氮气逸出，同时生成H+离子，化合物中的硫酸根、氯离子进入溶液与加入的氨水生成硫酸铵、氯化铵，铅化合物中的一氧化铅、二氧化铅还原为金属铅，同时释放出OH-与阳极生成的氢离子结合生成水。
  2. 如权利要求1所述的一种氯化铵氨电还原制取铅工艺，其特征是，所述工艺包括以下步骤：
    (1)装料：将铅物料装在阴极框架上；
    (2)配制电解液：调配电解质的浓度；
    (3)还原：在电解槽内施加直流电场，铅化合物在阴极获得电子直接还原为金属铅，在铅还原过程中阳极产生H+离子，使溶液PH值下降，加氨水控制PH；
    (4)出槽：还原结束，将阴极提起，取出还原铅；
    (5)压团：将还原铅压团脱去铅中水分；
    (6)熔铸铸锭：将铅团熔铸铸锭成产品；
    (7)电解废液苛化：将电解废液用石灰乳苛化脱铵，得到氨气返回电解，铅化合物在阴极放出的硫酸根以硫酸钙形式进入苛化渣带走，铅化合物中的氯离子以氯化钙形式回收利用。
  3. 如权利要求2所述的一种氯化铵氨电还原制取铅工艺，其特征是：所述铅化合物包括氯化铅、硫酸铅、一氧化铅、二氧化铅极其混合物。
  4. 如权利要求1或2所述的一种氯化铵氨电还原制取铅工艺，其特征是：所述电解质为氯化铵溶液。
  5. 如权利要求1或2所述的一种氯化铵氨电还原制取铅工艺，其特征是：所述阳极板为钛网，阴极板包括不锈钢板或铅板。
  6. 如权利要求5所述的一种氯化铵氨电还原制取铅工艺，其特征是：所述的钛网为涂有铱钌涂层的钛网。
  7. 如权利要求4所述的一种氯化铵氨电还原制取铅工艺，其特征是：所述氯化铵浓度为0.5-4mol/L。
  8. 如权利要求2所述的一种氯化铵氨电还原制取铅工艺，其特征是：所述 的步骤(3)中的还原电压2.0-2.7v，电流密度100-500A/m2，用氨水控制PH6-9。
  9. 如权利要求4所述的一种氯化铵氨电还原制取铅工艺，其特征是：所述的步骤(7)中的还原后的溶液包括氯化铵溶液。
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