WO2018014747A1 - 一种硫酸铵氨电还原制取铅工艺 - Google Patents
一种硫酸铵氨电还原制取铅工艺 Download PDFInfo
- Publication number
- WO2018014747A1 WO2018014747A1 PCT/CN2017/092332 CN2017092332W WO2018014747A1 WO 2018014747 A1 WO2018014747 A1 WO 2018014747A1 CN 2017092332 W CN2017092332 W CN 2017092332W WO 2018014747 A1 WO2018014747 A1 WO 2018014747A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- lead
- ammonium
- cathode
- reduction
- compound
- 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
Links
Images
Classifications
-
- 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
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
- C25B1/26—Chlorine; Compounds thereof
Definitions
- the invention belongs to a hydrometallurgical process technology, and in particular relates to a process for preparing lead by ammonium hydroxide ammonium 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 provides a process for preparing lead by ammonium hydroxide ammonium electroreduction. Specifically, an aqueous solution of ammonium sulfate 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, and a direct current electric field is applied in the electrolytic bath, and a lead compound is electronically reduced to metal lead at the cathode, and ammonia is The anode is oxidized to nitrogen and simultaneously generates H + ions. Sulfate and chloride ions in the compound enter the solution and the added ammonia water to form ammonium sulfate and ammonium chloride.
- Lead oxide and lead dioxide in the lead compound are reduced to metal.
- Lead 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:
- Electrolytic waste liquid treatment The sulfate and chloride ions released from the lead compound at the cathode are recovered in the form of ammonium sulfate or ammonium chloride.
- the material includes lead chloride, lead sulfate, lead monoxide, lead dioxide and mixtures thereof, such as waste lead battery paste, and the waste lead battery paste is metal lead and oxygen.
- the waste lead battery paste is metal lead and oxygen.
- the electrolyte is ammonium sulfate.
- 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 sulfate concentration is 0.5-4 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 electrolyzed solution in the step (7) includes an ammonium sulfate solution.
- the electrolyte does not contain lead, and the electrolytic waste liquid is easy to handle, and can be concentrated and crystallized to produce ammonium sulfate or ammonium chloride.
- the pH value of the solution in the whole process of ammonium reduction is neutral or weakly alkaline, and it is less corrosive to equipment.
- Reduction adopts direct reduction of ammonia electric solid, low reduction voltage, high current density, anode current density up to 400A/m 2 , low electric energy consumption, raw material is divalent lead (lead chloride, lead sulfate, lead monoxide)
- the lead consumption is 520-650 degrees, and the raw material is lead-acid battery paste.
- 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 producing lead by ammonium sulphate ammonium reduction.
- a process for preparing lead by electrochemical reduction of ammonium sulfate wherein the process is to obtain metal lead by electrochemical reduction of ammonia, specifically a method for directly reducing lead compound to obtain metal lead by using ammonium sulfate electrolyte at the cathode of the electrolytic cell, wherein
- the lead compound includes lead chloride, lead sulfate, lead oxide, lead dioxide and mixtures thereof such as waste lead battery paste, etc.
- the electrolytic bath comprises an anode plate, a cathode plate and a material layer.
- the process includes the following steps:
- the lead compound includes lead chloride, lead sulfate, lead oxide, lead dioxide, and an extreme mixture such as waste lead battery paste.
- the electrolyte is ammonium sulfate.
- 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 sulfate 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 cathode width is 10cm, and the height is 20cm;
- Pre-electrolysis liquid preparation prepare 2L/L ammonium sulfate solution 5L, add ammonia water 200ml;
- initial current 10.5A peak current 20.5A
- reduction power consumption 377.5wh ton lead power consumption 1006kwh
- anode current density 250-500A/m 2 lead recovery rate 99.4%
- ammonia consumption 310ml including NH 3 25-28%.
- the cathode width is 10cm, and the height is 20cm;
- Pre-electrolysis liquid preparation prepare 2L/L ammonium sulfate solution 5L, add ammonia water 200ml;
- initial current 12A peak current 23A
- reduction power consumption 411wh tons of lead power consumption 1094kwh
- lead recovery rate 99.9% ammonia water consumption 300ml (including NH 3 25-28%).
- the anode width is 10 cm, and the height is 20 cm;
- the cathode is 10 cm wide and 20 cm high;
- Electrolyte preparation take 5L of 2mol/L ammonium sulfate solution and add 200ml of ammonia water;
- initial current 10A peak current 21.8A
- reduction power consumption 336wh ton lead power consumption 523kwh
- anode current density 250-545A/m 2 lead recovery rate 99.8%
- ammonia consumption 890ml including NH3 25-28 %).
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
本发明属于湿法冶金工艺技术,涉及在硫酸铵水溶液中将铅化合物还原为金属铅的工艺。具体为一种使用硫酸铵水溶液为电解液,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,铅化合物在阴极直接还原为金属铅。
Description
本发明属于湿法冶金工艺技术,具体涉及一种硫酸铵氨电还原制取铅工艺。
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,提供了一种硫酸铵氨电还原制取铅工艺。具体为一种使用硫酸铵水溶液为电解质,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。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)电解废液处理:将铅化合物在阴极释放出的硫酸根、氯离子以硫酸铵或氯化铵形态进行回收。
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,所述电解质为硫酸铵。
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,所述硫酸铵浓度为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,用氨水控制PH 6-9。
作为优选的技术方案,所述的步骤(7)中的电解后的的溶液包括硫酸铵溶液。
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,生产过程中无火法熔炼的铅尘、铅烟气、二氧化硫烟气、二噁英等有害气体产生,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.电解液中不含铅,电解废液容易处理,可浓缩结晶生产硫酸铵或氯化铵。
5.铵电还原整个过程在常温下进行,能源消耗低,操作环境好。
6.铵电还原整个过程溶液PH值呈中性或弱碱性,对设备腐蚀性小。
7.还原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。
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为发明一种硫酸铵氨电还原制取铅工艺实施例的工艺流程图。
为了进一步说明本发明,下面结合附图进行说明:
一种硫酸铵氨电还原制取铅工艺,所述工艺为通过氨电还原得到金属铅,具体为一种使用硫酸铵电解质,在电解槽阴极上,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,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)还原废液处理:铅化合物中硫酸根、氯离子以硫酸铵、氯化铵形态回收利用。
所述铅化合物包括氯化铅、硫酸铅、氧化铅、二氧化铅极其混合物如废旧铅蓄电池膏泥等。
所述电解质为硫酸铵。
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。
所述硫酸铵浓度为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:
(1)取废铅酸蓄电池铅膏500g,含Pb75.04%(其中Pb5.2%、PbSO441.06%、PbO244.32%、PbO3.65%);
(2)取用凃有铱钌涂层的钛网两块作阳极,阳极宽为10cm、高为20cm;
(3)取用不锈钢一块作阴极,阴极宽为10cm,高为20cm;
(4)电解前液配制:配制2mol/L硫酸铵溶液5L,加氨水200ml;
(5)还原:恒压模式2.3v电压,进行还原24小时,用氨水控制PH8-9,还原结束,出槽;
(6)还原铅经压团后重379.8g,取样分析结果Pb98.6%。
主要技术指标:起始电流10.5A,峰值电流20.5A,还原耗电377.5wh,吨铅电耗1006kwh,阳极电流密度250-500A/m2,铅回收率99.4%,氨水消耗310ml(含NH325-28%)。
实施例2:
(1)取废铅酸蓄电池铅膏500g,含Pb75.04%(其中Pb5.2%、PbSO4 41.06%、PbO244.32%、PbO3.65%);
(2)取用凃有铱钌涂层的钛网两块作阳极,阳极宽为10cm、高为20cm;
(3)取用铅板一块作阴极,阴极宽为10cm,高为20cm;
(4)电解前液配制:配制2mol/L硫酸铵溶液5L,加氨水200ml;
(5)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;
(6)还原铅经压团后重380.1g,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%)。
实施例3:
(1)用凃有铱钌涂层的钛网两块作阳极,阳极宽为10cm,高为20cm;
(2)用不锈钢一块作阴极,阴极宽为10cm,高为20cm;
(3)投料:氯化铅1000g,其中Pb64.3%、Cl 22.4%;
(4)电解液配制:取2mol/L硫酸铵溶液5L,加氨水200ml;
(5)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;
(6)还原铅经压团后重656.2g,取样分析结果Pb98.5%;
主要技术指标:起始电流10A,峰值电流21.8A,还原耗电336wh,吨铅电耗523kwh,阳极电流密度250-545A/m2,铅回收率99.8%,氨水消耗890ml(含NH3 25-28%)。
以上所述仅为本发明较佳实施例而已,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)
- 一种硫酸铵氨电还原制取铅工艺,其特征是:所述工艺使用硫酸铵水溶液为电解液,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。
- 如权利要求1所述的一种硫酸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)电解废液处理:将铅化合物在阴极释放出的硫酸根、氯离子以硫酸铵或氯化铵形态进行回收。
- 如权利要求2所述的一种硫酸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、二氧化铅及其混合物。
- 如权利要求1或2所述的一种硫酸铵氨电还原制取铅工艺,其特征是:所述电解质为硫酸铵。
- 如权利要求1或2所述的一种硫酸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。
- 如权利要求5所述的一种硫酸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。
- 如权利要求4所述的一种硫酸铵氨电还原制取铅工艺,其特征是:所述硫酸铵浓度0.5-4mol/L。
- 如权利要求2所述的一种硫酸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PH 6-9。
- 如权利要求4所述的一种硫酸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硫酸铵溶液。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US16/318,712 US10584424B2 (en) | 2016-07-19 | 2017-07-10 | Process for preparing lead by electroreduction with ammonium sulfate and ammonia |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610569036.0 | 2016-07-19 | ||
| CN201610569036.0A CN106065485B (zh) | 2016-07-19 | 2016-07-19 | 一种硫酸铵氨电还原制取铅工艺 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO2018014747A1 true WO2018014747A1 (zh) | 2018-01-25 |
| WO2018014747A9 WO2018014747A9 (zh) | 2018-03-15 |
Family
ID=57206620
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CN2017/092332 Ceased WO2018014747A1 (zh) | 2016-07-19 | 2017-07-10 | 一种硫酸铵氨电还原制取铅工艺 |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US10584424B2 (zh) |
| CN (1) | CN106065485B (zh) |
| WO (1) | WO2018014747A1 (zh) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106065485B (zh) | 2016-07-19 | 2018-12-14 | 云南祥云飞龙再生科技股份有限公司 | 一种硫酸铵氨电还原制取铅工艺 |
| CN106048654B (zh) | 2016-07-19 | 2018-12-14 | 云南祥云飞龙再生科技股份有限公司 | 一种氯化铵氨电还原制取铅工艺 |
| CN109402668A (zh) * | 2018-12-18 | 2019-03-01 | 云南云铅科技股份有限公司 | 一种利用固体电解法从铅膏泥中高效回收铅的方法 |
| CN109763142B (zh) * | 2018-12-28 | 2021-01-29 | 祥云高鑫循环科技有限责任公司 | 一种废铅蓄电池铅膏固相电解湿法回收铅的方法 |
| CN114606538B (zh) * | 2022-01-24 | 2023-10-03 | 湘潭大学 | 一种废铅膏回收处理方法 |
| CN115094484A (zh) * | 2022-06-12 | 2022-09-23 | 马光甲 | 硫酸溶液中旋转阴极四排阳极连续固相、离子电解、氧化、机械分离处理废铅蓄电池工艺 |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4118219A (en) * | 1976-02-19 | 1978-10-03 | Gould Inc. | Process for recycling junk lead-acid batteries |
| CN85200287U (zh) * | 1985-04-01 | 1985-11-10 | 中国科学院化工冶金研究所 | 含铅物料固相电解的装置 |
| US5211818A (en) * | 1991-04-09 | 1993-05-18 | Moure Jr William B | Method for recovering lead from batteries |
| CN1470675A (zh) * | 2002-07-22 | 2004-01-28 | 佟永顺 | 废铅蓄电池回收铅技术 |
| CN101335370A (zh) * | 2008-07-11 | 2008-12-31 | 东莞市松山科技集团有限公司 | 一种可实现废旧铅酸蓄电池全循环再生的工艺方法 |
| CN101368280A (zh) * | 2007-08-17 | 2009-02-18 | 洛阳森韵热工设备有限公司 | 从铅膏中回收铅的电解装置 |
| CN102296325A (zh) * | 2011-06-15 | 2011-12-28 | 马光甲 | 旋转阴极连续固相电解处理废铅蓄电池工艺 |
| CN104711637A (zh) * | 2013-12-12 | 2015-06-17 | 沈阳有色金属研究院 | 一种从固体氧化铅中回收金属铅的方法 |
| CN106065485A (zh) * | 2016-07-19 | 2016-11-02 | 云南祥云飞龙再生科技股份有限公司 | 一种硫酸铵氨电还原制取铅工艺 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ITMI20072257A1 (it) * | 2007-11-30 | 2009-06-01 | Engitec Technologies S P A | Processo per produrre piombo metallico a partire da pastello desolforato |
| JP2009242845A (ja) * | 2008-03-31 | 2009-10-22 | Nippon Mining & Metals Co Ltd | 鉛の電解方法 |
| CN103540954B (zh) * | 2012-07-13 | 2016-06-08 | 张超 | 一种碱性溶液中的金属电解方法 |
-
2016
- 2016-07-19 CN CN201610569036.0A patent/CN106065485B/zh active Active
-
2017
- 2017-07-10 US US16/318,712 patent/US10584424B2/en active Active
- 2017-07-10 WO PCT/CN2017/092332 patent/WO2018014747A1/zh not_active Ceased
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4118219A (en) * | 1976-02-19 | 1978-10-03 | Gould Inc. | Process for recycling junk lead-acid batteries |
| CN85200287U (zh) * | 1985-04-01 | 1985-11-10 | 中国科学院化工冶金研究所 | 含铅物料固相电解的装置 |
| US5211818A (en) * | 1991-04-09 | 1993-05-18 | Moure Jr William B | Method for recovering lead from batteries |
| CN1470675A (zh) * | 2002-07-22 | 2004-01-28 | 佟永顺 | 废铅蓄电池回收铅技术 |
| CN101368280A (zh) * | 2007-08-17 | 2009-02-18 | 洛阳森韵热工设备有限公司 | 从铅膏中回收铅的电解装置 |
| CN101335370A (zh) * | 2008-07-11 | 2008-12-31 | 东莞市松山科技集团有限公司 | 一种可实现废旧铅酸蓄电池全循环再生的工艺方法 |
| CN102296325A (zh) * | 2011-06-15 | 2011-12-28 | 马光甲 | 旋转阴极连续固相电解处理废铅蓄电池工艺 |
| CN104711637A (zh) * | 2013-12-12 | 2015-06-17 | 沈阳有色金属研究院 | 一种从固体氧化铅中回收金属铅的方法 |
| CN106065485A (zh) * | 2016-07-19 | 2016-11-02 | 云南祥云飞龙再生科技股份有限公司 | 一种硫酸铵氨电还原制取铅工艺 |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2018014747A9 (zh) | 2018-03-15 |
| CN106065485A (zh) | 2016-11-02 |
| US20190242022A1 (en) | 2019-08-08 |
| CN106065485B (zh) | 2018-12-14 |
| US10584424B2 (en) | 2020-03-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2018014747A1 (zh) | 一种硫酸铵氨电还原制取铅工艺 | |
| Tan et al. | Developments in electrochemical processes for recycling lead–acid batteries | |
| CN106676270B (zh) | 一种从铅膏与硫化铅精矿中全湿法提取铅的方法 | |
| EP2312686B1 (en) | Method for implementing full cycle regeneration of waste lead acid battery | |
| CN102560535B (zh) | 一种湿法回收废铅酸蓄电池填料中铅的方法 | |
| CN104018186B (zh) | 一种铜铟镓硒的回收方法 | |
| CN106785174B (zh) | 一种基于电化学法从锂离子电池正极废料中浸出和回收金属的方法 | |
| WO2018014748A9 (zh) | 氯化铵氨电还原制取铅工艺 | |
| CN114039117B (zh) | 一种废旧磷酸铁锂电池中锂的选择性回收方法 | |
| CN113862479A (zh) | 一种废铅蓄电池中铅膏的资源化回收处理方法 | |
| CN102677095B (zh) | 一种废铅酸蓄电池铅膏中铅的回收方法 | |
| CN101942675A (zh) | 一种电解还原回收废水中Sn2+的方法 | |
| CN102367577B (zh) | 制备Na2[Pb(OH)4]溶液和从含铅废料中回收铅的方法 | |
| CN100590230C (zh) | 在氯盐介质中金属铅和二氧化锰同时电解的方法 | |
| CN110331284A (zh) | 一种利用软锰矿制备电解锰的方法 | |
| CN112323097A (zh) | 一种锌氨络合耦合过硫酸盐高级氧化技术脱除烟气中二氧化硫的方法及系统 | |
| Zhang et al. | A review on lead extraction from ore and spent lead paste by hydrometallurgical processes | |
| US11502344B2 (en) | Hydrometallurgical method for recycling lead from spent lead-acid battery paste | |
| CN107400781A (zh) | 一种铅冶炼废料含锌物料的回收方法 | |
| CN105624727B (zh) | 同一电解槽中同时生产电解金属锰和电解二氧化锰的方法 | |
| CN109055764A (zh) | 一种高氯低锌物料的综合回收方法 | |
| CN106544699A (zh) | 一种离子液体电解回收废铅蓄电池铅膏提铅的方法 | |
| CN110257638A (zh) | 一种分别回收固体废物中锰、铜、锌的方法 | |
| CN110331282B (zh) | 一种湿法炼锌浸出液循环亚铜离子除氯工艺 | |
| CN115028205A (zh) | 一种利用钛白粉副产物制备六氟铁酸钠的方法及应用 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 17830381 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 17830381 Country of ref document: EP Kind code of ref document: A1 |