氧化酸浸法从非对称电容电池中提取镍、钴和稀土  

Recovery of Nickel,Cobalt and Rare Earth from Negative Electrode Materials for Asymmetric Electrochemical Battery with Oxidizing Acid Leaching

作　　者：张亚莉[1] 蒋志军 于先进[1] 黄文强[1] 王青龙[1] 

机构地区：[1]山东理工大学化学工程学院,山东淄博255049 [2]淄博国利新电源科技有限公司,山东淄博255086 [3]淄博非对称大动力电容电池工程技术研究中心,山东淄博255086

出　　处：《稀有金属》2014年第6期1099-1105,共7页Chinese Journal of Rare Metals

基　　金：国家自然科学基金项目(51304129);山东省自然科学基金项目(ZR2013EEM005);山东省自主创新专项(2013CXA03073)资助

摘　　要：非对称电容电池兼具氢镍电池能量密度和非对称超级电容器功率密度的优势,具有广阔应用前景,从废弃非对称电容电池回收金属不仅是环境保护的需求,更是资源再生利用的需要。以H2O2为氧化剂从非对称电容电极负极材料中用氧化酸浸法提取镍、钴和稀土。研究了硫酸浸出过程中镍钴的浸出机制,发现当p H小于6.5时,Ni2+和Co2+具有较高的溶解度,且钴优先于镍浸出;同时研究了氧化剂用量、浸出温度、硫酸浓度、液固比和浸出时间等因素对非对称电容电极负极材料氧化酸浸过程中有价金属镍、钴和稀土浸出率的影响。结果表明,Ni,Co浸出率随温度升高而增加,在353 K时,浸出率均达到最大值,Ce则在常温下浸出效果较好;Ni,Co和Ce浸出率随氧化剂用量、硫酸浓度、液固比和浸出时间的增加而增大。最适宜的工艺条件为:硫酸浓度190 g·L-1,液固比为9∶1,H2O2用量8 ml,353 K温度下浸出20 min,流动水冷却到293 K,搅拌浸出90 min,Ni,Co和稀土的浸出率分别达99.4%,99.7%和96.5%。并提出了"硫酸钠回收稀土-苛碱回收镍钴"的后续分离净化流程,能有望应用于非对称电容电极负极材料及类似物料中有价金属的提取与分离的工业生产。Having the advantage of energy density of nickel-metal hydride battery and power density of asymmetric super capacitors,negative electrode materials for asymmetric electrochemical battery have a broad application prospect. It is not only the demand of environmental protection,but also the resource recycling to recovery metals from negative electrode materials for asymmetric electrochemical battery. Nickel,cobalt and rare earth were leached from negative electrode materials for asymmetric electrochemical battery in sulfuric acid using H2O2 as oxygenant. The leaching mechanism of nickel and cobalt was studied,it was found that Ni and Co had high solubility when the p H was less than 6. 5,and the leaching of cobalt took precedence over nickel. Also the influences of amount of oxygenant,leaching temperature,acid concentration,liquid-solid ratio and leaching time on leaching rates of nickel,cobalt and rare earth were investigated through single factor experiments. The results showed that the leaching rates of Ni and Co increased with the rise of temperature,and reached the maximum at 353 K. Yet the leaching effect of Ce was better at room temperature. The leaching rates of Ni,Coand Ce increased with the increase of the amount of oxygenant,acid concentration,liquid-solid ratio and leaching time. When the leaching efficiencies of nickel,cobalt and rare earth were 99. 4%,99. 7% and 96. 5%,respectively,the optimal conditions were as follows： the dosage of H2O2 was 8 ml,and c（ H2SO4） = 190 g·L^- 1,T = 353 ℃,L/S ratio = 9∶ 1,t = 20 min,then cooled to 293 K and agitation leached for 90 min. The proposed flow sheet was rare earth recovery by Na2SO4→nickel and cobalt recovery by Na OH. This process flow can be applied in the extraction of metals from negative electrode materials for asymmetric electrochemical battery and similar materials effectively in industry.

关 键 词：非对称电容电池 氧化酸浸 镍 钴 稀土 

分 类 号：TF811[冶金工程—有色金属冶金] TF816