粗铅电解精炼及提纯铅性能研究

硕士学位论文

粗铅电解精炼及提纯铅性能研究

INVESTIGATION OF ELECTROLYTIC REFINING OF CRUDE LEAD AND THE PERFORMANCE OF REFINED LEAD

王艳辉

2009年10月

国内图书分类号：TM912.1 学校代码：10213 国际图书分类号：621.355 密级：公开

工程硕士学位论文

粗铅电解精炼及提纯铅性能研究

工程硕士研究生：王艳辉

导师：戴长松教授

申请学位：工程硕士

学科：化学工程

所在单位：哈尔滨光宇蓄电池

股份有限公司

答辩日期：2009年10月21日

授予学位单位：哈尔滨工业大学

Classified Index: TM912.1

U. D. C. : 621.355

Dissertation for the Master Degree in Engineering

INVESTIGATION OF ELECTROLYTIC REFINING OF CRUDE LEAD AND THE PERFORMANCE OF REFINED LEAD

Candidate : Wang Yanhui

Supervisor : Prof. Dai Changsong

Academic Degree Applied for: Master of Engineering

Specialty : Chemical Engineering

Affiliation : Harbin Coslight Storage Battery

Co., ltd

Date of Defence : October 21, 2009

: Harbin Institute of Technology Degree-Conferring-

Institution

哈尔滨工业大学工程硕士学位论文

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摘 要

本文综述了粗铅电解精炼技术的研究现状，并对粗铅电解精炼工艺的技术参数进行了优化，然后将实验得到的电解铅与商业电解铅进行了制备板栅合金、铅粉、铅膏、极板和组装VRLA 的对比研究。

首先，通过研究了电解液的成分、电解液添加剂的补加量、电流密度、电解液的循环速度、阴阳极的距离和槽电压等工艺参数对电解精炼铅的质量和电能消耗等因素的影响，结果表明，氟硅酸浓度越高电解液的比电阻越低，在氟硅酸浓度一定的情况下，铅离子浓度越低电解液的比电阻越低，并确定较优的电解精炼工艺：电解液中总的氟硅酸浓度为 180 g/ L ；游离氟硅酸浓度为100 g/ L ；铅离子浓度到为95 g/ L ；骨胶的补加量为0.60 kg/t 析出铅；木质磺酸钙补加量0.75 kg/t 析出铅；电解电流密度为185A/m 2；阴阳极的距离为

75mm ；电解液的循环周期为 4 h ，并定期采用钢丝刷对电接点进行抛光处理，在电接点处涂抹甘油防止氧化。与传统工艺相比，采用改进后的工艺，降低槽电压0.10 V 左右，可降低直流电能消耗20 kWh/t

析出铅以上；析出电解铅的合格率由20 %提高到100 %；电能消耗降低13.13 %；年电解铅的产能提

高了13%；每年可节约资金15.14万元。

其次，采用直读光谱仪对改进工艺制备的电解铅与外购的电解铅进行了对比研究，结果表明，采用改进工艺制备的电解精炼铅，其杂质含量满足国标一号电解铅的要求，不需要再进行火法精炼去除超标的杂质，降低了对环境的污染，同时能够提高生产效率、降低电能消耗；且电解精炼铅制备的板栅合金和铅粉亦与商品的电解铅制备的板栅合金和铅粉就合金成分、杂质含量、铅粉的氧化度等方面没有质量区别。XRD ，SEM 和化学分析结果表明，采用改进工艺制备的电解精炼铅和商品电解铅制备的铅膏和极板的结晶结构、形貌和化学成分等方面均没有明显的区别。充放电测试结果表明，电解精炼铅和商品电解铅制备的VRLA 电池在容量保存率、放电容量、循环寿命、内阻等方面几乎没有差别。结果表明，采用改进工艺生产的电解铅完全可以直接用于阀控密封铅酸蓄电池的生产。

关键词：铅酸电池；板栅材料；电解精炼

哈尔滨工业大学工程硕士学位论文

Abstract

In this paper, development of electrolytic refining of crude lead was summarized, and the technique parameters of electrolytic refining were optimized. The obtained electrolytic lead was investigated in grid alloy, ceruse, diachylon, polar plate, and VRLA, compared with the commercial electrolytic lead.

First, the effects of the component of the electrolyte, addition amount of electrolyte additive, current density, and cycle time of electrolyte, the distance between cathode and anode, voltage of electro bath, and other technical parameters on the quality of electrolytic lead and energy consumption were investigated. And the result shows that a high concentration of fluosilicic acid results a low specific resistance of electrolyte, and at a certain concentration of fluosilicic acid, a low concentration of lead ions results a low the specific resistance of electrolyte. An optimum technology was obtained as follow: the concentration of fluosilicic acid was 180 g/L, the concentration of dissociative fluosilicic acid was 100 g/L, the concentration of lead ions was 95 g/L, quantity of bone gelatin added into the electrolyte was 0.60 kg/t lead, quantity of calcium lignosulfonate added into the electrolyte was 0.75 kg/t lead, current density was 185 A/m2, distance between cathode and anode was 75 mm, circulation velocity of the electrolyte was 4h. The connection point between electrode and copper bar was polished with wire brush termly, and coated with glycerin avoiding oxidation. Compared with the traditional techniques, the voltage of the electrolytic bath was decreased about 0.1V, and energy consumption decreased more than 20 kWh/t lead. And the qualification rate of refined lead increased from 20% to 100%, the energy consumption decreased 13.13%, the output of refined lead increased 13%, and 151.4 thousand RMB can be saved every year.

Second, direct-reading spectrometer was employed to study the electrolytic lead and commercial electrolytic lead comparatively. Electrolytic lead produced via new techniques conforms to the No. 1 level of the international electrolytic lead standard, pyro-refining was not needed to eliminate the impurity, with the pollution decreased, the productivity effect increased, the energy consumption decreased. No difference of oxidation degree, impurity contents and alloy contents of grid alloy and ceruse produced from as-prepared electrolytic lead and commercial lead was observed. XRD, SEM and chemical analysis revealed that there are no difference of crystal form, morphology and chemical composition of diachylon and polar plate made from as-prepared electrolytic lead and commercial lead. Charge/discharge test reveals that the battery produced from electrolytic lead has the same quality the VRLA produced from commercial electrolytic lead, such as capacity retention, discharge

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