碱性木糖醇体系回收废铅蓄电池铅膏的研究
发布时间：2018-08-08 14:46
【摘要】：人类社会对铅需求不断增长,但铅精矿产资源日益减少,因此回收再生铅成为铅工业可持续发展的一条重要途径。同时废铅蓄电池若不加以合理回收,将会对环境造成很大威胁。铅膏作为废铅蓄电池的重要组成部分,因其成分复杂而成为回收的重点和难点。传统火法回收能耗大,铅回收率低,产生的铅尘和SO2,对环境威胁较严重。而湿法处理工艺由于金属直收率高、低污染等优点而日益引起了人们的关注。这其中有机物处理体系以其低污染的优势成为一个重要的研究方向。论文首先分别采用两种还原剂FeSO_4和Na_2SO_3对PbO_2进行还原转化,采用两种脱硫剂NaOH和Na_2CO_3对PbSO_4进行脱硫;其次考察了铅膏的主要组分PbO_2和PbSO_4在碱性木糖醇体系的浸出行为,并对铅膏在碱性木糖醇体系的浸出行为进行了研究;最后对碱性木糖醇铅溶液的电积工艺进行初步探索。利用X射线衍射(XRD)、扫描电镜(SEM)、能谱(EDAX)等手段分析了反应过程中不溶物的物相、元素组成和形貌的演变,采用傅里叶变换红外光谱(FTIR)分析了浸出液中有机基团的变化。本论文的主要研究成果如下:PbO_2的还原实验结果表明,Na_2SO_3的还原效果明显优于FeSO_4。FeSO_4还原最佳条件为:FeSO_4过量系数为1~1.1,反应时间90~120min,反应温度90℃,H_2SO_4与PbO_2的摩尔比为3:1,但PbO_2还原率最高仅为52.4%。Na_2SO_3还原最佳条件:Na_2SO_3过量系数为6.0,反应时间为90~120min,反应温度为90℃时,PbO_2的还原率可达到100%。PbSO_4的脱硫转化实验结果表明,NaOH脱硫的最佳条件:时间60~120min,温度90℃,过量系数1.4,脱硫率仅为88.88%。Na_2CO_3脱硫的最佳条件:时间60~90min,温度90℃,过量系数1.3,脱硫率仅为80.61%。红外光谱分析结果表明,在碱性木糖醇溶液中PbO_2可以将木糖醇中的-OH氧化成-COO-,在溶液中与Pb以金属有机化合物的形式存在。木糖醇浓度、NaOH浓度对PbO_2浸出率影响很大。PbO_2浸出率会随着木糖醇浓度的增加呈现先增大后减小再增大的趋势。木糖醇浓度的变化会导致PbO_2不同的溶解机制。碱性木糖醇体系PbO_2浸出的最佳条件:NaOH浓度1.5~2mol/L,木糖醇浓度为0.53~0.79mol/L,浸出温度70℃,浸出时间30~60min,PbO_2浸出率可达99.18%。PbSO_4在碱性木糖醇体系中的浸出研究表明,木糖醇、NaOH浓度对PbSO_4的溶解量影响最大,时间和温度影响较小。溶液中仅存在木糖醇组分时,PbSO_4不会与其发生反应。PbSO_4在碱性木糖醇体系中的溶解是在木糖醇和NaOH共同作用下完成的。PbSO_4在碱性木糖醇体系浸出的最佳条件:反应时间60~90min,反应温度90℃,木糖醇浓度50~80g/L,NaOH浓度60~80g/L,PbSO_4的浸出率可达100%。对铅膏在碱性木糖醇体系中进行了直接浸出研究,得出铅膏浸出的最佳条件:反应时间30~60min,反应温度90℃,木糖醇浓度80~120g/L,NaOH浓度60~80g/L。铅膏在碱性木糖醇体系的浸出率可达96.24%,在该体系下可实现铅膏的短流程浸出。对碱性木糖醇体系含铅溶液进行电沉积的初步研究发现:当电流密度为140A/m~2,温度40℃,NaOH浓度100g/L,木糖醇浓度120g/L,溶液铅浓度100g/L,极距4cm,电解液循环速度15m L/min条件下时,电流效率可达99.68%,阴极能耗为381.71k Wh/t,生成的阴极铅表面相对平整,枝晶较少。
[Abstract]:The demand for lead is increasing in human society, but the mineral resources of lead concentrate are decreasing. Therefore, the recycling of lead has become an important way for the sustainable development of lead industry. At the same time, if the waste lead battery is not reasonably recovered, it will cause a great threat to the environment. As an important part of the waste lead storage pool, the lead paste is an important part of the waste lead storage pool, because its composition is complicated. In order to recover the key and difficult points, the traditional fire method has the advantages of high energy consumption, low lead recovery, lead dust and SO2, which are serious to the environment. And the wet process technology has attracted more and more attention due to the advantages of high direct metal yield and low pollution. The organic matter treatment system has become an important research with its low pollution advantages. The paper firstly uses two reductant FeSO_4 and Na_2SO_3 to reduce and transform PbO_2, and uses two kinds of desulfurizer, NaOH and Na_2CO_3 to remove PbSO_4. Secondly, the leaching behavior of the main component PbO_2 and PbSO_4 in the alkaline xylitol system is investigated, and the leaching behavior of the lead paste in the alkaline xylitol system is also carried out. At last, the electrodeposition process of alkaline xylitol and lead solution was preliminarily explored. By means of X ray diffraction (XRD), scanning electron microscopy (SEM) and energy spectrum (EDAX), the evolution of the phase of the insoluble substances and the composition and morphology of the insoluble compounds were analyzed. The Fourier transform infrared spectroscopy (FTIR) was used to analyze the change of the organic groups in the leaching solution. The main research results of the paper are as follows: the results of PbO_2 reduction show that the reduction effect of Na_2SO_3 is obviously better than that of FeSO_4.FeSO_4 reduction: FeSO_4 excess coefficient is 1~1.1, reaction time 90~120min, reaction temperature 90 C, and the molar ratio of H_2SO_4 to PbO_2 is 3:1, but the highest reduction rate of PbO_2 is only the best condition of 52.4%.Na_2SO_3 reduction. The Na_2SO_3 excess coefficient is 6, the reaction time is 90~120min, the reaction temperature is 90 C, the reduction rate of PbO_2 can reach 100%.PbSO_4, the result of desulfurization transformation experiment shows that the best condition of NaOH desulfurization is time 60~120min, temperature 90, and excess coefficient 1.4. The desulfurization rate is only the best condition of 88.88%.Na_2CO_3 desulphurization: time 60~90min, temperature 90 C, The excessive coefficient of 1.3, the desulfurization rate is only 80.61%. infrared spectrum analysis results show that in the alkaline xylitol solution, PbO_2 can oxidize the -OH in xylitol to -COO-, and in the solution and Pb in the form of metal organic compounds. The concentration of xylitol, NaOH concentration affects the PbO_2 leaching rate and the.PbO_2 leaching rate will follow the concentration of xylitol. The increase of the increase first and then decrease and then increase. The variation of xylitol concentration will lead to the different dissolution mechanism of PbO_2. The optimum conditions for the leaching of PbO_2 in alkaline xylitol system are NaOH concentration 1.5~2mol/L, the concentration of xylitol 0.53~0.79mol/L, the leaching temperature of 70, the leaching time 30~ 60min, and the leaching rate of PbO_2 to 99.18%.PbSO_4 in alkaline xylose The leaching study in the alcohol system showed that the concentration of xylitol and NaOH had the greatest influence on the dissolution of PbSO_4, and the time and temperature had little effect. When only xylitol components were found in the solution, PbSO_4 would not react with the reaction of.PbSO_4 in the alkaline xylitol system, which was performed under the co action of xylitol and NaOH in the alkaline xylitol. The optimum conditions of the system leaching are: reaction time 60~90min, reaction temperature 90 C, xylitol concentration 50~80g/L, NaOH concentration 60~80g/L, the leaching rate of PbSO_4 can reach 100%. direct leaching of alkaline xylitol system, and the best condition of lead extract leaching is obtained: reaction time 30~60min, reaction temperature 90, xylitol 80~120g/ L, the leaching rate of NaOH concentration 60~80g/L. plaster in alkaline xylitol system can reach 96.24%. Under this system, the short process leaching of lead paste can be realized. Preliminary study on electrodeposition of lead containing solution of alkaline xylitol system found that when the current density is 140A/m~2, the temperature is 40, NaOH concentration 100g/L, the concentration of xylitol 120g/L, and the solution lead concentration 100g/L, At the extreme distance of 4cm and the electrolyte circulation rate of 15m L/min, the current efficiency can reach 99.68% and the energy consumption of the cathode is 381.71k Wh/t. The surface of the cathode lead is relatively flat and the dendrite is less.
【学位授予单位】：河南科技大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：X705;TF812
本文编号：2172124
[Abstract]:The demand for lead is increasing in human society, but the mineral resources of lead concentrate are decreasing. Therefore, the recycling of lead has become an important way for the sustainable development of lead industry. At the same time, if the waste lead battery is not reasonably recovered, it will cause a great threat to the environment. As an important part of the waste lead storage pool, the lead paste is an important part of the waste lead storage pool, because its composition is complicated. In order to recover the key and difficult points, the traditional fire method has the advantages of high energy consumption, low lead recovery, lead dust and SO2, which are serious to the environment. And the wet process technology has attracted more and more attention due to the advantages of high direct metal yield and low pollution. The organic matter treatment system has become an important research with its low pollution advantages. The paper firstly uses two reductant FeSO_4 and Na_2SO_3 to reduce and transform PbO_2, and uses two kinds of desulfurizer, NaOH and Na_2CO_3 to remove PbSO_4. Secondly, the leaching behavior of the main component PbO_2 and PbSO_4 in the alkaline xylitol system is investigated, and the leaching behavior of the lead paste in the alkaline xylitol system is also carried out. At last, the electrodeposition process of alkaline xylitol and lead solution was preliminarily explored. By means of X ray diffraction (XRD), scanning electron microscopy (SEM) and energy spectrum (EDAX), the evolution of the phase of the insoluble substances and the composition and morphology of the insoluble compounds were analyzed. The Fourier transform infrared spectroscopy (FTIR) was used to analyze the change of the organic groups in the leaching solution. The main research results of the paper are as follows: the results of PbO_2 reduction show that the reduction effect of Na_2SO_3 is obviously better than that of FeSO_4.FeSO_4 reduction: FeSO_4 excess coefficient is 1~1.1, reaction time 90~120min, reaction temperature 90 C, and the molar ratio of H_2SO_4 to PbO_2 is 3:1, but the highest reduction rate of PbO_2 is only the best condition of 52.4%.Na_2SO_3 reduction. The Na_2SO_3 excess coefficient is 6, the reaction time is 90~120min, the reaction temperature is 90 C, the reduction rate of PbO_2 can reach 100%.PbSO_4, the result of desulfurization transformation experiment shows that the best condition of NaOH desulfurization is time 60~120min, temperature 90, and excess coefficient 1.4. The desulfurization rate is only the best condition of 88.88%.Na_2CO_3 desulphurization: time 60~90min, temperature 90 C, The excessive coefficient of 1.3, the desulfurization rate is only 80.61%. infrared spectrum analysis results show that in the alkaline xylitol solution, PbO_2 can oxidize the -OH in xylitol to -COO-, and in the solution and Pb in the form of metal organic compounds. The concentration of xylitol, NaOH concentration affects the PbO_2 leaching rate and the.PbO_2 leaching rate will follow the concentration of xylitol. The increase of the increase first and then decrease and then increase. The variation of xylitol concentration will lead to the different dissolution mechanism of PbO_2. The optimum conditions for the leaching of PbO_2 in alkaline xylitol system are NaOH concentration 1.5~2mol/L, the concentration of xylitol 0.53~0.79mol/L, the leaching temperature of 70, the leaching time 30~ 60min, and the leaching rate of PbO_2 to 99.18%.PbSO_4 in alkaline xylose The leaching study in the alcohol system showed that the concentration of xylitol and NaOH had the greatest influence on the dissolution of PbSO_4, and the time and temperature had little effect. When only xylitol components were found in the solution, PbSO_4 would not react with the reaction of.PbSO_4 in the alkaline xylitol system, which was performed under the co action of xylitol and NaOH in the alkaline xylitol. The optimum conditions of the system leaching are: reaction time 60~90min, reaction temperature 90 C, xylitol concentration 50~80g/L, NaOH concentration 60~80g/L, the leaching rate of PbSO_4 can reach 100%. direct leaching of alkaline xylitol system, and the best condition of lead extract leaching is obtained: reaction time 30~60min, reaction temperature 90, xylitol 80~120g/ L, the leaching rate of NaOH concentration 60~80g/L. plaster in alkaline xylitol system can reach 96.24%. Under this system, the short process leaching of lead paste can be realized. Preliminary study on electrodeposition of lead containing solution of alkaline xylitol system found that when the current density is 140A/m~2, the temperature is 40, NaOH concentration 100g/L, the concentration of xylitol 120g/L, and the solution lead concentration 100g/L, At the extreme distance of 4cm and the electrolyte circulation rate of 15m L/min, the current efficiency can reach 99.68% and the energy consumption of the cathode is 381.71k Wh/t. The surface of the cathode lead is relatively flat and the dendrite is less.
【学位授予单位】：河南科技大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：X705;TF812
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