电解锰渣回收锰及处理含铜废水的研究
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摘要
分析了电解锰渣中锰的形态及其对环境的影响。结果表明,某电解锰厂锰渣中的锰主要以水溶性锰离子、碳酸锰盐及二氧化锰的形式存在,其中水溶性锰离子占总锰的50%左右,最高析出量可达到3.7mg/ml,远远超过了国家排放标准;电解锰渣浸出液的pH值均在5左右,即锰渣呈酸性,若直接排放,将对周边环境造成严重的污染。
通过正交实验确定的用硫酸回浸法处理电解锰渣的适宜工艺条件为:固液比1:3、硫酸浓度20%、酸浸温度为90℃、酸浸时间3h,锰的最高浸出率可达到96%;经两步除杂法后,可得到纯度为91%的硫酸锰产品。采取单因素法分析了用铵盐焙烧法处理电解锰渣的各焙烧条件对锰渣浸出率的影响,确定其较优的焙烧条件为:铵矿比为1:1、焙烧时间为1h、焙烧温度为450℃,锰的最高浸出率为83%,通过除杂可得到98%的硫酸锰产品。对两种方法的工艺过程和环境效益进行了分析比较,从工艺上讲,用铵盐焙烧法制取电解锰渣较为合适。
在分析不同方法处理后剩余残渣成分基础上,选用比表面积较大的铵盐焙烧渣进行了处理含铜废水的研究。结果表明,在实验室常温条件下,对铜离子浓度为60mg/L模拟废水,当锰渣投加量为1.5g,在pH为6、反应时间为2.5h条件下,锰渣对铜离子的吸附效果最好,吸附率可达96%。
The Mn forms in waste residue of electrolytic manganese metal (EMM) and its influence to the environment was analyzed. The forms of Mn in EMM waste residue are chiefly the dissociated Mn2+, carbonate, and MnO2. There are about 50% of total Mn is Mn2+ dissolved by water, and the best leaching concentrate is up to 3.7mg/ml which is much higher than that of nation’s discharge standard. The pH of the leaching liquid is 5, and it means the waste residue is acidic. If the waste residue of EMM is discharged directly to land, it will cause serious pollution environment.
When the waste residue of EMM was leached with sulfuric acid, the leaching conditions are obtained by the orthogonal experiment. Namely, the liquid-solid ratio of the reaction system is 3:1, the concentration of sulfuric acid is 20%, the leaching temperature is 90℃and the leaching time is 3h. The results were shown that the leaching ratio of manganese is up to 96%. Finally, 91% of MnSO4 could be obtained by the method of two steps depuration .
By the method of single factor, the effect of roasting conditions on Mn leaching ratio for treating EMM residue with ammonium salt has been researched. When the mixture of the waste residue of EMM and(NH4)2SO4 (1:1) was roasted for 1h at 450℃, Mn leaching ratio is up to 83%. Finally, 98% purity of MnSO4 has been obtained through remove of impurity. The process, economic efficiency and enviornmental benefit on the above two methods have been compared. From considering only the process, the roasting with ammonium salt is more suitable method.
Based on the analyze of different residue’s components, the residue after roasting with ammonium salt method, which has bigger specific surface area, was chose to remove the copper ion in the wastewater. The results was shown that the residue has a better disposal efficiency for copper ion in 60mg/L of containing copper wastewatert. When the pH of the wastewater is 6, the mass residue is 1.5g and treating time is 2.5 hoursm, the removal ratio of Cu2+ was reached 96% at room temperature.
通过正交实验确定的用硫酸回浸法处理电解锰渣的适宜工艺条件为:固液比1:3、硫酸浓度20%、酸浸温度为90℃、酸浸时间3h,锰的最高浸出率可达到96%;经两步除杂法后,可得到纯度为91%的硫酸锰产品。采取单因素法分析了用铵盐焙烧法处理电解锰渣的各焙烧条件对锰渣浸出率的影响,确定其较优的焙烧条件为:铵矿比为1:1、焙烧时间为1h、焙烧温度为450℃,锰的最高浸出率为83%,通过除杂可得到98%的硫酸锰产品。对两种方法的工艺过程和环境效益进行了分析比较,从工艺上讲,用铵盐焙烧法制取电解锰渣较为合适。
在分析不同方法处理后剩余残渣成分基础上,选用比表面积较大的铵盐焙烧渣进行了处理含铜废水的研究。结果表明,在实验室常温条件下,对铜离子浓度为60mg/L模拟废水,当锰渣投加量为1.5g,在pH为6、反应时间为2.5h条件下,锰渣对铜离子的吸附效果最好,吸附率可达96%。
The Mn forms in waste residue of electrolytic manganese metal (EMM) and its influence to the environment was analyzed. The forms of Mn in EMM waste residue are chiefly the dissociated Mn2+, carbonate, and MnO2. There are about 50% of total Mn is Mn2+ dissolved by water, and the best leaching concentrate is up to 3.7mg/ml which is much higher than that of nation’s discharge standard. The pH of the leaching liquid is 5, and it means the waste residue is acidic. If the waste residue of EMM is discharged directly to land, it will cause serious pollution environment.
When the waste residue of EMM was leached with sulfuric acid, the leaching conditions are obtained by the orthogonal experiment. Namely, the liquid-solid ratio of the reaction system is 3:1, the concentration of sulfuric acid is 20%, the leaching temperature is 90℃and the leaching time is 3h. The results were shown that the leaching ratio of manganese is up to 96%. Finally, 91% of MnSO4 could be obtained by the method of two steps depuration .
By the method of single factor, the effect of roasting conditions on Mn leaching ratio for treating EMM residue with ammonium salt has been researched. When the mixture of the waste residue of EMM and(NH4)2SO4 (1:1) was roasted for 1h at 450℃, Mn leaching ratio is up to 83%. Finally, 98% purity of MnSO4 has been obtained through remove of impurity. The process, economic efficiency and enviornmental benefit on the above two methods have been compared. From considering only the process, the roasting with ammonium salt is more suitable method.
Based on the analyze of different residue’s components, the residue after roasting with ammonium salt method, which has bigger specific surface area, was chose to remove the copper ion in the wastewater. The results was shown that the residue has a better disposal efficiency for copper ion in 60mg/L of containing copper wastewatert. When the pH of the wastewater is 6, the mass residue is 1.5g and treating time is 2.5 hoursm, the removal ratio of Cu2+ was reached 96% at room temperature.
引文
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[25]常方方,曲久辉,刘锐平等.铁锰复合氧化物的制备及吸附除砷性能[J].环境科学学报,2006,26(11):1769-1773.
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[29]葛晓霞,田野,徐东慧等.硫酸锰废渣浸出毒性及淋溶特性研究[J].环境污染治理技术与设备,2005,3(6):56-60.
[30]葛晓霞,蔡固平,曾光明.硫酸锰废渣无害化及资源化研究[J].中国锰业,2004,22(1):10-14.
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[37]朱国才,李赋屏,肖明贵.采用硫酸铵焙烧方法从低品位碳酸锰矿中富集回收锰.桂林工学院学报,2005,25(4):534-537.
[38]靳晓珠,杨仲平,陈祝炳等.低品位碳酸锰矿铵盐焙烧富锰工艺研究[J].中国锰业,2006,24(1):28-29.
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[40]实用化学手册编写组.实用化学手册[M].北京:科学出版社:2000.
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[42] Mallin, J.W. Crystallization[M]. 2nd,Ed.Butter Worths:1972.
[43]彭爱国,贺周初,郑贤福等.硫酸锰深度除杂研究[J].精细化工中间体,2002,32(2):52-53.
[44]沈水发,陈耐生.利用高岭土制备聚合氯化铝净水剂[J].无机盐工业,1999,31(5):33-35.
[44]田宝珍,张云.铝铁共聚合絮凝剂的研制及应用[J]业水处理,1998,18(1):17-20.
[45] BAYLIS TK. Silicates as Aid to Coagulation[J]. JAWWA,1937,29(9):1355-1396.
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[2]刘胜利.电解金属锰废渣的综合利用[J].中国锰业,1998,16(4):35-36.
[3]曾湘波.国外电解金属锰的生产概况[J].中国锰业,2000,18(2):7-11.
[4]谭柱中. 196-2006年中国电解锰工业的发展与展望[J].中国锰业,2007,25(1):5-10.
[5]张径生.中国锰业面临的机遇和挑战[J].中国锰业,2007,25(1):1-4.
[6]王聪寿.我国电解金属锰的现状、问题及对策[J].中国锰业,1995,13(5):44-47.
[7]谭柱中.中国电解金属锰工业现状[J].中国锰业,2005,23(2):5-6.
[8] P. Lakshmipathiraj, B.R.V. Narasimhan, S. Prabhakar, G. Bhaskar Raju. Adsorption studies of arsenic on Mn-substituted iron oxyhydroxide[J]. Journal of Colloid and Interface Science 2006,304:317-322.
[9] Arsent'ev,V.A. Experimental processing of vorkutinsk manganese ores by hydrometallurgical methods[D].Obogashch.Rud,1992,(6):17-18.
[10] Dzhaparidze,P.N. Chemical reactions during the leaching of manganese ores and slurries with sulfuric acid[J].Soobshch.Akad.NaukGruz,1971,61(2):8-345.
[11]查进.磷渣锰渣路面基层材料的应用[D].武汉理工大学硕士论文,2005.
[12]谢显明.电锰渣及其研制品的肥效特性分析[J].中国锰业,1999,17(4):46-49.
[13]贾云,原金海,谭世语.以富锰渣制备4A分子筛[J].无机盐工业,2006,(6):51-54.
[14]李坦平,周学忠,曾利群等.电解锰渣的理化特征及其开发应用的研究[J].中国锰业,2006,24(2):13-16..
[15]杨新国.我国硫酸锰的发展近况及前景[J].中国锰业,1990,8(2):17-21.
[16]原金海.富锰渣的综合利用工艺研究[D].重庆大学硕士论文,2005.
[17]岩石矿物分析编写小组.岩石矿物分析(第一版)[M].地质出版社,1974.
[18]马艳梅,马鑫.氟硅酸钾容量法测定二氧化硅[J].辽宁建材,2005(2):47-48.
[19]韦善良,罗天盛.天然锰矿中铁的测定[J].电池,1994,(4):193-194.
[20]李彩华.高锰中铬高铝钢中铝的测定[A].湖南冶金,2006,34(1):43-44.
[21]田宗平,孙际茂,邓美文等.电解金属锰和锰盐生产排放的酸浸废渣中锰的形态研究[J].中国锰业,2006,24(1):25-27.
[22]葛晓霞,蔡固平,曾光明.硫酸锰废渣无害化及资源化研究[J].中国锰业,2004,22(1):10-14.
[23]姚俊.电解锰废水及水底沉积物中重金属元素对流域污染的研究[J].吉首大学学报,1999,20(3):30.
[24]李坦平,周学忠,曾利群等.电解锰渣的理化特征及其开发应用的研究[J].中国锰业,2006,24(2):13-16.
[25]常方方,曲久辉,刘锐平等.铁锰复合氧化物的制备及吸附除砷性能[J].环境科学学报,2006,26(11):1769-1773.
[26] FRANCIS W.Y.Mo. SulpHuric acid leaching of the Nsuta manganese carbonate ore[J]. Hhydrometallurgy,1996,40:123-124.
[27]姚俊,吴文学,杨小瑞等.电解锰中重金属元素与流域污染[J].吉首大学学报,1999,20(3):74-77.
[28]黄典文,黄伟锋.氧化溴酚蓝褪色光度法测定微量锰[J].冶金分析,2001,21(5):7-8.
[29]葛晓霞,田野,徐东慧等.硫酸锰废渣浸出毒性及淋溶特性研究[J].环境污染治理技术与设备,2005,3(6):56-60.
[30]葛晓霞,蔡固平,曾光明.硫酸锰废渣无害化及资源化研究[J].中国锰业,2004,22(1):10-14.
[31]伍福智,钟国清,蒋礼.酸解法制备硫酸锰的研究[J].无机盐工业,1994,(5):44-46.
[32]黄映恒.软锰矿直接浸取硫酸锰副产聚合硫酸铁的实验[J].河池师专学报,1995,15(2):97-100.
[33]胡德斌,张胜涛.贫锰矿酸浸制取硫酸锰的工艺研究[J].电源技术,1999,23(6):304-306,337.
[34]丁揩如,余逊贤.锰矿开发与加工技术[M].长沙:湖南科学技术出版社,1992.07.
[35]李文郁.从贫锰矿制取硫酸锰的工艺初探[J].无机盐工业,1991,(4):14-17.
[36]杨仲平,靳晓珠,朱国才.铵盐焙烧法处理低品位锰矿的工艺研究[J].中国锰业,2006,24(3):12-14.
[37]朱国才,李赋屏,肖明贵.采用硫酸铵焙烧方法从低品位碳酸锰矿中富集回收锰.桂林工学院学报,2005,25(4):534-537.
[38]靳晓珠,杨仲平,陈祝炳等.低品位碳酸锰矿铵盐焙烧富锰工艺研究[J].中国锰业,2006,24(1):28-29.
[39]杭州大学化学系分析化学教研室.分析化学手册(第二分册)化学分析[M].北京:化学工业出版社,1982.
[40]实用化学手册编写组.实用化学手册[M].北京:科学出版社:2000.
[41] Laudise, R.A. The growth of single Crystals[M]. prentice-Halt:1970.
[42] Mallin, J.W. Crystallization[M]. 2nd,Ed.Butter Worths:1972.
[43]彭爱国,贺周初,郑贤福等.硫酸锰深度除杂研究[J].精细化工中间体,2002,32(2):52-53.
[44]沈水发,陈耐生.利用高岭土制备聚合氯化铝净水剂[J].无机盐工业,1999,31(5):33-35.
[44]田宝珍,张云.铝铁共聚合絮凝剂的研制及应用[J]业水处理,1998,18(1):17-20.
[45] BAYLIS TK. Silicates as Aid to Coagulation[J]. JAWWA,1937,29(9):1355-1396.
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