铁矾渣还原焙烧自硫化研究
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摘要
为解决铁矾渣大量堆存带来的资源浪费和重金属污染,及传统焙烧回收处理工艺会产生SO_2等二次污染的问题,同时实现铁矾渣中主要有价金属的回收利用,提出了铁矾渣还原焙烧固硫的预处理方法。以铁矾渣热分解过程和热力学计算为基础,通过考察焙烧条件对铁矾渣中主要有价金属锌的硫化率、硫的固定率及物相转变的影响,对铁矾渣还原焙烧自硫化过程进行了研究。结果表明:在焙烧温度为900℃,碳粉添加量为18%,碳酸钠添加量为5%,焙烧时间为90min的条件下,锌的硫化率和硫固化率分别可达93.47%和87.69%。焙烧产物主要以硫化物形式存在,可通过浮选等方式富集。铁矾渣还原焙烧可以实现Zn等主要有价金属的综合回收预处理并避免焙烧过程中SO_2的排放。该研究对其它重金属硫酸盐的清洁处理具有重要的指导意义。
In order to solve the problems such as the waste of resources and the heavy metal pollution caused by large-scale storage of jarosite residues,and the SO_2 emissions caused by traditional roasting and recycling process,at the same time,to realize the recycling and utilization of the main metal in the jarosite residues,the pretreatment method for the reduction roasting and sulfur fixation of jarosite residues was put forward.Based on the thermodynamics calculation and the research of the thermal decomposition process of jarosite residues,the process of reduction roasting self-sulfidation of jarosite residues were studied,in which the effects of roasting condition on the sulfurfidation degree of zinc,the fixation extent of sulfur and the change of the phase were investigated.The results show that the sulfidation extent of Zinc and the fixation extent of S reaches up to 93.47% and 87.69%,respectively,under the following optimum conditions,which the roasting temperature is 900 ℃,carbon powder addition is 18%,the amount of sodium carbonate is 5%,and the calcination time is 90 min.The roasting product mainly exists in the form of sulfide and can be separated by flotation.The reduction roasting of jarosite residues can achieve the comprehensive recovery of Zn and other valuable metals and avoid the emission of SO_2 in the roasting process.This study is of great significance for the cleaning treatment of other heavy metal sulfates.
In order to solve the problems such as the waste of resources and the heavy metal pollution caused by large-scale storage of jarosite residues,and the SO_2 emissions caused by traditional roasting and recycling process,at the same time,to realize the recycling and utilization of the main metal in the jarosite residues,the pretreatment method for the reduction roasting and sulfur fixation of jarosite residues was put forward.Based on the thermodynamics calculation and the research of the thermal decomposition process of jarosite residues,the process of reduction roasting self-sulfidation of jarosite residues were studied,in which the effects of roasting condition on the sulfurfidation degree of zinc,the fixation extent of sulfur and the change of the phase were investigated.The results show that the sulfidation extent of Zinc and the fixation extent of S reaches up to 93.47% and 87.69%,respectively,under the following optimum conditions,which the roasting temperature is 900 ℃,carbon powder addition is 18%,the amount of sodium carbonate is 5%,and the calcination time is 90 min.The roasting product mainly exists in the form of sulfide and can be separated by flotation.The reduction roasting of jarosite residues can achieve the comprehensive recovery of Zn and other valuable metals and avoid the emission of SO_2 in the roasting process.This study is of great significance for the cleaning treatment of other heavy metal sulfates.
引文
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[22]姜涛,刘牡丹,李光辉,等.钠盐对高铝褐铁矿还原焙烧铝铁分离的影响[J].中国有色金属学报,2010,20(6):1226-1233.JIANG Tao,LIU Mudan,LI Guanghui,et al.Effects of sodium-salt on Al-Fe separation by reduction roasting for high-aluminum content limonite[J].The Chinese Journal of Nonferrous Metals,2010,20(6):1226-1233.
[2]黎红兵,周志辉,陈志飞,等.黄钾铁矾法炼锌的沉矾过程研究[J].湖南有色金属,2010,26(4):27-29.LI Hongbing,ZHOU Zhihui,CHEN Zhifei,et al.Study on the jarosite process in zinc hydrometallurgy[J].Hunan Nonferrous Metals.2010,26(4):27-29.
[3]马菲菲.湿法炼锌浸出沉矾沉铁工艺探讨[J].中国有色冶金,2017,46(2):19-22.MA Feifei.Discussion on vanadium and iron precipitation process in zinc hydrometallurgy[J].China Nonferrous Metallurgy,2017,46(2):19-22.
[4]娄永刚,郭学益,田庆华.中国铅锌工业发展探析[J].世界有色金属,2015,30(4):50-54.LOUYonggang, GUOXueyi, TIANQinghua.Development of lead and zinc industry in China[J].World Nonferrous Metals,2015,30(4):50-54.
[5]LIU P,ZHANG Y,WANG L,et al.Thermodynamics and nucleation mechanism of ammonium jarosite in sulfuric acid solution[J].Journal of Crystal Growth,2017,478:52-57.
[6]VUMMIDI LAKSHMAN S,MOHAN S,DREIZIN E L,et al.Kinetics of thermal decomposition of a synthetic KH3Ojarosite analog[J].Journal of Thermal Analysis and Calorimetry,2014,115(1):609-620.
[7]SPRATT H,RINTOUL L,AVDEEV M,et al.The thermal decomposition of hydronium jarosite and ammoniojarosite[J].Journal of Thermal Analysis and calorimetry,2014,115(1):101-109.
[8]LAKSHMAN S V,MOHAN S,DREIZIN E L,et al.Kinetics of thermal decomposition of a synthetic K-H3O jarosite analog[J].Journal of Thermal Analysis and Calorimetry,2014,115(1):609-620.
[9]KEROLLI-MUSTAFA M,MANDIC V,CURKOVIC L,et al.Investigation of thermal decomposition of jarosite tailing waste[J].Journal of Thermal Analysis and Calorimetry,2016,123(1):421-430.
[10]曹晓恩,洪陆阔,周和敏,等.铁矾渣热分解过程研究[J].矿冶工程,2016,36(2):67-70.CAO Xiaoen, HONG Lukuo,ZHOU Hemin,et al.Thermal Decomposition Process of Jarosite Residue[J].Mining and Metallurgical Engineering,2016,36(2):67-70.
[11]马红周,桂海平,樊鹏斌,等.湿法炼锌黄钾铁矾渣资源化的新探索[J].工业加热,2016,45(2):8-11.MA Hongzhou,GUI Haiping,FAN Pengbin,et al.New exploration of jarosite slag resources produced in zinc hydrometallurgy[J].Industrial Heating,2016,45(2):8-11.
[12]HAN H,SUN W,HU Y,et al.Anglesite and silver recovery from jarosite residues through roasting and sulfidization-flotation in zinc hydrometallurgy[J].Journal of Hazardous Materials,2014,278:49-54.
[13]JU S,ZHANG L,PENG J,et al.Thermodynamics of leachingroastedjarositeresiduefromzinc hydrometallurgy in NH4Cl system[J].Transactions of Nonferrous Metals Society of China,2013,23(4):1179-1183.
[14]曹晓恩,洪陆阔,齐渊洪,等.转底炉煤基直接还原铁矾渣回收铁锌联合工艺[J].有色金属(冶炼部分),2016,68(4):4-7.CAO Xiaoen,HONG Lukuo,QI Yuanhong,et al.Combined process to recover iron and zinc from jarosite residue by coal-based direct reduction in rotary hearth furnace[J].Nonferrous Metals(Extractive Metallurgy),2016,68(4):4-7.
[15]刘鹏飞,张亦飞,游韶玮,等.热酸浸出回收黄钾铁矾渣中有价元素[J].过程工程学报,2016,41(4):584-589.LIU Pengfei,ZHANG Yifei,YOU Shaowei,et al.Recovery of valuable elements in jaroaite residue by hot acid leaching[J].The Chinese Journal of Process Engineering,2016,41(4):584-589.
[16]马菲菲,李志强.湿法炼锌铁矾渣处理改造实践[J].中国有色冶金,2015,44(3):25-28.MA Feifei,LI Zhiqiang.Practice of jarosite residue treatment in Zn hydrometallurgy[J].China Nonferrous Metallurgy,2015,44(3):25-28.
[17]刘超,巨少华,张利波,等.用微波硫酸化焙烧—水浸新工艺从铁矾渣中回收有价金属[J].湿法冶金,2016,35(1):36-39.LIU Chao,JU Shaohua,ZHANG Libo,et al.A new process for recovery valuable metals from jarosite slag by microwave roasting with sulfuric acid and water leaching[J].Hydrometallurgy of China,2016,35(1):36-39.
[18]张楠楠,南姣,谭宏斌,等.煤掺量对焙烧铁矾渣中硫物相和含量的影响[J].陕西理工学院学报(自然科学版),2016,32(6):29-33.ZHANG Nannan,NAN Jiao,TAN Hongbin,et al.Effect of the phase and content of sulfur by baking of jarosite residue on percentages of powdery coal[J].Journal of Shaanxi Shaanxi University of Technology(Natural Science Edution),2016,32(6):29-33.
[19]LIU C,JU S H,ZHANG L B,et al.Recovery of valuable metals from jarosite by sulphuric acid roasting using microwave and water leaching[J].Canadian Metallurgical Quarterly,2017,56(1):1-9.
[20]路殿坤,金哲男,谢峰,等.铁矾渣还原焙烧制备磁铁矿的研究[J].铜业工程,2013,30(1):6-11.LU Diankun,JIN Zhenan,XIE Feng,et al.Research on magnetite preparation by reductive baking of jarosite residue[J].Copper Engineering,2013,30(1):6-11.
[21]李光辉,饶明军,姜涛,等.红土镍矿钠盐还原焙烧-磁选的机理[J].中国有色金属学报,2012,22(1):274-280.LI Guanghui, RAO Mingjun,JIANG Tao,et al.Reduction roasting-magnetic separation mechanisms of nickelferous laterite ore in presence of sodium salts[J].The Chinese Journal of Nonferrous Metals,2012,22(1):274-280.
[22]姜涛,刘牡丹,李光辉,等.钠盐对高铝褐铁矿还原焙烧铝铁分离的影响[J].中国有色金属学报,2010,20(6):1226-1233.JIANG Tao,LIU Mudan,LI Guanghui,et al.Effects of sodium-salt on Al-Fe separation by reduction roasting for high-aluminum content limonite[J].The Chinese Journal of Nonferrous Metals,2010,20(6):1226-1233.