低品位氧化锌矿的浸出工艺研究及活性氧化锌的制备
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摘要
近年来,我国锌产品的生产能力大幅增长,造成锌资源供应日益紧张、锌矿石品位逐渐下降,因此提高各种锌资源利用率成为必然趋势。开发低品位氧化锌矿石的有效利用方法,对促进我国冶锌工业持续发展具有重要的意义。本文采用湿法冶金方法提取低品位氧化锌矿石中的锌,研究不同浸出条件对锌金属浸出率的影响,通过净化、沉淀和煅烧制备出活性氧化锌。
对云南兰坪地区低品位氧化锌矿石进行矿物学分析,矿样中的锌主要以菱锌矿和异极矿形式存在。分别以H2SO4和NH3·H2O-NH4HCO3体系为浸出剂对比研究了酸浸和氨浸两种浸出工艺,考察了浸出剂浓度、浸出温度、矿样粒度、液固比及浸出时间等因素的影响,确定了氧化锌矿石浸出的最佳工艺条件。在此条件下,酸浸和氨浸的锌一段浸出率分别为86.0%和87.2%,经过二段浸出,锌浸出率分别提高至94.0%和95.9%。
在氧化锌浸出液净化过程中,酸浸液采用漂白粉氧化除铁及锌粉还原除杂两步净化,氨浸液采用锌粉还原除杂一步净化。综合考虑浸出、净化两步工艺,酸浸过程中硅元素大量进入浸出液,氨浸过程硅元素较少进入浸出液；净化后,氨浸液中Fe、Mn含量为痕量,与酸浸液相比明显金属杂质的种类少、含量低；氨浸液的净化具有操作简单、能耗少、对环境友好的优点。
研究了氧化锌氨净出液的蒸氨温度、蒸氨时间、陈化时间和煅烧时间等对氧化锌粒径的影响,得到优化的活性氧化锌制备工艺条件：蒸氨温度120℃,蒸氨时间2.0h,陈化时间10min,煅烧温度350℃,煅烧时间0.5h。经过理化性能测定,由低品位氧化锌矿制备出的活性氧化锌符合化工行业标准HG/T 2572-2006。
With the rapid growth of zinc productivity in recent years, it is becoming more and more significant to make better use of various raw materials as the deposit of zinc resources and the quality of zinc ores are decreasing. Therefore, there is a great interest in exploring low-grade zinc oxide sources which contributes to the sustainable development of domestic metallurgic industry. In this paper, zinc is leached from low-grade zinc oxide ore and the optimum conditions have been figured with hydrometallurgical processing. Activated zinc oxide is also prepared from leaching solution via purification, precipitation and calcination.
The mineralogical characters of the low-grade zinc oxide ore are studied. The results show that the main zinc minerals are smithsonite and hemimorphite. Based on this, H2SO4 and NH3·H2O-NH4HCO3 solutions are used to leaching Zinc from Zinc oxide ore, respectivly. The influence on the leaching rates of zinc including reaction time, temperature, concentration of leaching agent, particle size and liquid-solid ratio are investigated and screened out. Under the best conditions which are fixed by these single factor optimizing experiments, the leaching rates of Zinc which are 86.0% and 87.2% in the two different leaching agents, respectively. It can be dramatically promoted to 94.0% and 95.9% via two stages leaching process.
The solution of acid leaching is purified containing two steps which are de-ironing reaction and replacing reaction, while that of ammonium leaching solution includes only replacing reaction. The results of leaching and purifying prcesses indicate that ammonium leaching process takes the advantages of lower concentration of silicon in leaching solution, less variaties of metalline impurity and advantages of simplified process, low power consumption and environmetal friendliness.
In order to obtain highly actived zinc oxide, experiments of factors influencing particle size of activated zinc oxide are studied systematically. The optimum processes are as follow:the distilling ammonia time is 2.Oh, temperature is 120℃, aging time is l0min and the calcination time is 0.5h。And the calcination temperature is 350℃based on the DTG-TA analysis of zinc subcarbonate. Results show that properties of the product well agree to the Industry Standard of Chemical Engineering HG/T 2572-2006.
对云南兰坪地区低品位氧化锌矿石进行矿物学分析,矿样中的锌主要以菱锌矿和异极矿形式存在。分别以H2SO4和NH3·H2O-NH4HCO3体系为浸出剂对比研究了酸浸和氨浸两种浸出工艺,考察了浸出剂浓度、浸出温度、矿样粒度、液固比及浸出时间等因素的影响,确定了氧化锌矿石浸出的最佳工艺条件。在此条件下,酸浸和氨浸的锌一段浸出率分别为86.0%和87.2%,经过二段浸出,锌浸出率分别提高至94.0%和95.9%。
在氧化锌浸出液净化过程中,酸浸液采用漂白粉氧化除铁及锌粉还原除杂两步净化,氨浸液采用锌粉还原除杂一步净化。综合考虑浸出、净化两步工艺,酸浸过程中硅元素大量进入浸出液,氨浸过程硅元素较少进入浸出液；净化后,氨浸液中Fe、Mn含量为痕量,与酸浸液相比明显金属杂质的种类少、含量低；氨浸液的净化具有操作简单、能耗少、对环境友好的优点。
研究了氧化锌氨净出液的蒸氨温度、蒸氨时间、陈化时间和煅烧时间等对氧化锌粒径的影响,得到优化的活性氧化锌制备工艺条件：蒸氨温度120℃,蒸氨时间2.0h,陈化时间10min,煅烧温度350℃,煅烧时间0.5h。经过理化性能测定,由低品位氧化锌矿制备出的活性氧化锌符合化工行业标准HG/T 2572-2006。
With the rapid growth of zinc productivity in recent years, it is becoming more and more significant to make better use of various raw materials as the deposit of zinc resources and the quality of zinc ores are decreasing. Therefore, there is a great interest in exploring low-grade zinc oxide sources which contributes to the sustainable development of domestic metallurgic industry. In this paper, zinc is leached from low-grade zinc oxide ore and the optimum conditions have been figured with hydrometallurgical processing. Activated zinc oxide is also prepared from leaching solution via purification, precipitation and calcination.
The mineralogical characters of the low-grade zinc oxide ore are studied. The results show that the main zinc minerals are smithsonite and hemimorphite. Based on this, H2SO4 and NH3·H2O-NH4HCO3 solutions are used to leaching Zinc from Zinc oxide ore, respectivly. The influence on the leaching rates of zinc including reaction time, temperature, concentration of leaching agent, particle size and liquid-solid ratio are investigated and screened out. Under the best conditions which are fixed by these single factor optimizing experiments, the leaching rates of Zinc which are 86.0% and 87.2% in the two different leaching agents, respectively. It can be dramatically promoted to 94.0% and 95.9% via two stages leaching process.
The solution of acid leaching is purified containing two steps which are de-ironing reaction and replacing reaction, while that of ammonium leaching solution includes only replacing reaction. The results of leaching and purifying prcesses indicate that ammonium leaching process takes the advantages of lower concentration of silicon in leaching solution, less variaties of metalline impurity and advantages of simplified process, low power consumption and environmetal friendliness.
In order to obtain highly actived zinc oxide, experiments of factors influencing particle size of activated zinc oxide are studied systematically. The optimum processes are as follow:the distilling ammonia time is 2.Oh, temperature is 120℃, aging time is l0min and the calcination time is 0.5h。And the calcination temperature is 350℃based on the DTG-TA analysis of zinc subcarbonate. Results show that properties of the product well agree to the Industry Standard of Chemical Engineering HG/T 2572-2006.
引文
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[9]李国民.高硅氧化锌矿浸出脱硅工艺的研究.中国有色冶金,2005,(4)：32-35
[10]Qin W Q, Li W Z, Lan Z Y, et al. Simulated small-scale pilot plant heap leaching of low-grade oxide zinc ore with integrated selective extraction of zinc. Minerals Engineering,2007,20(7):694-700
[11]蓝卓越,胡岳华,黎维中.低品位氧化锌矿硫酸浸出工艺研究.矿冶工程,2002,22(3)：63-65
[12]Langova S, Lesko J, Matysek D. Selective leaching of zinc from zinc ferrite with hydrochloric acid. Hydrometallurgy,2009,95:179-182
[13]Souza A D, Pina P S, Leao V A, et al. The leaching kinetics of a zinc sulphide concentrate in acid ferric sulphate. Hydrometallurgy,2007,89:72-81
[14]Kazinczy B, Kotai L, Gacs I, et al. Study on ammoniacal leaching of zinc from sludges containing iron and zinc hydroxides. Hungarian Journal of Industrial Chemistry,2000,28(3):207-210
[15]Harvey T G. The hydrometallurgical extraction of zinc by ammonium carbonate: A review of the Schnabel Process. Mineral Processing and Extractive Metallurgy Review,2006,27(4):231-279
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[17]张保平,唐谟堂.氨浸法在湿法炼锌中的优点及展望.江西有色金属,2001,15(4)：27-28
[18]刘晓丹,张元福.铵盐浸出氧化锌矿动力学的研究.贵州工业大学学报(自然科学版),2004,33(2)：82-85
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