分类号：密级：公开
学号：******* 单位代码：10407
硕士学位论文论文题目: 氨性体系加压浸出氧化铜钴矿的工艺研究 研究方向湿法冶金
专业名称有金属冶金
研究生姓名黄涛
导师姓名、职称刘建华副教授
周亦舟事件二零一二年五月二十八日
终身制
江西·赣州
摘要
钴是重要的战略金属，被广泛应用于航空、电器、化学工业等方面，同时也是超级合金和合金钢的重要添加剂。伴随着世界工业化、城镇化的步伐加快，能源日显紧缺，电池的用途愈来愈广，而钴是电池中的重要金属，预计钴资源的开发和利用在未来的一段时间内将出现新的高潮。我国钴资源短缺，原料基本依靠进口。本课题来源于国内某钴冶炼厂，其原料是刚果进口的氧化铜钴矿，原矿铜钴品位较低，运输成本高，如在原矿产地采用氨性加压浸出，氨浸液直接经蒸氨得到钴铜混合料，蒸氨冷凝液与残液返回浸矿，钴铜混合料运输回国，可大大降低运输成本。钴铜混合料运回国内后，采用传统的酸溶、萃取分离钴铜与少量杂质金属离子，生产钴盐工艺，可节约大量的酸碱用量及劳动力，减少废渣和废水的排放，达到更清洁化生产的目的。 现有钴冶炼工艺主要是采用酸法浸出，本课题提出了氨法加压浸出氧化铜钴矿的新方法。在氨性体系中，浸出具有选择性，钴、铜、镍、锌等有价金属以氨配离子形式进入浸出液，而钙、镁、铁等金属几乎不进入浸出液。
本课题在研究NH3-(NH4)2SO4-H2O体系的加压浸出实验过程中，考察了总氨浓度、氨铵比、还原剂用量、温度、液固比、时间及矿样粒度对Cu、Co浸出率的影响。同时通过合理的设计实验工艺流程，达到了降低还原剂用量的目的，确定了浸出的最佳条件为：两段浸出、矿样粒度95%≤300目、高 压浸出温度100℃、液固比为6、氨铵比为2:1、总氨浓度为7mol·L-1的条件下，一段浸出和二段浸出还原剂用量分别为所取矿中钴总量0.5倍和1倍（摩尔比）。试验证明铜钴浸出率均可达到95%以上。
蒸氨过程中考察了蒸馏量与沉钴的关系。实验证明，当蒸馏量达30%时，蒸馏残液中钴浓度仅为0.0071g·L-1，蒸馏沉渣中钴为34.49%、铜为18.39%，与原矿相比钴、铜含量提高了约5～10倍。蒸氨冷凝液与残液调液后返回浸矿，实验证明调液后返回浸矿与原液浸矿效果相同，铜钴浸出率仍可达到95%以上。
在国内如采用氨性加压浸出氧化铜钴矿工艺，考虑到直接蒸馏产品为钴铜混合料，后续工艺流程仍然较长，酸耗大，成本高。故本课题还初步探索了氨浸液用(NH4)3PO4沉淀法除Ca、Mg、Fe，除杂后液用P204除杂P507萃钴或除杂后液用D001树脂离子交换法分离铜钴，得到精制钴产品。实验证明，氨浸除杂后液用P204除杂P507萃钴效果不好。除杂后液用D001树脂离子交换法可以达到铜钴分离的目的，各金属离子与D001交换能力强弱顺序为：Cu>Ni>Mn >Zn>Fe>Mg >Co。
关键词：氧化铜钴矿，氨浸，蒸氨，离子交换，萃取
Abstract
Cobalt is not only an important strategic metals, which is widely applied in aviation, electrical applian
ces, chemical industry, battery, etc, but also an important additive of superalloy and alloy steel. With the acceleration development of industrialization and urbanization in the world, resource of energy is becoming increasingly reduced and the application of the battery is widely. However, cobalt is a vital metal consist of battery. The exploitation and utilization of cobalt resource is predictly reach a new climax in the next period of time. Since the shortage of cobalt resources in our country, raw materials are basically relied on imports. This subject comes from a domestic cobalt smelter, the raw material is oxidized copper and cobalt ores which is import from Congo. The oxidized copper and cobalt ores is low copper and cobalt grade with high transportation costs, If in the crude ore origin of ammonia high leaching, ammonium leaching solution directly through the ammonia evaporation get cobalt copper mixture, ammonia evaporation condensate and residual liquid return to dip ore, cobalt copper mixture transportation to return China, greatly reduces the transportation cost, cobalt and copper mixture shipped back to home after, the use of the traditional acid soluble, extraction, copper and cobalt to separation and other impurities separation, production of cobalt salt process, can save much acid and alkali amount and labor, reduce the waste residue and wastewater discharge, to achieve the purpose of more clean production.
Existing cobalt smelting process is mainly the acid leaching method, this topic put forward the metho
d of ammonia high pressure leaching oxidized copper and cobalt ores new method, in ammonia sex system, leaching selective, cobalt, copper, nickel, zinc and other valuable metals with ion form in ammonia into leaching solution, but calcium, magnesium, iron and other metal almost not enter the leaching solution.
This topic research NH3-(NH4)2SO4-H2O system in high pressure of leaching process. Through a lot of experiments, examine the total ammonia concentration, ammonia, the liquid-solid ratio than ammonium, reductant dosage, time, temperature and ore sample size to copper and cobalt leaching rate influence. Also through expanding the experiment, the more reasonable design experimental process, reduce the dosage of the reducing agent. Determined the best comprehensive leaching process conditions: leaching process using two paragraphs leaching, Ore sample size 95% ≤300 mesh, in high pressure kettle inside, temperature of 100 ℃, liquid-solid
ratio for six, ammonia and ammonium salt than 2:1, total ammonia concentration for 7 mol•L-1 conditions, a leaching and two sections of leaching reductant dosage from ore in respectively three price cobalt content 0.5 times and 1 times. Copper and cobalt leaching rate were above 95%.
In ammonia evaporation process, Investigation the distillation quantity and cobalt sink relationship. E
xperiments show, when distillation quantity of 30%, Distillation residual liquid cobalt concentration in just 0.0071 g•L-1, Distillation of sediment cobalt content for 34.49%, copper for 18.39%, Compared with the cobalt ore, copper and content increases about 5 ~ 10 times. Ammonia evaporation condensate and residual liquid return to dip ore, the test shows returned after mines with liquid leaching ones, dip the result is same mine, copper and cobalt leaching rate still can achieve 96% above.
Considering direct distillation products are cobalt copper mixtures, if we use the technique of Ammonia pressure of leaching copper oxide cobalt ore in domestic, the follow-up process is still time-consuming, high acid consumption, high cost. So this project simply explore the soaking liquid ammonia use (NH4)3PO4precipitation in addition to Ca, Mg, Fe, and use the P204 impurity P507 gathers cobalt from the after removing impurity liquid ,or detach copper from cobalt in after removing impurity liquid by means of D001 resin ion exchange method and to get refined cobalt products, the former performance reception is poor through the experiment, using the ion -exchange resin method in after removing impurity liquid of D001 can achieve the purpose of the separation of copper and cobalt. The strength order of the exchange capacity Metal ions and D001is as follows: Cu>Ni>Mn >Zn>Fe>Mg >Co.
Key words: Oxidized copper and cobalt ores, Ammonium leaching,
Ammonia evaporation, Ion exchange, Extraction
目录
摘要................................................................................................................................ I Abstract ......................................................................................................................... II 第一章文献综述. (1)
1.1 概述 (1)
1.1.1 钴矿物 (1)
1.1.2 钴的用途 (2)
metis1.2 钴的重要化合物 (2)
1.2.1 钴的氧化物 (2)
1.2.2 钴的氢氧化物 (3)
1.2.3 钴的盐类 (3)
1.2.4 钴氨络合物 (5)
1.3 钴的生产方法 (5)
1.3.1 钴生产方法概述 (5)
1.3.2 钴硫精矿提钴工艺 (6)
1.3.3 砷钴矿提钴工艺 (8)
1.3.4 以水淬富钴琉为原料生产氧化钴工艺 (9)氧化锌油
1.3.5 以镍精炼钴渣为原料可溶阳极电解法生产电钴工艺 (10)
1.3.6 以镍系统钴渣为原料溶剂萃取除杂生产电钴工艺 (11)
1.3.7 以含钴合金废料为原料提钴 (11)
1.4 我国钴湿法冶金的发展 (12)
1.4.1 我国钴湿法冶金发展概况 (12)
1.4.2 我国钴湿法冶金的发展方向 (13)
丙烯酸乙酯1.5 本课题研究的背景、意义及内容 (14)
1.5.1 本课题研究的背景和意义 (14)
1.5.2 本课题研究内容 (15)
第二章实验原料、设备与方法 (17)
2.1 实验原料及试剂 (17)
2.1.1 钴铜矿原料 (17)
2.1.2 实验试剂 (17)内蒙古乾坤金银精炼股份有限公司
2.2 实验设备 (18)
2.3 实验方法 (18)
2.3.1 浸出实验 (18)
2.3.2 蒸氨及净化等实验 (18)
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