铜冶炼废酸提取铼及分析方法的研究.pdf

合肥工业大学硕士学位论文铜冶炼废酸提取铼及分析方法的研究姓名：张永中申请学位级别：硕士专业：化学工程指导教师：杨则恒2011-04III铜冶炼废酸提取铼及分析方法的研究铜冶炼废酸提取铼及分析方法的研究 摘摘 要要 铼是一种稀散金属， 其理化性质与难熔金属相似， 可用于炼油催化剂、高温超耐热合金等方面铜冶炼废酸中含有微量的铼，国内外从铜冶炼废酸中回收铼的工艺主要有萃取法、离子交换法、化学沉淀法等化学沉淀法工艺简单、铼沉淀率高且环境友好本文对沉淀剂的加入量、反应时间、温度、 加入方式以及废酸中铼含量变化对铼沉淀率的影响做了大量的试验研究，优化出最佳沉淀条件并对富铼渣进行浸出试验研究，从双氧水的用量、反应时间、温度以及样品粒度等方面优化最佳浸出条件；对浸出液采用氨水中和沉铜、离子交换吸附铼制取铼酸铵进行了试验研究铼的沉淀率平均达到97.10%，沉淀后废液中含铼小于0.30 mg/L；富铼渣浸出率大于95%，浸出渣含铼小于0.45%；铼酸铵含量大于99%在试验过程中，对铜冶炼废酸、富铼渣以及铼酸铵等进行了大量的分析测试方面试验，包括实际样品的加标回收以及精密度试验等， 建立了从废酸提取铼工艺过程一系列配套的分析测试方法，对整个工艺过程起着重要指导作用。

关键词: 关键词: 铜冶炼废酸；富铼渣；回收；铼；分析测试 IVExtraction and Analysis of Rhenium from Copper Smelting Waste Acid ABSTRACT Rhenium is a rare and scattered metal, with physical and chemical properties similar to refractory metals. It can be applied for oil-refining catalyst, high temperature superalloy and so on. Copper smelting waste acid contains trace amounts of Rhenium. Conventional methods to recover Rhenium from the copper smelting waste acid include extraction, ion exchange, chemical precipitation and so on. Chemical precipitation method has advantages of simple process, high Rhenium sedimentation rate and environment friendliness。

In this paper, the effects of precipitating agent dosage, reaction time, temperature, addition method and the Rhenium content in waste acid on the precipitation rate of Rhenium were investigated and the precipitation conditions were optimized. On the other hand, leaching experiment of Rhenium from Rhenium-rich slag was studied from hydrogen peroxide dosage, reaction time, temperature and slag particle size. The leaching solution was neutralized with ammonia to precipitate copper. Then the Rhenium was adsorbed through ion exchange and used to produce Re ammonium. Experiment results show that average sedimentation rate of Re is 97.10%，with less than 0.30mg/L Rhenium left in the solution after precipitation; the leaching rate of Re from slag is more than 95%, with a Re residue of less than 0.45% and Re ammonium content is more than 99%. In the above extraction experiments, a lot of testing analyses were made on copper smelting waste acid, Rhenium-rich slag and Re ammonium, including the actual recovery of spiked samples, the precision of focus and a series of supporting test methods, which play an important role in guiding the Re recovery process. Keywords：： Copper Smelting Waste Acid; Rhenium-rich slag; Recovery; Rhenium; Analysis VIII插图清单插图清单 图 1-1 萃取提铼工艺流程图 ..................................................................4 图 2-1 硫酸与 RE、MO、SE回收率关系图 .........................................11 图 3-1 废酸沉铼工艺流程图 ..............................................................15 图 3-2 沉淀剂 M 与铼沉淀率关系图...................................................18 图 3-3 反应时间与铼沉淀率关系图 ......................................................19 图 3-4 转速与铼沉淀率关系图 .............................................................20 图 3-5 废酸含铼量与铼沉淀率关系图 ................................................21 图 4-1 富铼渣提取铼工艺流程图..........................................................25 图 4-2 双氧水的加入量与铼浸出率关系图 ............................................26 图 4-3 反应时间与铼浸出率关系图 ......................................................27 图 4-4 试样粒度与铼浸出率关系图 ......................................................28 图 4-5 温度与铼浸出率关系图 .............................................................29 图 4-6 PH 与沉铜率的关系图...............................................................31 图 4-7 流速与铼吸附率关系图 .............................................................33 IX表格清单 表格清单 表 1-1 不同底液而选择的不同电位的测定结果表.................................7 表 2-1 仪器工作条件 .........................................................................10 表 2-2 硫酸含量对测定结果的影响 ....................................................11 表 2-3 各待测元素的分析谱线 ...........................................................12 表 2-4 元素检出限.............................................................................12 表 2-5 铼、钼、硒回收率 ..................................................................13 表 2-6 精密度试验结果 .....................................................................13 表 2-7 综合样化验结果表 ..................................................................14 表 3-1 铜冶炼废酸成分表 ..................................................................15 表 3-2 试验试剂及设备 .....................................................................16 表 3-3 沉铼后液和富铼渣化学成分表 ................................................16 表 3-4 沉淀剂 M 不同加入量结果比较表............................................17 表 3-5 不同反应时间的比较表 ...........................................................18 表 3-6 不同搅拌速度下铼的沉淀情况比较表 ......................................19 表 3-7 加入方式不同沉铼比较表 .......................................................20 表 3-8 铼含量对铼沉淀率影响比较表 ................................................21 表 3-9 富铼渣精密度试验结果 ...........................................................23 表 4-1 富铼渣成分表 .........................................................................24 表 4-2 不同双氧水的加入量富铼渣浸。