有色冶炼行业低价值物料的高值化利用研究

发布时间：2018-03-27 11:55

  本文选题：烟道灰　切入点：次氧化锌　出处：《山东大学》2015年硕士论文

【摘要】：我国有色冶炼行业每年产生大量固体废弃物,如：炉底废渣、烟道灰等,这些废弃物对环境造成了一系列恶劣影响,对其进行高效、清洁治理已刻不容缓。同时,现有传统工艺资源利用率较低,副产很多低价值中间产品,亟需高值化利用。针对目前有色行业固废及低端产品积压严重的现状,本文以有色冶炼行业较常见的两种低价值物料：烟道灰和次氧化锌为代表,开展了全湿法处理有色行业低价值物料的新工艺研究,以实现物料有价金属的绿色、低成本、高值化利用。主要研究内容及成果如下：(1)成功设计了湿法处理烟道灰的工艺流程为：水洗-磁选-酸浸-后续分离。发现：不溶性砷酸盐是所测烟道灰物料中锌和砷的主要存在形式,水溶性锌、砷主要以硫酸锌和三氧化二砷的形式被水洗浸出。磁选后,磁性物质的铁品位达到36.8%,主要成分为Fe和Fe3O4。通过对比单一硫酸、盐酸及混合硫酸硝酸、混合盐酸硝酸四种酸浸体系,发现硫酸-硝酸混酸体系为最优,在优化工艺条件为：硝酸用量8 mL/100 g,反应温度80℃,反应时间2h时,其Cu、Zn、As、Bi的浸出率分别为92.14%、92.34%、90.00%,10.01%,而Pb没有浸出。(2)深入研究了水洗液锌砷分离过程,在单一硫酸铁和氧化钙除砷工艺的基础上,原创性地提出了硫酸铁-氧化钙-氨水三步锌砷选择性分离新工艺。在优化工艺条件下,As的脱除率大于98.9%,而Zn的损失小于10%。进一步的机理研究发现：体系pH值在2-3之间变化时,As的脱出率无明显改变；而Zn的脱除率变化较大,其原因不仅与溶度积常数有关,Fe3+、Ca2+的竞争吸附也产生了一定影响。(3)确定了次氧化锌制备纳米氧化锌的工艺流程为：酸浸-除杂-前驱体制备-煅烧。考察了一步法及两步法酸浸工艺过程对硫酸锌溶液的影响；优化了ZnO-硫酸铜/锌粉-锌粉除杂顺序,得到了合格的硫酸锌溶液。(4)通过对比碳酸氢铵、碳酸钠、氨水三种沉淀体系,原创性地提出了超声-阳离子表面活性剂耦合沉淀新工艺,获得了六方晶系结构的优级品纳米氧化锌样品,其BET数值达到46.99 m2/g。
[Abstract]:A large number of solid wastes are produced every year in China's nonferrous smelting industry, such as furnace bottom slag, flue ash and so on. These wastes have caused a series of adverse effects on the environment, so it is urgent to carry out high efficiency and clean treatment. At the same time, The utilization ratio of traditional technology resources is low, and the by-products are many low-value intermediate products, which are in urgent need of high-value utilization. In view of the serious backlog of solid waste and low-end products in the colored industry at present, In this paper, two kinds of low value materials: flue ash and zinc oxide, which are more common in nonferrous smelting industry, are taken as the representative, and the new process of treating low value materials in non-ferrous industry by full wet process is carried out in order to realize the green and low cost of the valuable metals of the materials. The main contents and results of this study are as follows: 1) the process of wet flue ash treatment is as follows: water washing, magnetic separation, acid leaching and subsequent separation. It is found that the insoluble arsenate is the zinc in the flue ash. And the main forms of arsenic, Water soluble zinc and arsenic are washed out by water in the form of zinc sulfate and arsenic trioxide. After magnetic separation, the iron grade of magnetic material reaches 36.8, the main components are Fe and Fe _ 3O _ 4. By comparing the single sulfuric acid, hydrochloric acid and mixed nitric acid, Four kinds of acid leaching systems of mixed hydrochloric acid and nitric acid were found to be the best. The optimum technological conditions were as follows: the amount of nitric acid 8 mL/100 g, reaction temperature 80 鈩，

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