Pavlović Jelena, Stopić Srećko, Friedrich Bernd, Kamberović Zeljko
University of Belgrade, Faculty of Technology and Metallurgy, Department of Metallurgical Engineering, Karnegijeva 4, 11120 Belgrade, Serbia and Montenegro.
Environ Sci Pollut Res Int. 2007 Nov;14(7):518-22. doi: 10.1065/espr2006.09.345.
GOAL, SCOPE AND BACKGROUND: This paper is a part of the research work on 'Integrated treatment of industrial wastes towards prevention of regional water resources contamination - INTREAT' the project. It addresses the environmental pollution problems associated with solid and liquid waste/effluents produced by sulfide ore mining and metallurgical activities in the Copper Mining and Smelting Complex Bor (RTB-BOR), Serbia. However, since the minimum solubility for the different metals usually found in the polluted water occurs at different pH values and the hydroxide precipitates are amphoteric in nature, selective removal of mixed metals could be achieved as the multiple stage precipitation. For this reason, acid mine water had to be treated in multiple stages in a continuous precipitation system-cascade line reactor.
All experiments were performed using synthetic metal-bearing effluent with chemical a composition similar to the effluent from open pit, Copper Mining and Smelting Complex Bor (RTB-BOR). That effluent is characterized by low pH (1.78) due to the content of sulfuric acid and heavy metals, such as Cu, Fe, Ni, Mn, Zn with concentrations of 76.680, 26.130, 0.113, 11.490, 1.020 mg/dm3, respectively. The cascade line reactor is equipped with the following components: for feeding of effluents, for injection of the precipitation agent, for pH measurements and control, and for removal of the process gases. The precipitation agent was 1M NaOH. In each of the three reactors, a changing of pH and temperature was observed. In order to verify. efficiency of heavy metals removal, chemical analyses of samples taken at different pH was done using AES-ICP.
Consumption of NaOH in reactors was 370 cm3, 40 cm3 and 80 cm3, respectively. Total time of the experiment was 4 h including feeding of the first reactor. The time necessary to achieve the defined pH value was 25 min for the first reactor and 13 min for both second and third reactors. Taking into account the complete process in the cascade line reactor, the difference between maximum and minimum temperature was as low as 6 degrees C. The quantity of solid residue in reactors respectively was 0.62 g, 2.05 g and 3.91 g. In the case of copper, minimum achieved concentration was 0.62 mg/dm3 at pH = 10.4. At pH = 4.50 content of iron has rapidly decreased to < 0.1 mg/dm3 and maintained constant at all higher pH values. That means that precipitation has already ended at pH=4.5 and maximum efficiency of iron removal was 99.53%. The concentration of manganese was minimum at pH value of 11.0. Minimum obtained concentration of Zn was 2.18 mg/dm3 at a pH value of 11. If pH value is higher than 11, Zn can be re-dissolved. The maximum efficiency of Ni removal reached 76.30% at a pH value of 10.4.
Obtained results show that efficiency of copper, iron and manganese removal is very satisfactory (higher than 90%). The obtained efficiency of Zn and Ni removal is lower (72.30% and 76.31%, respectively). The treated effluent met discharge water standard according to The Council Directive 76/464/EEC on pollution caused by certain dangerous substances into the aquatic environment of the Community. Maximum changing of temperature during the whole process was 6 degrees C.
This technology, which was based on inducing chemical precipitation of heavy metals is viable for selective removal of heavy metals from metal-bearing effluents in three reactor systems in a cascade line.
The worldwide increasing concern for the environment and guidelines regarding effluent discharge make their treatment necessary for safe discharge in water receivers. In the case where the effluents contain valuable metals, there is also an additional economic interest to recover these metals and to recycle them as secondary raw materials in different production routes.
目标、范围和背景:本文是“工业废物综合处理以防止区域水资源污染——INTREAT”项目研究工作的一部分。它探讨了塞尔维亚博尔铜矿和冶炼厂(RTB - BOR)硫化矿开采和冶金活动产生的固体和液体废物/废水所带来的环境污染问题。然而,由于通常在受污染水中发现的不同金属的最低溶解度出现在不同的pH值,且氢氧化物沉淀本质上是两性的,因此可以通过多阶段沉淀实现混合金属的选择性去除。出于这个原因,酸性矿山废水必须在连续沉淀系统——级联线反应器中进行多阶段处理。
所有实验均使用化学成分与博尔铜矿和冶炼厂(RTB - BOR)露天矿废水相似的合成含金属废水进行。由于含有硫酸和重金属,如铜、铁、镍、锰、锌,其浓度分别为76.680、26.130、0.113、11.490、1.020mg/dm³,该废水的特点是pH值较低(1.78)。级联线反应器配备了以下组件:用于废水进料、用于注入沉淀剂、用于pH测量和控制以及用于去除工艺气体。沉淀剂为1M氢氧化钠。在三个反应器中的每一个中,均观察到pH值和温度的变化。为了验证重金属去除效率,使用AES - ICP对在不同pH值下采集的样品进行化学分析。
反应器中氢氧化钠的消耗量分别为370cm³、40cm³和80cm³。实验总时间为4小时,包括向第一个反应器进料的时间。第一个反应器达到规定pH值所需时间为25分钟,第二个和第三个反应器均为13分钟。考虑到级联线反应器中的整个过程,最高温度与最低温度之差低至6摄氏度。反应器中固体残渣的量分别为0.62g、2.05g和3.91g。对于铜,在pH = 10.4时达到的最低浓度为0.62mg/dm³。在pH = 4.50时,铁的含量迅速降至<0.1mg/dm³,并在所有更高的pH值下保持恒定。这意味着在pH = 4.5时沉淀已经结束,铁的最大去除效率为99.53%。锰的浓度在pH值为11.0时最低。锌在pH值为11时获得的最低浓度为2.18mg/dm³。如果pH值高于11,锌会重新溶解。镍在pH值为10.4时的最大去除效率达到76.30%。
所得结果表明,铜、铁和锰的去除效率非常令人满意(高于90%)。锌和镍的去除效率较低(分别为72.30%和76.31%)。处理后的废水符合欧盟理事会关于某些危险物质对共同体水生环境造成污染的第76/464/EEC号指令规定的排放水标准。整个过程中温度的最大变化为6摄氏度。
这种基于诱导重金属化学沉淀的技术对于在级联线中的三个反应器系统中从含金属废水中选择性去除重金属是可行的。
全球对环境的日益关注以及关于废水排放的指导方针使得对其进行处理以安全排放到受纳水体中成为必要。如果废水中含有有价值的金属,回收这些金属并将其作为二次原料在不同生产路线中循环利用还具有额外的经济利益。