高砷烟尘酸性氧化浸出砷和锌的试验研究

采用酸性氧化浸出工艺对某冶炼厂高砷烟尘进行湿法浸出砷、锌的试验研究。通过单因素试验确定最佳浸出工艺条件。结果表明,采用pH值为2的稀硫酸溶液,在浸出温度80℃、浸出时间105min、液固体积质量比10∶1、H2O2添加量1.75mL/g(烟灰)、搅拌速度705r/min的条件下,砷、锌浸出率分别达到78.25%和85.42%。     

A novel hydrothermal method for zinc extraction and separation from zinc ferrite and electric arc furnace dust

A novel hydrothermal process was developed to extract zinc from pure zinc ferrite (ZnFe₂O₄) nanopowder and zinc-containing electric arc furnace (EAF) dust using hexahydrated ferric chloride (FeCl₃·6H₂O) as a decomposing agent. The effects of solid FeCl₃·6H₂O to ZnFe₂O₄ ratio by mass (R_F/Z), hydrothermal reaction temperature, and time on zinc extraction were systematically investigated. In the results, when the hydrothermal reaction is conducted at 150℃ for 2 h with R_F/Z of 15:20, the efficiency of zinc extraction from ZnFe₂O₄ reaches 97.2%, and the concentration of ferric ions (Fe3+) in the leaching solution is nearly zero, indicating a high selectivity for zinc. In addition, the zinc extraction efficiency from the EAF dust reaches 94.5% in the case of the hydrothermal reaction performed at 200℃ for 10 h with the solid FeCl₃·6H₂O to EAF dust ratio by mass (R_{F/EAF dust}) of 15:10. Zinc and iron separation is achieved by adjusting the pH value of the leaching solution according to the different precipitation pH values of metal hydroxides.     

New pyrometallurgical process of EAF dust treatment with CaO addition

The non-carbothermic zinc pyrometallurgical processing of electric arc furnace (EAF) dust was investigated on a laboratory scale. The main objective of this process was to convert highly stable zinc ferrite (ZnFe₂O₄), which accounts for more than half of total zinc in the EAF dust, into ZnO and Ca₂Fe₂O₅ by CaO addition. The EAF dust was mixed with CaO powder in various ratios, pressed into pellets, and heated in a muffle furnace in air at temperatures ranging from 700 to 1100℃ for a predetermined holding time. All ZnFe₂O₄ was transformed into ZnO and Ca₂Fe₂O₅ at a minimum temperature of 900℃ within 1 h when sufficient CaO to achieve a Ca/Fe molar ratio of 1.1 was added. However, at higher temperatures, excess CaO beyond the stoichiometric ratio was required because it was consumed by reactions leading to the formation of compounds other than ZnFe₂O₄. The evaporation of halides and heavy metals in the EAF dust was also studied. These components could be preferentially volatilized into the gas phase at 1100℃ when CaO was added.     

Sulfuric acid leaching of high iron-bearing zinc calcine

Sulfuric acid leaching of high iron-bearing zinc calcine was investigated to assess the effects of sulfuric acid concentration, liquid-to-solid ratio, leaching time, leaching temperature, and the stirring speed on the leaching rates of zinc and iron. The results showed that the sulfuric acid concentration, liquid-to-solid ratio, leaching time, and leaching temperature strongly influenced the leaching of zinc and iron, whereas stirring speed had little influence. Zinc was mainly leached and the leaching rate of iron was low when the sulfuric acid concentration was less than 100 g/L. At sulfuric acid concentrations higher than 100 g/L, the leaching rate of iron increased quickly with increasing sulfuric acid concentration. This behavior is attributed to iron-bearing minerals such as zinc ferrite in zinc calcine dissolving at high temperatures and high sulfuric acid concentrations but not at low temperatures and low sulfuric acid concentrations.     

氨法处理高炉瓦斯灰制取等级氧化锌研究

以氨-碳酸氢铵混合液为浸出剂浸出高炉瓦斯灰中的有价金属锌,经净化、蒸氨、煅烧得到等级氧化锌,对相关工艺参数进行优化选择。结果表明,最佳浸出条件为:[氨水]/[NH4HCO3]=2、液固比为4、总氨浓度为5mol·L-1,浸出时间为3h,此条件下锌浸出率为82.55%;最佳净化条件为:锌粉用量为1.5g·L-1、净化时间为2.5h,此条件下铅的脱除率为97.70%;最佳蒸氨条件为90℃下蒸氨至终点溶液pH值为6~7,此条件下蒸氨后锌的沉淀率可达99.95%。沉淀物在500℃下煅烧1h,得到纯度为96.03%的氧化锌粉末,达到了HG/T2527—94的一级标准。     

从高炉除尘灰中综合回收碳、铁和锌的试验研究

基于选冶联合工艺,对某厂排放的高炉除尘灰进行综合回收铁、锌、碳的试验研究。先采用浮选-磁选法回收碳和铁,再采用酸浸-除杂-电积湿法回收锌,重点对影响锌浸出的工艺因素和条件进行了考察。结果表明,通过选冶联合工艺处理高炉除尘灰获得较好的选别指标,且可回收碳品位为86.52%和回收率为92.80%的碳精矿、铁品位为54.16%和回收率为45.47%的铁精矿以及纯度为95.2%的锌产品,锌总回收率达到87%以上。     

Deep cleaning of a metallurgical zinc leaching residue and recovery of valuable metals

Huge quantities of zinc leaching residues (ZLRs) generated from zinc production are dumped continuously around the world and pose a potential environmental threat because of their considerable amounts of entrained heavy metals (mainly lead). Most ZLRs have not been properly treated and the valuable metals in them have not yet been effectively recovered. Herein, the deep cleaning of a ZLR and recovery of valuable metals via a hydrometallurgical route were investigated. The cleaning process consists of two essential stages:acid leaching followed by calcium chloride leaching. The optimum conditions for extracting zinc, copper, and indium by acid leaching were a sulfuric acid concentration of 200 g·L-1, a liquid/solid ratio of 4:1 (mL/g), a leaching time of 2 h, and a temperature of 90℃. For lead and silver extractions, the optimum conditions were a calcium chloride concentration of 400 g·L-1, a pH value of 1.0, a leaching time of 1 h, and a temperature of 30℃. After calcium chloride leaching, silver and lead were extracted out and the lead was finally recovered as electrolytic lead by electrowinning. The anglesite phase, which poses the greatest potential environmental hazard, was removed from the ZLR after deep cleaning, thus reducing the cost of environmental management of ZLRs. The treatment of chlorine and spent electrolyte generated in the process was discussed.     

FeCl2处理电炉炉尘的热力学计算

电炉炉尘中富含Zn、Pb、Cd等元素，简单地将这些炉尘倾倒野外或填埋，Pb、Cd等重金属元素的浸出会污染环境，而直接将炉尘返回钢铁厂内循环使用，Zn在高炉内富集会缩短炉衬寿命，而又这些元素向钢水的转移还会降低钢材品质。为减少电炉炉尘对环境的污染和实现其综合利用，必须寻求经济高效的新方法脱除炉尘中Zn、Pb、Cd等有害元素。通过热力学计算分析了采用FeCl2去除电炉炉尘中Zn、Pb的可能性，比较了不同反应条件下的作用效果。计算结果表明，在600-900℃下，炉尘中ZnO、ZnFe2O4、CuO、PbO和CdO几乎全部转化为气相氯化物。对于CaO含量较高的炉尘，添加SiO2有利于提高炉尘中有害元素的脱除效率，Zn的脱除率约96％-98％。当反应温度超过950℃，炉尘中Zn的脱除率有降低的趋势。     

锗烟尘浸出过程热力学分析

贵州、云南锗烟尘主要含锌、铅、锗、银等有价金属。对锗烟尘酸性浸出过程进行了热力学分析，讨论了锗烟尘中主要物质在浸出过程的行为。     

含碳球团还原法处理含锌电炉粉尘的试验分析

为综合利用含锌电炉粉尘,提出运用含碳球团的还原处理方法,并进行了扩大性试验,得到了还原焙烧法的合理工艺条件.试验表明:配碳的碳氧比C/O=1.2、还原温度1 150 ℃、料层厚度30 mm、加热时间65 min可取得较好的效果;还原后的球团为半金属化球团,其w(TFe)为50%左右,金属化率60%～70%,球团的残Zn含量在2%以下,是较好的高炉原料;Zn的还原挥发率达到90%左右,收集粉中ZnO含量在90%左右;PbO含量在2%以下,已达到等级氧化锌的标准,实现了含锌电炉粉尘的无害化和资源化利用.     

铜冶炼闪速炉烟尘氧化浸出与中和脱砷

介绍了废酸氧化浸出铜冶炼闪速炉烟尘和漫出液中和沉淀砷、铁过程。从化学热力学和实验2方面研究了浸出液中以砷酸铁形式中和沉淀脱砷过程，并对砷酸铁沉淀的稳定性进行了研究。研究结果表明：闪速炉烟尘中铜、砷和铁的浸出率分别可达到83％，92％和30％，浸出液中的铁和砷的量比n（Fe）／n（As）约为1．50；控制适当的pH值中和沉淀砷、铁，可使铜存留于溶液中，而砷以砷酸铁形式进入固相中，从而达到铜、砷分离的目的；不稳定的砷酸铁沉淀物进一步转型后，则可作为无毒稳定渣丢弃。     

Preparation of manganese sulfate from low-grade manganese carbonate ores by sulfuric acid leaching

In this study, a method for preparing pure manganese sulfate from low-grade ores with a granule mean size of 0.47 mm by direct acid leaching was developed. The effects of the types of leaching agents, sulfuric acid concentration, reaction temperature, and agitation rate on the leaching efficiency of manganese were investigated. We observed that sulfuric acid used as a leaching agent provides a similar leaching efficiency of manganese and superior selectivity against calcium compared to hydrochloric acid. The optimal leaching conditions in sulfuric acid media were determined; under the optimal conditions, the leaching efficiencies of Mn and Ca were 92.42% and 9.61%, respectively. Moreover, the kinetics of manganese leaching indicated that the leaching follows the diffusion-controlled model with an apparent activation energy of 12.28 kJ·mol-1. The purification conditions of the leaching solution were also discussed. The results show that manganese dioxide is a suitable oxidant of ferrous ions and sodium dimethyldithiocarbamate is an effective precipitant of heavy metals. Finally, through chemical analysis and X-ray diffraction analysis, the obtained product was determined to contain 98% of MnSO₄·H₂O.     

用草酸在硫酸溶液中从中性浸出渣中还原浸出铟

The present study evaluates the reductive leaching of indium from indium-bearing zinc ferrite using oxalic acid as a reducer in sulfuric acid solution. The effect of main factors affecting the process rate, including the oxalic-acid-to-sulfuric-acid ratio, stirring rate, grain size, temperature, and the initial concentration of synergic acid, was precisely evaluated. The results confirmed the acceptable efficiency of dissolving indium in the presence of oxalic acid. The shrinking-core model with a chemical-reaction-controlled step can correctly describe the kinetics of indium dissolution. On the basis of an apparent activation energy of 44.55 kJ/mol and a reaction order with respect to the acid concentration of 1.14, the presence of oxalic acid was found to reduce the sensitivity to temperature changes and to increase the effect of changes in acid concentration. Finally, the equation of the kinetic model based on the factors under study is presented.     

Zn(Ⅱ)-(NH4)2SO4-H2O体系浸出锌烟尘

提出硫酸铵浸出法处理锌烟尘的新工艺。该工艺利用不同温度下锌在硫酸铵溶液中的溶解度的差别,先在高温下将锌浸入溶液然后降温冷却,使锌呈含F和Cl很低的复盐析出,然后回收。以株冶集团锌烟尘为试料,对浸出过程进行研究。研究结果表明:浸出温度和硫酸铵浓度显著影响锌的浸出率;最佳浸出条件是:液固比为16?1,硫酸铵浓度为4.0 mol/L,pH值为5.5,浸出温度为90℃,浸出时间为4 h,在该条件下,按渣含锌计算的浸出率达到85.16%。     

Study on mechanisms of different sulfuric acid leaching technologies of chromite

The extraction of chromate from chromite via the sulfuric acid leaching process has strong potential for practical use because it is a simple and environmentally friendly process. This paper aims to study the sulfuric acid leaching process using chromite as a raw material via either microwave irradiation or in the presence of an oxidizing agent. The results show that the main phases in Pakistan chromite are ferrichromspinel, chrompicotite, hortonolite, and silicate embedded around the spinel phases. Compared with the process with an oxidizing agent, the process involving microwaves has a higher leaching efficiency. When the mass fraction of sulfuric acid was 80% and the leaching time was 20 min, the efficiency could exceed 85%. In addition, the mechanisms of these two technologies fundamentally differ. When the leaching was processed in the presence of an oxidizing agent, the silicate was leached first and then expanded. By contrast, in the case of leaching under microwave irradiation, the chromite was dissolved layer by layer and numerous cracks appeared at the particle surface because of thermal shock. In addition, the silicate phase shrunk instead of expanding.     

硫氧混合铅锌矿中锌的氧化氨浸动力学

常压低温条件下在NH3-(NH4)2 SO4体系中使用过硫酸铵作为氧化剂对硫氧混合铅锌矿中的锌进行浸出实验,系统研究了搅拌速度、浸出剂浓度、氧化剂浓度与温度对于锌浸出率的影响.结果表明,在最优条件下锌的浸出率可达93.2%,且浸出过程中几乎没有其他离子进入溶液,实现了锌的选择性高效浸出,从而简化了后续的浸出液净化与材料制备过程.动力学研究表明,硫氧混合铅锌矿中锌的氧化氨浸过程遵循固体产物层扩散控制的未反应核收缩模型,浸出反应的表观活化能为17.89 kJ·mol-1.     

基于烟气成分分析的电弧炉炼钢脱碳模型

为了连续地预测电弧炉熔池中碳含量,实现对冶炼终点碳含量的控制,以红外烟气分析技术和物质质量守恒计算为基础,结合入炉总碳量和供氧量等生产数据,建立了电弧炉炼钢脱碳数学模型.对莱芜钢铁股份有限公司特殊钢厂50tUHP电弧炉实际冶炼数据的模拟计算表明,该模型能实现对熔池碳含量的连续预测和终点控制.模拟计算结果还表明,电弧炉冶炼过程中,脱碳速度主要受供氧流量的影响,最大可达0.12%～0.16%min-1.该模型用于电弧炉供氧优化后,氧气消耗明显降低.     

高炉粉尘Fe和Zn非熔态分离工艺

开发一种高炉粉尘再资源化处理工艺,采用"非熔态还原--磁选分离--Zn的回收、富集"方法对典型高炉粉尘进行Fe、Zn非熔态分离研究.结果表明:在910～1 010℃,使用纯H2、CO为还原剂进行非熔态还原,同时实现粉尘中Fe2O3(s)→Fe(s)和ZnO(s)→Zn(g)的高度转变,金属化率达到90%以上,气化脱锌率达到99%以上,且还原过程未发生烧结.还原产物直接经磁选分离、富集得到TFe品位90%的富Fe物料;含锌挥发物经回收、富集得到ZnO含量92%的富Zn物料.成功地将高炉粉尘全部转化为MFe、ZnO等有价资源,实现了零排放,且分离过程不需高温熔融,过程能耗低,无环境污染.     

采用焙烧-水浸法从报废锂离子动力电池中回收金属

锂离子动力电池在新能源汽车中已获得广泛应用,其报废后Li、Ni、Co、Mn等金属清洁高效回收对促进有色金属循环利用具有重要意义.从LiNi_0.5Co_0.2Mn_0.3O₂为正极材料的锂离子动力电池中回收Li、Ni、Co、Mn,并采用TG-DSC、XRD、ICP-OES、XPS、热力学分析等研究了回收过程物相演变规律及影响金属回收率的主要因素.结果表明:由LiNi_0.5Co_0.2Mn_0.3O₂与NaHSO₄·H₂O组成的混合物,经过焙烧后Li、Ni、Co、Mn元素的赋存状态发生改变,从不溶于水的复杂金属氧化物形式,转化为可溶于水的金属硫酸盐形式.焙烧产物在一定条件下用水浸出后,Li、Ni、Co、Mn元素以金属离子的形式转移到水溶液中获得回收.混合物的组成、焙烧温度对Li、Ni、Co、Mn元素在焙烧产物中的赋存形式呈现制约关系,也是影响Li、Ni、Co、Mn金属回收率的主要因素.     

低共熔溶剂浸出高炉瓦斯泥-电沉积锌的研究

本文采用氯化胆碱-尿素低共熔溶剂体系浸出高炉瓦斯泥,再直接电沉积得到锌.实验考察了液固比、浸出时间、搅拌速度对锌浸出率的影响.浸出实验结束后,我们分别对体系进行了循环伏安测试和电沉积实验.实验结果表明:液固比为10 mL/g,浸出时间为30 h,搅拌速度为300 r/min,温度为70℃的条件下,锌的浸出率达到71%;循环伏安测试确定还原电位为-1.4 V;X射线衍射和能谱分析表明,镀层为纯度较高的金属锌;通过对镀层形貌分析发现电沉积得到了1μm左右团簇状晶粒组成的锌镀层.