造锍捕金机理及富氧熔炼过程贵金属分配行为

贵金属在高温熔锍中分配行为受熔炼体系和组元热力学性质影响,高温熔锍捕集贵金属有利于降低体系总吉布斯自由能;Au、Ag在渣中损失形式,与Cu损失类似,除少量溶解外,大部分为机械夹杂,占总渣损失的90%以上;引入分配系数和机械悬浮率对贵金属多相平衡模型进行修正,并利用修正模型计算了富氧熔炼铜锍和炉渣中贵金属含量,铜锍中Au、Ag的含量分别为13.29 g/t、825.84 g/t,炉渣中Au、Ag的含量分别为0.53 g/t、33.29g/t,与实际生产结果一致;入炉精矿成分(Cu、S)和工艺参数(铜锍品位、氧矿比)波动时,对Au、Ag在富氧熔炼过程中分配行为有影响,随着精矿中Cu含量的升高和S含量的降低以及铜锍品位和氧矿比的升高,Au、Ag在铜锍中的分配比例降低,渣中损失增加;降低铜锍机械悬浮率,有利于减少贵金属在渣中的损失、提高贵金属的回收率。     

熔渣中金属液滴沉降过程流体力学模拟（英文）

建立熔炼渣中金属液滴沉降过程的数学模型，研究不同粘性模型下金属/熔渣界面张力对液滴沉降速度以及拖曳力的影响。结果表明：对于较小直径的液滴，Laminar模型和RNG k-ε湍流模型能够准确预测液滴最终沉降速度；界面张力对液滴沉降速度有影响，且影响作用随着液滴尺寸增大而逐渐增大；“RNG+CSS”模型可以准确描述液滴沉降过程和液滴沉降速度的变化。结合数学模型和实验数据，推导出耦合界面张力作用下拖曳力系数计算公式。该模型揭示熔炼渣中金属液滴沉降过程机理，为实际生产中降低渣中有价金属含量提供理论指导。     

铜复杂资源造锍熔炼过程中MgO对铜锍和二氧化硅饱和铁硅渣相平衡的影响（英文）

采用高温平衡实验及电子探针微区分析方法研究铜复杂资源中MgO对造锍熔炼平衡体系铜锍及熔炼渣成分(FeO_x-SiO₂-MgO)的影响。结果表明，在1300℃、p(SO₂)=10 k Pa熔炼条件下，增加熔炼渣中MgO含量可降低渣中FeO的活度，进而降低渣中氧分压(p(O₂))、减少铜在渣中化学溶解损失量；同时，渣中FeO活度降低可促进铜锍中Fe S氧化进渣，提高铜锍品位。在高硅渣型中，过量MgO易在渣中形成固相夹杂颗粒(Mg₂SiO₄-Fe₂SiO₄)，导致渣黏度升高、增加渣中铜损失。当熔炼温度由1200℃升至1300℃及p(O₂)为10^-6 k Pa时，FeO_x-SiO₂-MgO渣中MgO的最大溶解量由3%增至8%(质量分数)；渣中MgO含量增加时，可通过添加SiO₂熔剂调整渣型、升高熔炼温度，进而降低渣...     

氧气底吹铜熔炼工艺分析及过程优化

通过分析氧气底吹铜熔炼渣及铜锍,结合冶金过程原理,研究渣-铜锍间多组元含量的映射关系及熔炼过程优化。结果表明:铜锍中Cu、S、Fe含量之间呈现出较强的相关性;渣中Cu、SiO_2、Fe含量及渣型铁硅比m_(Fe)/m_(SiO_2)相互之间也呈现出一定的相关性;铜锍中Cu、Fe、S含量对渣中S含量的映射关系较为明显;基于铜锍中S、Cu含量和渣中S含量,或基于渣型铁硅比m_(Fe)/m_(SiO_2)和铜锍品位都可对渣中Cu含量进行预测,后者的准确度较高,说明铜锍品位和渣型对渣中Cu含量有较大影响。     

砷铅高杂铜锍富氧强化吹炼机理研究及工艺优化

砷铜锍(Cu₃As)、铅铜锍(Cu₂S、PbS)是粗铅精炼除铜渣熔炼副产物,属于毒性危险废物。本文提出富氧底吹强化吹炼法处理砷铜锍、铅铜锍,富集回收Cu和分离脱除Pb、As。通过热力学计算,阐明了Cu、Pb、As吹炼反应机理及元素物相演变规律,确定吹炼优化条件,并开展工业生产。结果表明：1250℃下,砷铜锍、铅铜锍富氧底吹强化吹炼经氧化、还原两阶段产出粗铜、吹炼渣及烟气。粗铜中Cu、As含量(质量分数)分别为93.94%、3.85%;原料中60.42%Cu富集至粗铜,27.43%Cu损失于吹炼渣;Pb在吹炼渣、烟气的分配率分别达到82.77%、17.22%;As在烟气和吹炼渣的分配率达89.46%。砷铜锍、铅铜锍富氧底吹强化吹炼实现了Cu向粗铜中定向富集,并将Pb、As脱除至吹炼渣和烟气,可用于含砷复杂资源高效处理。     

渣-金界面气泡夹带行为数值物理模拟EI北大核心CSCD

利用物理模拟和数值模拟研究气泡和熔渣不同物性参数对气泡在渣-金界面夹带量的影响。研究结果表明,影响气泡夹带量和渣-金界面面积的主要因素是气泡直径,其次是渣层密度,渣黏度和界面张力对气泡夹带影响相对较小。气泡初始直径由10 mm增大到16 mm,气泡夹带量增大了7.41倍,渣-金界面面积增量最大值增大3.67倍。渣层密度由2000 kg/m^(3)增大到5000 kg/m^(3),气泡夹带量增大了62.3%,渣-金界面面积最大值增大了13.1%。渣-金界面张力和黏度增大,气泡夹带量和渣-金界面面积均降低。渣-金界面张力从0.65 N/m增大到1.10 N/m,气泡夹带量减小了30.6%,渣-金界面面积最大值减小6.4%。渣层黏度由0.05 Pa·s增大到2.0 Pa·s时,气泡夹带量降低18.4%,渣-金界面面积最大值减小10.2%。     

基于数值模拟的闪速连续炼铜炉型结构研究

分析4种闪速连续炼铜炉型的本质特性,提出将闪速连续炼铜过程视为由相对独立的闪速造锍熔炼过程和连续吹炼造铜过程构成,分别建立闪速造锍熔炼多相平衡数学模型和连续吹炼造铜局域平衡数学模型,并通过中间物料的传递将两模型有机结合,从而构建完整的闪速连续炼铜过程热力学模型。运用此模型,考察炉型结构对闪速连续炼铜过程的粗铜生成条件、Fe3O4行为、铜在渣中损失以及铜直收率等因素的影响。结果表明：相对于其他3种炉型,甩渣吹炼双烟道D型炉是比较理想的连续炼铜炉体;对于闪速连续炼铜,造锍熔炼段和铜锍吹炼段宜在相对独立的分区进行,各自炉渣和烟气也应分开排出炉体。     

造锍熔炼富集含砷难处理金矿中金的研究

在含砷难处理金矿中添加氧化铜造锍熔炼,将金和银富集在铜锍中。通过单因素实验法研究了造锍熔炼过程中主要元素的行为,得到造锍熔炼的最佳条件为:质量比m(CaO)/m(SiO2)=0.5、m(FeO)/m(SiO2)=2.0,物料中铜的总含量为5%,熔炼温度为1300℃,保温时间为60 min,此时金银在铜锍中得到有效富集。金在锍相中的品位为78.3 g/t,回收率可达到99.98%;锍相中铜的回收率为98.64%;渣相中砷和硫含量都很低。物相分析表明铜锍相中的铜和铁主要是以CuFeS2、FeS、Cu2S和Cu存在,对金具有富集作用。     

铜渣组分含量对渣锍高温沉降分离效果的影响

本文利用高温沉降实验对FeO-SiO_2-Fe_3O_4-CaO-Al_2O_3-MgO系中不同组分含量以及温度对铜渣、铜锍分离效果的影响进行研究,同时利用热力学计算软件FactSage结合含固相熔渣的黏度、密度计算公式,对不同渣型炉渣的黏度和密度进行计算,进而研究其对渣锍分离效果的影响。结果表明,当炉渣黏度大于0.5Pa·s时,黏度升高对渣锍分离有着十分不利的影响。当炉渣各组分控制在SiO_2/Fe比(w(SiO_2)/w(Fe))0.82%～0.97%、w(CaO)0～6.2%、w(Al_2O_3)2%～7%、w(MgO)0～1.25%和w(Fe_3O_4)0～10%,且沉降温度在1230℃以上时,熔渣具有良好的流动性,其密度也在理想的范围内,沉降后渣中的含铜量低于1%。由沉降后渣的矿相分析表明,难以沉降的铜物相主要为呈点状分布的微米级黄铜矿和少量大粒径的辉铜矿。     

氧分压对有价金属在镍造锍熔炼渣−锍间分配的影响

硫化镍造锍熔炼中,炉渣成分和体系氧分压对渣性能、渣中Fe3O4含量、渣?低镍锍分离特性及有价金属损失影响显著.利用Factsage软件绘制不同氧分压下NiO-FeO-CaO-SiO2-MgO系液相区和Fe-Ni-Cu-S-O系优势区,探讨pO2和pS2对低镍锍和炉渣成分的影响;通过渣?锍平衡实验并结合X射线衍射、原子吸...     

Moderate Dilution of Copper Slag by Natural Gas

To enable use of copper slag and extract the maximum value from the contained copper, an innovative method of reducing moderately diluted slag to smelt copper-containing antibacterial stainless steel is proposed. This work focused on moderate dilution of copper slag using natural gas. The thermodynamics of copper slag dilution and ternary phase diagrams of the slag system were calculated. The effects of blowing time, temperature, matte settling time, and calcium oxide addition were investigated. The optimum reaction conditions were identified to be blowing time of 20 min, reaction temperature of 1250°C, settling time of 60 min, CaO addition of 4% of mass of slag, natural gas flow rate of 80 mL/min, and outlet pressure of 0.1 MPa. Under these conditions, the Fe₃O₄ and copper contents of the residue were 7.36% and 0.50%, respectively.     

氧气底吹铜熔池熔炼过程的机理及产物的微观分析

对氧气底吹熔炼过程气体喷吹行为、造锍熔炼化学反应机理及熔炼炉内热工作状态进行理论分析及水模型实验和取样分析验证。结果表明,氧气底吹气流能使熔体形成均匀的扩散区,实现熔体的搅拌,在气体连续相区和液体连续相区,气液、液液之间的相互作用强烈,为炉内化学反应及传热传质提供了良好的动力学条件;氧气底吹熔炼过程在零配煤的情况下能达到自热熔炼,在节能减排方面,该工艺具有很强的优势;获得了铜渣、冰铜和蘑菇头中各组分的形貌,确定了铜渣、冰铜和蘑菇头的物相组成,渣样主要由冰铜相、磁铁矿相、铁橄榄石相和玻璃体相组成,熔炼内的氧势和硫势分布有利于反应的进行,能有效抑制Fe3O4的形成以及降低渣含铜。     

闪速炉沉淀池中熔体流动特性的数值模拟(英文)

采用CFX4.3对闪速炉沉淀池中的熔体流动和温度分布进行数值模拟研究。针对1个出渣口对应1个冰铜出口(1-to-1)与1个出渣口对应2个冰铜出口(1-to-2)这两种操作方案共设立16种计算工况。模拟结果表明,两种方案下熔体流动相似,但采用1-to-2操作方案时,熔池中可见明显的回流。仿真中还发现,渣口与冰铜出口的不同组合方式对沉淀池中熔体温度分布的影响显著,其中在1-to-2操作方案下,沉淀池中的熔体温度更均匀。在实际生产中,当采用远离沉淀池入口的放铜口进行操作时将更有利于实现沉淀池内熔体温度的均匀分布。     

Minimization of Copper Losses in Copper Smelting Slag During Electric Furnace Treatment

In the quest to achieve the highest metal recovery during the smelting of copper concentrates, this study has evaluated the minimum level of soluble copper in iron-silicate slags. The experimental work was performed under slag-cleaning conditions for different levels of Fe in the matte and for a range of Fe/SiO₂ ratios in the slag. All experiments were carried out under conditions where three phases were present (copper?Cmatte?Cslag), which is the condition typically prevailing in many slag-cleaning electric furnaces. The %Fe in the electric furnace matte was varied between 0.5?wt.% and 11?wt.%, and two different Fe/SiO₂ ratios in the slag were used (targeted values were 1.4 and 1.6). All experiments were performed at 1200°C. From thermodynamic considerations, from industrial experience, and from the results obtained in this study, the minimum soluble copper content in the electric furnace slag is expected to be near 0.55?wt.% Cu. This level does not account for a portion of the copper present as mechanically entrained matte/metal droplets. Taking this into account, the current authors believe an overall copper level in discard slag between 0.7?wt.% and 0.8?wt.% can be obtained with optimal operating conditions. For these conditions, the copper losses in the slag are roughly 75% as dissolved copper and 25% as entrained matte and copper. Such conditions include operating the electric furnace at metallic copper saturation, maintaining the %Fe in the electric furnace matte between 6?wt.% and 9?wt.%, not exceeding a slag temperature of 1250°C, and controlling the Fe/SiO₂ ratio in the smelting furnace slag at ??1.5. In addition, magnetite reduction needs to be performed efficiently during the slag-cleaning cycle so as to maintain a total magnetite content of ??7?wt.% in the discard slag. The authors further consider that under exceptionally well-controlled conditions, a copper content in electric furnace discard slag between 0.55?wt.% and 0.7?wt.% can be obtained, by minimizing entrained matte and copper solubility in the discard slag.     

Thermodynamic Assessment of Slag–Matte–Metal Equilibria in the Cu-Fe-O-S-Si System

Equilibria among the slag, matte and metal phases in the Cu-Fe-O-S-Si system are critically assessed using thermodynamic modeling. The relationships among matte grade, temperature, partial pressure of SO₂, Fe/SiO₂ in the slag, and the copper concentration in the slag are described by the model, as well as the concentrations of other elements in all phases. A thermodynamic database is created, which can be used for understanding and improving the pyrometallurgical production of copper. An extensive experimental dataset includes the most recent results obtained by the equilibration/quenching/EPMA analysis technique. These data allow to distinguish the physical entrainment of the matte and solid phases in the slag from chemical solubility. As a result, it is possible to describe the copper solubility in the slag with high accuracy and establish the relationship between copper and sulfur in the slag. The thermodynamic database of the present study is consistent with previously reported thermodynamic evaluations of binary, ternary and quaternary subsystems. The slag phase is modeled using the two-sublattice modified quasichemical model in the quadruplet approximation. The matte and metal liquid phases are modeled as one solution using the single-sublattice modified quasichemical model in the pair approximation.     

铜复杂资源熔炼过程中杂质锑脱除的热力学模拟（英文）

研究铜冶炼过程Sb的反应机理,分析Sb在4种典型铜冶炼工艺中多相分配差异。建立富氧底吹铜冶炼工艺的多相平衡模型,研究原料中Cu、S和Sb含量对Sb多相分配比的影响。同时,应用该模型研究铜锍品位、富氧浓度、熔炼温度和氧矿比(标准状态下氧气流量与精矿加料速率之比)等工艺参数对Sb分配行为的影响。结果 表明,计算数据与实际生产结果和文献数据吻合良好。提高精矿中Cu含量、降低S和Sb含量,提高铜锍品位、富氧浓度和氧矿比,同时适当降低冶炼温度,有利于Sb向炉渣中定向富集。模拟结果可为复杂资源清洁高效处理及伴生元素综合回收提供理论指导。     

连铸结晶器内卷渣过程的数学模型

基于功能原理和速度边界层理论,建立了一个数学模型来研究结晶器内渣金卷混机理,提出了引起界面卷渣的钢液临界流速和渣滴直径计算公式,并利用物理模型进行了验证。结果表明：钢液临界流速决于渣钢密度、粘度和它们之间的界面张力,在实际生产中,钢液临界流速为０．５－０．８ｍ／ｓ,产生的渣滴直径约为３ｍｍ。     

Recovery of valuable metals from spent lithium ion batteries by smelting reduction process based on FeO–SiO2–Al2O3 slag system

A novel smelting reduction process based on FeO–SiO₂–Al₂O₃ slag system for spent lithium ion batteries with Al cans was developed, while using copper slag as the only slag former. The feasibility of the process and the mechanism of copper loss in slag were investigated. 98.83% Co, 98.39% Ni and 93.57% Cu were recovered under the optimum conditions of slag former/battery mass ratio of 4.0:1, smelting temperature of 1723 K, and smelting mass ratio of time of 30 min. The FeO–SiO₂–Al₂O₃ slag system for the smelting process is appropriate under the conditions of m(FeO):m(SiO₂)=0.58:1–1.03:1, and 17.19%–21.52% Al₂O₃ content. The obtained alloy was mainly composed of Fe–Co–Cu–Ni solid solution including small amounts of matte. The obtained slag mainly consisted of fayalite and hercynite. Meanwhile, the mechanism of copper loss is the mechanical entrainment from strip-like fayalite particles in the main form of copper sulfide and metallic copper.     

Mass balance calculations in copper flash smelting by means of genetic algorithms

This paper presents mass balance calculations using genetic algorithms for copper smelting in an Outokumpu flash furnace. Based on the elemental composition of the copper concentrates being fed to the reactor, the mineralogical composition of the concentrate mixture is adjusted by means of genetic algorithms. The macroscopic mass balance equations for the species entering and leaving the furnace are solved and the compositions and flow rates of matte, slag, and the off-gas stream are computed. Good agreement between the predicted and plant data was obtained in terms of matte and slag flow rates, matte grade, and copper, iron, magnetite, and silica contents in the slag. Predictions are more suitable and faster to obtain with this method than a conventional method in which the mineralogical composition of the feed is not adjusted. Future applications of the formulation are discussed. For more information, contact V.M. Sanchez-Corrales, Universidad de Sonora, Departamento de Ingeniería Química y Metalurgia, Blvd. Luis Encinas y Rosales, Hermosillo, Sonora, 83000, Mexico; +662-259-2105; fax +662-259-2105; e-mail vsanchez@guaymas.uson.mx.