Thermodynamic modeling of antimony removal from complex resources in copper smelting process

This work investigated the reaction mechanism of Sb in copper smelting process. The difference of multi-phase distribution of Sb in four typical copper smelting processes was analyzed. A multi-phase equilibrium model of the oxygen-enriched bottom-blow copper smelting process was developed. The impacts of Cu, S, and Sb concentrations in raw materials on Sb distribution in multiphases were researched. This model was also used to investigate the effect of process factors such as copper matte grade, oxygen-enriched concentration, smelting temperature, and oxygen/ore ratio (ratio of oxygen flow rate under standard conditions to concentrate charge rate) on Sb distribution behavior. The results showed that calculation data were in good agreement with the actual production results and literature data. Increasing the Cu content and decreasing the S and Sb contents in the concentrate, increasing the copper matte grade, oxygen/enriched concentration, and oxygen-ore ratio, and at the same time appropriately reducing the smelting temperature are conducive to the targeted enrichment of Sb into the slag. Modeling results can provide theoretical guidance for the clean and efficient treatment of complex resources and the comprehensive recycling of associated elements.     

EFFECTS OF TEMPERATURE ON DISTRIBUTION BEHAVIORS OF MINOR ELEMENTS IN COPPER FLASH SMELTING──COMPUTER SIMULATION

ＥＦＦＥＣＴＳＯＦＴＥＭＰＥＲＡＴＵＲＥＯＮＤＩＳＴＲＩＢＵＴＩＯＮＢＥＨＡＶＩＯＲＳＯＦＭＩＮＯＲＥＬＥＭＥＮＴＳＩＮＣＯＰＰＥＲＦＬＡＳＨＳＭＥＬＴＩＮＧ──ＣＯＭＰＵＴＥＲＳＩＭＵＬＡＴＩＯＮ￥ＴａｎＰｅｎｇｆｕ；ＺｈａｎｇＣｈｕａｎｆｕ（Ｄｅ...     

铜闪速熔炼中微量元素行为的计算机模拟

在热力学平衡的基础上，利用描述闪速熔炼中微量元素行为的数学模型，结合闪速熔炼整体平衡计算结果，对Ａｓ，Ｓｂ，Ｂｉ在铜闪速熔炼中的行为进行计算机模拟。计算结果与文献结果及工业观测数据吻合较好。     

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。     

Mathematical model of pyritic smelting process for copper-nickel mineral in oxygen top-blown furnace

1　INTRODUCTIONTheideaofrefiningcopperandnickelwithpyriticsmeltingprocessinoxygentop blownfurnacehascomeintobeingforitsachievementinoxygen converterofsteelmaking processfrom 196 0s.Thefirstpyriticsmeltingfurnacewithoxygentop blownsmeltingnickelhadbeenputintoproductionatNorthNickelCo .ofRussianin 1986 .Nowadays ,thistech nologyhasbeenimportedandemployedinJinchuanNonferrousMetalCo .ofChina .Inthepastdecades ,theutilizationofflashsmeltingfurnaceinnonferrous makinghasgotextensivedevelopmen…     

铜闪速炉沉淀池渣中锍液滴沉降机理及其影响因素

通过分析沉淀池内锍液滴的沉降机理,导出了渣中最大锍液滴直径的计算公式。根据闪速炉的实际生产条件,计算出渣中最大锍液滴直径的理论值为0.063 mm,并用矿相显微镜对沉淀池出口处的渣样进行了观察,渣中最大锍颗粒粒径为0.06 mm,两者结果一致。由此证明了沉降机理分析的正确性。在此基础上,进一步分析渣中锍夹带损失影响因素。结果表明:增大熔体中离散态分布的锍液滴直径是降低渣中铜夹带损失的重要措施;其次是升高渣温度有助于渣中锍的沉降;减小渣层厚度等措施对降低渣中铜夹带损失作用不大。     

Kinetics of the reactions in the smelting furnace of the Mitsubishi process

In this paper, the authors present the results of theoretical calculations on the rates at which copper concentrate particles and silica particles dissolve in the matte in the smelting furnace of Mitsubishiprocess. Those calculations indicate that the concentrate particles dissolve rapidly in matte, in less than 1 ms, whereas silica particles dissolve at a much slower rate, and they dissolve mainly in the bulk matte in the smelting furnace. Some advantages of bath smelting over flash smelting are given. For more information, contact Zenjiro Asaki, Mitsubishi Materials Corporation, Central Research Institute, 1-297 Kitabukuro-cho, Omiya, Saimtama, 330-8508, Japan.     

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.     

Direct Production of Copper

The use of commercially pure oxygen in flash smelting a typical chalcopyrite concentrate or a low grade comminuted matte directly to copper produces a large excess of heat. The heat balance is controlled by adjusting the calorific value of the solid feed. A portion of the sulfide material is roasted to produce a calcine which is blended with unroasted material, and the blend is then autogeneously smelted with oxygen and flux directly to copper. Either iron silicate or iron calcareous slags are produced, both being subject to a slag cleaning treatment. Practically all of the sulfur is contained in a continuous stream of SO₂ gas, most of which is strong enough for liquefaction. A particularly attractive feature of these technologies is that no radically new metallurgical equipment needs to be developed. The oxygen smelting can be carried out not only in the Inco type flash furnace but in other suitable smelters such as cyclone furnaces. Another major advantage stems from abolishion of the ever-troublesome converter aisle, which is replaced with continuous roasting of a fraction of the copper sulfide feed.     

Thermodynamic Consideration for Oxygen Pressure in a Copper Flash Smelting Furnace at Toyo Smelter

JOM - Based on the emf measurements of the galvanic cell (Fe, MgO/O in slag or matte) and the equilibrium calculations, the oxygen pressure in a copper flash smelting furnace at Toyo smelter is...     

Top-blown injection smelting and converting: The Mitsubishi process

The Mitsubishi process is a continuous copper smelting and converting process comprising three steps—smelting of raw materials by injection, separation of slag and matte, and direct converting of high-grade matte. Since commercial operation began in 1974, the hearth productivity has been doubled, and several other improvements have been made, including higher-grade matte smelting and the treatment of various secondary materials. Because the Mitsubishi process is superior to the conventional process, it was decided to construct a larger unit of the Mitsubishi furnaces to replace the two existing smelter lines. This article discusses various technical considerations.     

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。     

Matte Entrainment by SO2 Bubbles in Copper Smelting Slag

JOM - The attachment of copper matte by bubbles in slags, during the copper smelting process, plays a key role in the copper loss. This paper aims to provide an in-depth insight into the copper...     

闪速熔炼在中国的进展与研究--冷风技术及"非接触冶金"

从环境保护角度阐述了世界铜、镍闪速熔炼的发展与现状,讨论了"冷风节能"及其工业应用技术.介绍了中国在"闪速炉扩产"、"闪速冶金事故监控"、"水套新材料"、"闪速炉连续炼铜"等方面的研究成果.为根本解决强化冶金对炉衬的腐蚀,提出了"非接触冶金"的思路,描述了中心旋涡柱闪速熔炼方法,并介绍了旋涡喷嘴基本设计及计算机仿真实验.     

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.     

Chemical Degradation Mechanisms of Magnesia–Chromite Refractories in the Copper Smelting Furnace

Magnesia–chromite refractory has been extensively used in the copper-making industry. It is necessary to understand the degradation mechanisms of the current refractory to develop new refractories. In the present study, post mortem refractories from a smelting furnace were analyzed and compared with the results of static corrosion tests on magnesia–chromite refractories in the laboratory at high temperatures. The microstructure and phase composition were carefully investigated by electron probe x-ray microanalysis to understand the degradation mechanisms of the magnesia–chromite refractory in copper smelting conditions. The degradation mechanisms between the magnesia–chromite refractory and the copper smelting slag and CuO transformed from matte are discussed based on the analysis of the post mortem refractory samples and laboratory tests. These results will enable optimization of the industrial process and development of new refractories for copper smelting furnaces.     

基于遗传算法的铜闪速熔炼过程控制优化

基于已建立的铜闪速熔炼神经网络模型,以能耗费用最低为目标,在工艺指标控制范围内,采用遗传算法对铜闪速熔炼过程的工艺参数进行了仿真优化计算。结果表明,当空气、分配风、工艺氧和中央氧的市场价格折合比值分别为0.05、0.1、0.4和0.45,精矿量为128 t,其成分(质量分数)为Cu 20.61%、S 27.59%、Fe 24.72%、SiO2 11.64%和MgO 1.39%时,铜闪速熔炼工艺参数的遗传优化值为空气15 011 m3、分配风1 302 m3、工艺氧17 359 m3、中央氧1 000 m3、熔剂13.6 t;与实践平均值相比,若采用优化工艺参数控制,熔炼能耗费用可降低4.6%。     

汽车尾气催化剂中铂族金属回收工艺概述

我国铂族金属资源稀缺,从二次资源中回收铂族金属,对于实现可持续发展和环境保护都具有重要意义。综述了目前从报废汽车尾气净化催化剂中回收铂族金属的研究进展,包括预处理、富集和精炼与分离过程。预处理作用是打开废催化剂的包裹或增大与溶液的接触面积。富集是最回收废催化剂最为关键的步骤,湿法富集过程繁琐,周期较长、废水量较多,回收率不稳定。火法富集,以铁、铅、铜、锍的金属熔炼捕集为主,铅、锍熔炼过程会产生毒性物质,铜价格昂贵,而铁捕集具有经济廉价、且工艺流程短、无污染等特点,是未来处理汽车尾气催化剂的发展方向之一。精练与分离步骤包括沉淀、萃取、离子交换以及电解,其中电解法是未来的方向。     

Flash smelting copper concentrates

Flash smelting is a comparatively new method of smelting copper and nickel sulfide concentrates. It takes place when the concentrate, with or without additional fuel, is suspended in gases containing oxygen whereby the heat of oxidation reactions bring the suspended particles to a smelting temperature. From the suspended state the hot particles are separated and molten slag and matte are deposited on the furnace hearth.     

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.