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.     

Using polyethylene glycols as alternative inhibitors in copper electrorefining

Polyethylene glycols (PEGs) with well-defined molecular weight ranges are interesting alternative additives for copper electrorefining. In comparison to glue, PEGs offer high thermal stability and slow chemical decomposition at higher temperatures, with high cathodic polarization. Thosefactors are advantages for an optimized process control in copper electrorefining. Investigations into cathodic polarization as a function of molecular weight and concentration at 500 A/m², and also into the half-life of PEGs, were conducted in typical copper electrolyte.     

The mineralogy of copper electrorefining

The impurities in copper anodes occur both in solid solution in the copper metal matrix and in discrete inclusions at the copper grain boundaries. During electrorefining, all the impurities undergo extensive chemical and/or morphological changes. These changes impact significantly on anode passivation, cathode quality, electrolyte purification and, of course, the subsequent recovery of by-products from the anode slimes. Recently, mineralogical studies have been undertaken to characterize the various impurities and elucidate their transformations during copper electrorefining.     

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。     

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。     

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。     

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...     

Chlorine inclusion mechanism in high purity copper electrorefining from nitric acid system

A practical approach was introduced to study the inclusion mechanism of chlorine in high purity copper electrorefining from nitric acid system via cyclic voltammetry (CV) combined with electrodeposition experiments. The CV curves display an obvious reduction peak of CuCl intermediate, which can provide an insight into the electrochemical behavior of this inclusion. Experimental results show that the increase of HNO₃ concentration is favorable to reducing the quantity of chlorine inclusion although there is a slight decline in cathodic current efficiency. The optimum conditions for copper electrorefining in nitric acid system are HNO₃ concentration in solution of 1−2 mol/L, moderate temperature of ~35 °C with current density not exceeding 25 mA/cm². Based on the theoretical studies, an optimized copper electrorefining experiment was designed to simulate the industrial electrolysis, by which high purity copper can be obtained with chlorine inclusion less than 10 μg/g and current efficiency higher than 90%.     

Intelligent prediction model of matte grade in copper flash smelting process

Due to the importance of detecting the matte grade in the copper flash smelting process, the mechanism model was established according to the multi-phase and multi-component mathematic model. Meanwhile this procedure was a complicated production process with characteristics of large time delay, nonlinearity and so on. A fuzzy neural network model was set up through a great deal of production data. Besides a novel constrained gradient descent algorithm used to update the parameters was put forward to improve the parameters learning efficiency. Ultimately the self-adaptive combination technology was adopted to paralleled integrate two models in order to obtain the prediction model of the matte grade. Industrial data validation shows that the intelligently integrated model is more precise than a single model. It can not only predict the matte grade exactly but also provide optimal control of the copper flash smelting process with potent guidance.     

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...     

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.     

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.     

Removal of Antimony and Bismuth from Copper Electrorefining Electrolyte: Part II—An Investigation of Two Proprietary Solvent Extraction Extractants

Antimony and bismuth recovery from copper electrorefining electrolyte could reduce the impacts of these problem elements and produce a new primary source for them. Two proprietary phosphonic acid ester extractants were examined (REX-1 and REX-2) for the removal of antimony and bismuth from copper electrorefining electrolytes. Experimentation included shakeout and break tests to determine the basic parameters for the extractants in terms of maximum loading, break times, and extraction and stripping efficiency. Five permutations of extractant mixtures (100 wt.% REX-1 and 25 wt.%, 50 wt.%, 75 wt.% and 100 wt.% REX-2) were studied. It was determined that REX-2 was able to extract Sb and Bi from the electrolyte, but required some mixture with REX-1 to better facilitate stripping with 400 g/L sulfuric acid. The laboratory electrorefining electrolyte containing glue had faster disengagement times than a synthetic solution without glue.     

Kinetics of acid-oxygen leaching of low-sulfur Ni-Cu matte at atmospheric pressure

The leaching of low-sulfur Ni-Cu matte in acid-oxygen (CuSO4-H2SO4-O2) solution at atmospheric pressure was researched. This matte was obtained from high grade Ni-Cu matte by magnetic separation, which mainly contained Ni-Cu alloy and a small quantity of sulfides. The effects of temperature, agitation speed, oxygen flow rate, particle size, acid concentration and concentration of copper ion were studied. It is found that the matte particles are leached by shrinking core mechanism and the leaching process is electrochemically controlled. In a temperature range of 30-60 ℃, the surface reaction is rate-limiting step, with an apparent activation energy of 41.9 kJ/mol. But at higher temperature (70-85℃), the rate process is controlled by diffusion through the product layer, with an apparent activation energy of 7.3 kJ/mol.     

Continuous converting of copper mattes

A continuous process for converting copper mattes to blister copper is discussed. The thermodynamics of the converter reactions are analyzed on the basis of their free enthalpies, and it is concluded that the three layers formed in the converter—converter slag, white matte, and blister copper—make possible the continuous converting of mattes. The results of three years of experimental operation of a continuous converter at the Technical University at Kosice, Czechoslovakia, are reported.     

Recovering Bi and Sb from electrolyte in copper electrorefining

The separation of antimony and bismuth in copper electrorefining is somewhat difficult and costly. An ion-exchange technique for the removal of the metals from the electrolyte has been practiced recently, although the metals recovered require further processing. Sumitomo Metal Mining has developed a process to recover antimony and bismuth directly from the eluant by an electrowinning process using a mixture of sulfuric acid and sodium chloride as an eluant for the desorption from the resin. The content of bismuth in the antimony metal recovered by this process was less than 0.2%, while the content of antimony in the bismuth metal was less than 0.4%. K. Ando earned his M.Sc. in metallurgical engineering at Kumamoto University in 1986. He is currently a senior scientist at Sumitomo Metal Mining Company. N. Tsuchida earned his Ph.D. in mineral science at Murdoch University, Western Australia, in 1986. He is currently manager of the Niihama nickel refinery at Sumitomo Metal Mining Company.     

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…     

喷砂工艺对首饰金表面组成和形貌影响的研究

喷砂处理工艺可在金饰品表面产生哑光效果,耐久美观,但也会使得X射线荧光光谱(XRF)测定时出现较大的偏差。分别在宏观与微观下进行表面观测,采用XRF和火试金对18K金饰品材料和成品进行对比测定,研究其表面成分和形貌的差异。结果表明,样品表面存在酸反应痕迹,部分元素(主要是合金中的铜)在酸洗过程中有损失。     

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.     

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

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