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By J. Phillip Mackey

The Peter Hayes Symposium on Pyrometallurgy, held as part of Extraction 2018, is an acknowledgement of his contributions to the basic science and principles underpinning modern pyrometallurgical processing. After completing his PhD at Strathclyde University, Scotland, in 1974, Peter took up a teaching position at The University of Queensland, Brisbane, Queensland, Australia in 1976. Peter Hayes’ research at the University since then has been focussed on: • The mechanisms and kinetics of heterogeneous solid/solid, gas/solid and liquid/ solid reactions, and • Experimental measurement of phase equilibria in complex high temperature metallurgical systems. This paper provides a brief biography of Dr. Peter Hayes and gives a full listing of Peter Hayes’ publications.

By C. Kathryn Sole

The close proximity of cobalt and nickel on the Periodic Table and their frequent occurrence together in nature means that their separation in primary hydrometallurgical flowsheets is not only often necessary, but requires the use of innovative chemistry to achieve high selectivity. Today, increasingly stringent demands for the high-purity cobalt and nickel salts required for battery applications in consumer electronics, electric vehicles, and solar applications are again challenging the state of the art. The evolution of cobalt–nickel separations is traced from the basic precipitation technologies employed in 1960s, through commissioning of the first cobalt solvent-extraction plant in South Africa in 1974, to the commercialisation of organophosphinic-acid extractants (which provided a step-change improvement in selectivity) and their eventual widespread use in the 1980s and ’90s. This was followed later by their sulphur analogue, which enabled different possibilities for laterite processing in the new millennium. Separations in chloride media, which take advantage of the different speciation chemistries, and nickel extraction by oximes in ammoniacal systems are also discussed. More recently, chelating and solvent-impregnated resins have added further dimensions to the possibilities for flowsheet design and enabled higher purity products to be attained from both primary and secondary sources. Selected case studies and flowsheets are described.

By Miao Tian

Large quantities of copper complex resources are produced globally and urgent to be cleanly processed. This article presents a thermodynamic analysis of mixed smelting process including low-grade polymetallic copper sulfide concentrates, high copper content sulfide concentrates, metallurgical by-products (copper removal slag from lead metallurgy), and copper powder from electronic waste. A top blown smelting reactor to simulate mixed smelting process is developed using a metallurgical process simulator, METSIM. Reactor parameters, heat loss and phase distributions are estimated from actual plant data. The proper proportion between complicated primary and secondary copper resources is determined by analyzing the influence of the feed rates of various resources, oxygen, silica flux and revert on the smelting performance. Autogenous smelting process is built by optimized matching materials of copper complex resources, in terms of the reactor temperature, copper content in matte and slag, and the percentage of magnetite in slag.

By C. Alexandru Sonoc

Donnan Dialysis uses ion exchange membranes to extract and separate cations. The driving force is provided by differences in chemical potential, rather than by electric fields or pressure. A Donnan Dialysis based process to recover lithium, nickel, cobalt, manganese, and organic acid lixiviant from recycled lithium ion battery cathodes is under development. In this paper we present a model of Donnan Dialysis and results of simulations of the aforementioned process. The simulations show that 170 m2 of membranes can process 1000 L of leachate ([Li+] = 0.285 M, [Co2+] = [Ni2+] = [Mn2+] = 0.095 M, pH 2) in two days and recover 94.1% of the lithium (as lithium carbonate), 99.4% of the transition metals (as mixed sulphates ready for solvent extraction), and all of the organic acid using 423 mol of H2SO4 and 268 mol of KHCO3.

By Jan Steinhoff

The design options of a gravity separator are still limited and rely on the study of settling behavior. A methodology will be presented where an experimentally given inlet droplet size distribution (DSD) is the basis for the calculation of the dispersion layer in a gravity separator. A pilot-scale continuous gravity separator is presented and CFD (computational fluid dynamic) results are validated. A transmitted light measurement technique for the determination of the DSD is presented up to a holdup of 15% dispersed phase. The resulting DSD was in the range of 20–2000 μm depending on flow rate and phase ratio. Furthermore, correlations of the real DSD with the settling behavior of the dispersion in a settling cell are discussed. The new approach to the description of gravity separators will be presented and the applied CFD methods showed good results with the system water/paraffin.

By Zhigan Deng

Cooling crystallization was used to separate iron (III) and nickel (II) from acidic sulfate solution produced by leaching of molybdenum-nickel black shale. The effect of K2SO4 concentration, crystallization temperature, solution pH and crystallization time on recovery of nickel (II) and precipitation of iron (III) was investigated, in order to obtain effective separation of nickel and iron. The optimum parameters determined were as follows: 200 g/L K2SO4, 10 °C crystallization temperature, solution pH of 0.5 and 24 h crystallization. Under these conditions, 97.6% nickel (II) was recovered as K2Ni(SO4)2, 6H2O crystals and only 2.0% of the total iron (III) was precipitated. Recrystallization yielded K2Ni(SO4)2, 6H2O crystals with a purity of 98.4%.

By Mike Dry

While McCabe-Thiele plots are useful for designing single-component solvent extraction systems, not least because of their simplicity, they are less useful for multi-component solvent extraction. This paper presents a relatively simple method, compared to other approaches, for modelling solvent extraction as chemical equilibrium reactions between the various aqueous and organic species. The essence of this approach is how values for the equilibrium constants can be extracted from standard laboratory data. Synergistic solvent extraction of nickel is used to illustrate the method.

By Stephanie Trant

Montana Tech has been engaged in fundamental research on the processing of critical materials for more than a decade. Efforts include examining novel reagents for the flotation of Rare Earth Minerals (REMs). For this paper, research results on a collector, salicyl hydroxamic acid (SHA), are presented. Various REMs were examined and include the rare earth oxides (REOs), carbonates (RECs), and phosphates (REPs) of a suite of Rare Earth Elements (REEs). Differences are attributed to solution and surface chemistry, coordination number, and ionic diameter. SHA adsorption follows an ion-exchange process that leads to chemisorbed and surface-precipitated states, depending mostly on pH. Many effects are directly attributed to lanthanide contraction. Results should also be applicable to other REM/collector systems and further suggest that REM flotation should consider dual collectors.

By Christoph Zschiesche

Managing complex material streams within a lead smelting/reduction process has a long history at Aurubis. After modernization of the secondary lead smelter in 1991, Aurubis operates an electric furnace and a Peirce Smith converter to process complex secondary materials. This process links the copper and the lead metallurgy allowing Aurubis to properly combine primary and secondary process lines to optimize the processing of complex raw materials and smelter intermediates. However, combination of copper and lead metallurgy processing requires a continuous evaluation as raw material quality and composition varies. This paper describes Aurubis lead smelter processing and provides some fundamental considerations to optimize the lead processing, in particular with aspects related to speiss formation

By Gregor Kücher

Lack of basic knowledge on the semi-direct recycling methods for hard metals hinders the application on an industrial scale. However, advantages like reduced expenses and lower environmental impact draw interest at future potentials. Consequently, this report aims to offer insight into the influence of varying bulky hard metal substrates during their lixiviation in acidic media with an oxidant. The statistical software Modde 11 assisted in the development of a design of experiments (DOE) for evaluation of the impact of average grain size, binder and tantalum carbide (TaC) content on the leaching characteristics. The other experimental parameters were constant. Among them were temperature, solution concentration and quantity, duration and substrate surface exposed to liquid volume. Eventually, prediction plots and factors of the computed model equation describe the effects of varying substrate qualities on leached binder metal and selectivity.

By O. Norman Lotter

The formulation and use of mixed collector suites in sulphide flotation can be traced back as far as 1957 with the work of Glembottskii and his co-workers in Moscow. The subject was reviewed by Lotter and Bradshaw in 2010, and proposed a synergy between ideally-selected different reagent types to deliver improved performance, in particular the in situ catalysis of a xanthate to dixanthogen by a dithiocarbamate. Correctly formulated for a particular application, an optimally arranged mixed collector suite delivers the following improvements to the flotation process: • An increase in the flotation kinetics • Improvement in coarse, or middling, particle recovery • Reduction in total dosage requirement • Best results are found from testing the ratios of the collectors. This is of critical importance. In all an optimally formulated mixed collector system usually delivers an increase in paymetals recovery of 1–4% absolute, with a gain in concentrate grade in the range 10–20% relative. In recent years, the addition of semi-conductor theory and associated electrochemistry has contributed significantly to this toolbox by way of identifying optimum domains of Eh and pH for the flotation of individual minerals. In the case of mixtures of minerals, this is where the mixed collector system delivers significant value by way of presenting a mixed set of collector radicals and dimers in a common Eh and pH domain for overall performance. This calls on a fundamental understanding of organic chemistry, mineralogy, semiconductor theory, and electrochemistry. Whereas the selection of grinding media type effectively influences the Eh, the pH can be easily controlled by pH modifiers. The theory of this system, and some industrial case studies, are discussed.

By Jun Enriquez

Kennecott Utah Copper aims to extend anode furnace campaigns to more than three years. As part of that goal improvements are sought on anode-furnace tuyere-area refractory performance. Kennecott and Praxair developed high pressure nitrogen refining for the Oxidation Stage which shortened anode furnace fire refining cycles by up to two hours per cycle. Future developments include optimizing the Reduction Stage’s steam-gas reforming and achieving coherent jet tuyereless refining.

By Youn-Bae Kang

In order to overcome weak points of steel for its engineering applications, in particular, for environmentally benign, energy-efficient, lightweight engineering systems, a number of new steels have been proposed, especially to improve strength-to-weight ratio (specific strength). Mass production of these steels, however, has encountered a serious roadblock particularly in the steel refining and casting processes. This is because their chemistries and cleanliness requirements are vastly different from those of the conventional steels, and thus an incremental improvement of the prevailing process technologies is found hard to meet the requirements. In this study, a new process is proposed, which employs inert gas bubbles in the shroud nozzle, liquid steel drops in the degassing chamber, and the siphon transport for continuous casting. The proposed process which integrates the final refining and cleaning steps prior to casting is expected to be a technologically disruptive innovation on the conventional counterpart. The effectiveness of the individual steps is discussed with experimental results.

By Björn Saxen

Outotec atmospheric Direct Leaching has so far been implemented for zinc production capacities of around 100,000 t/a. Lately, there has been growing interest for small scale direct leaching plants, producing circa 30,000 t/a of Zn. Such small leaching plants can provide extra front-end capacity in existing roaster-based plants and enable treatment of feed materials not suitable for roasting. In small scale plants the proven OKTOP® 9000 Direct Leaching reactors are not readily applicable, due the large size. For smaller installations a modular approach is proposed providing multiple advantages, such as reducing the construction time and amount of the site work required causing less disturbance to regular plant operation with reduced cost. In this paper, we present advantages that can be achieved by using modular OKTOP®C reactors and discuss also process design when connecting a small scale direct leaching process to an existing zinc plant. Also benefits of direct leaching expansion are presented.

By Kimberly Conner-Mills

Due to increasingly stringent worldwide environmental regulations for gaseous, aqueous and solid waste emissions, conventional smelting technology cannot effectively process arsenic containing materials. Many globally significant copper properties have copper sulfide mineralogy that has a high arsenic content present as enargite with significant contained precious metals. As global copper, silver and gold demand increases while significant world resources decrease, treatment of sulfide orebodies with enargite is becoming increasingly important. Methods to selectively dissolve and fix arsenic, leaving behind clean copper and precious metals-bearing concentrates could effectively treat these ores.

By C. Coetzee

Additives are commonly used in copper electrowinning to improve cathode morphology. Polysaccharides such as guar are generally favoured as additives due to their compatibility with solvent extraction. Polyacrylamides are, however, being considered as possible alternatives. Understanding the influence of the structural chemistry of additives on electrowinning performance is critical to utilise them efficiently. This paper investigated polyacrylamide additives which are structurally different; their effects on copper electrodeposition were characterized and compared to that of guar. Electrochemical impedance spectroscopy (EIS) were used to characterize the effects of molecular weight and ionic charge of the polyacrylamides on electrodeposition. The findings were compared against results obtained with an industrially used guar product. Equivalent circuit modelling of EIS data indicated that an increase in polyacrylamide concentration and a decrease in additive molecular weight increased the overall system resistance.

By Eren Hüseyin Obuz

In this study, the leaching kinetics of rare-earth elements were investigated using HCl and HNO3 solutions. A standard crushed complex ore was utilized as raw material. The complex ore (particle size of under 54 μm) contains REE (Ce, La, Nd, Pr, etc.). Different leaching durations were selected for the kinetic studies. The highest leaching efficiency was obtained in HCl solution, and the leaching mechanism was identified to diffusion through a product layer. The rate constants of Ce, La, Nd, and Pr were calculated as 1.08 × 10−2, 0.86 × 10−2, 1.87 × 10−2, and 1.34 × 10−2 h−1, respectively.

By Broggi Andrea

Condensates produced by SiO(g) and CO(g) have a crucial importance in silicon production. Condensation will follow the reactions 3 SiOðgÞ+COðgÞ→ 2 SiO2 + SiC and 2 SiO ðgÞ→Si+SiO2. Solid compounds generated during silicon production contain Si, SiO2 and SiC in different microstructures and amounts. In industrial systems, condensates limit the SiO(g) escape to the off-gas system. On the other hand, they can block the gas flowing from the high temperature zone, hence the necessity of studying an optimized condensation process. This review discusses SiO(g) condensation and its interaction with CO(g). The report gives an overview of the condensates found both at laboratory and at industrial scale. The two main compounds are the Si–SiO2 and the SiOx–SiC mixtures. The hypothesis on the mechanism of formation of SiC–SiOx condensates is presented through a wide selection of performed works. The advantages and disadvantages of the former experimental procedures are discussed.

By A. Navarra

Peirce-Smith converting (PSC) is applied for roughly 50% of primary nickel and 70% of primary copper production. PSC cycles produce batches of ironfree sulfide matte (or blister copper, in the case of copper smelters), that are subject to further processing. However, the number of cycles that can be performed simultaneously is limited by the offgas handling system. Moreover, PSC suffers from variation in the yield and duration of the cycles. This variation is managed by conventional smelter designs, in which the upstream smelting capacity exceeds the nominal converting capacity; PSC is thus a major bottleneck in conventional nickel and copper smelters. Stabilization and standardization of PSC operations can therefore increase smelter throughput. The current paper presents a discrete event simulation (DES) framework to assist in smelter debottlenecking. It features random number generation to represent cycle variability, and time-adaptive finite differences to represent thermochemical complexity. Preliminary computations are presented.

By M. Wallin

Millions of tons of sludge from different metallurgical processes are produced worldwide annually, and the environmental impact of landfilling these often hazardous sludges stresses the need to understand their role as valuable resources. The current work explores the potential of producing a saleable low-phosphorous ferromanganese alloy by utilizing sludge from the silicomanganese industry together with an iron source. The aim of the project is to explore the feasibility and practical challenges related to reduction and dissolution of manganese and silicon from the sludge to liquid metal and slag. Parameters such as ratio of input material as well as the effect of adding limestone and coke to the mixture were explored by thermodynamic calculations and adapted experimentally. Results show that a ferromanganese alloy, in fact, can be formed, while silicon and calcium forms a complex slag that captures a significant amount of impurities.