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By J. Phillip Mackey

A whole new group of non-ferrous pyrometallurgical processes with the ability to utilize tonnage oxygen and capture sulphur dioxide were developed and commercialized over the period 1940s–1980s. Many of these earlier process developments were undertaken with limited knowledge of the process chemistry and influence of key process variables; in many cases, piloting helped provide much new physico-chemical data, but gaps remained. The second generation versions of these technologies of today provide all the primary copper, nickel and lead produced worldwide by pyro-metallurgical smelting. Further, process development has continued and a new generation of copper and lead smelting technologies have also been developed in China since the 1990s. The older reverberatory and blast furnaces have been progressively replaced by the newer technologies—a good example being the introduction in 1992 of the copper IsaSmelt technology at the Mt. Isa smelter in Australia where the former fluid bed roaster and reverberatory furnaces were replaced by a single new smelting unit, together with an acid plant for sulphur dioxide collection. The development of these new technologies was made possible by investment in fundamental and applied research. The lesson for the future is, in order to sustain these improvements, continued investment in research and development capability is required—to do otherwise is to risk obsolescence and lack of competiveness in the world market. Dr. Peter Hayes at The University of Queensland is one of the many researchers and process engineers who have contributed to the fundamental understanding of metallurgical processes over this period of rapid change in technologies. The present paper briefly outlines some of the many contributions Peter Hayes has made to the understanding of kinetics, mechanisms and phase equilibria in metallurgical systems, and metallurgical process development.

By James Vaughan

Australia is a major miner of ore that requires hydrometallurgical processing. According to the 2016 US Geological Survey Minerals Commodities Summaries, the country is 1st for aluminium (bauxite) and lithium, 2nd for gold, zinc and cobalt, 4th for nickel and silver, and 6th for copper mining, not to mention its wealth in coal and iron ore. In this paper, examples of recent Australian hydrometallurgical activities are summarised. Then, selected research projects from the University of Queensland hydrometallurgy research group are profiled. The projects profiled are related to fundamental aspects of processing bauxite with organics and reactive silica as well as the development of a synergistic hydro- and pyrometallurgical process for copper. The process context and motivation for the research is introduced, key results are highlighted with the associated relevant references.

By Filipe de Menezes Torres, Augusto Pereira de Sa, Itavahn Alves da Silva, Eliana Ferreira Rodrigues, Carlos Antonio da Silva, Varadarajan Seshadri

Top slag eye opening which happens as a result of gas injection is a function of the gas flow rate in addition to other factors such as ladle geometry, porous plug location as well as slag properties. Slag eye opening leads to entrapment of atmospheric nitrogen, oxygen by the steel melt affecting adversely the steel quality. In this work aspects of mixing and eye formation in steel making ladles with inert gas injection have been analyzed through physical and mathematical modeling techniques. Influence of ladle, gas flow rate and distribution and slag properties has been assessed. A correlation for estimating eye opening has been developed. Results from PIV measurements and images of eye opening obtained using a camera have been utilized to validate results from CFD simulation.

Jan 1, 2015

By Theodore Ineich

The “BIOMOre” project aims to prove the technical feasibility of indirect in situ bioleaching of sulfide minerals contained in a deep underground deposit, by bringing together the disciplines required to make a success. The underground location in Poland was provided by project partner KGHM inside an operating copper mine. Key components of this project were the design and construction of a pilot plant, and its operation in an underground environment. This project also included a ∼250 t (100 m3) fragmented rock reactor hydraulically connected to the pilot plant. The pilot plant consisted of several tanks and pumps, a fluidised bed ferric iron generating bioreactor containing immobilised acidophilic iron oxidation biomass, and all the required instrumentation and utilities. Before the bioleaching phase could start, the rock reactor had to be flushed continuously firstly with water to remove chloride salts that are corrosive and also harmful for the bacteria used in the bioreactor, and secondly, with sulfuric acid solution to react with the carbonates present in the ore matrix. This paper summarizes the design, construction, commissioning, and operation of the pilot plant.

By T. K. Bundtzen

Placer gold in the Iditarod and Innoko mining camps of western Alaska is derived from a suite of comagmatic, Late Cretaceous to Early Tertiary, alkali-calcic, meta-aluminous. volcanic-plutonic complexes and peralumi-nous rhyolite sills that intrude Mesozoic flysch. Heavy-mineral concentrates from 42 mining operations and streams draining known mineralized areas in the igneous complexes contain placer gold and a variety of ore minerals derived from epithermal to hypothermal conditions of formation. The minerals include cassiterite, ilmenorutile, samarskite, cinnabar, scheelite, chromite, stibnite, silver sulfosalts, monazite, and zircon. Results of the study show that 1) cinnabar. stibnite, and quartz formed with the bulk of the placer gold in an epithermal lode environment, 2) chromite appears to have originated in mafic phases of monzonite plutons and alkalic basalts, and 3) niobium-tin-tungsten-uranium-silver values may have been derived from stockwork accumulations in cupolas of monzonite plutons.

Jan 1, 1987

By Willem P. C. Duyvesteyn

A novel hydrometallurgical process for Escondida copper concentrates has been developed by The Minerals Laboratory of BHP. The Escondida Process consists of concentrate leaching, solution purification, electrowinning and residue flotation. Part of the copper will be sold as high grade concentrate and part as high purity SX-EW copper. Contrary to previous efforts for the development of a hydrometallurgical process for copper concentrates, this patented process does not advocate the total dissolution of copper. It only aims for the copper that is readily soluble in a mildly oxidizing environment with an ammoniacal or acidic lixiviant. Both lixiviants were studied, but ammonia was preferred because of fast kinetics at ambient temperatures and pressures. By controlling the oxidation potential, the formation of sulfate ions and, consequently, of an ammonium sulfate byproduct, is precluded. These mild leaching conditions also prevent the dissolution of unwanted impurities and result in the production of ultra-high purity electrowon copper. Solution purification is carried out by solvent extraction with LIX-54. The very high loading capacity of this organic results in a compact SX circuit, consisting of two loading, one scrubbing, and one stripping stage. As the organic is selective for simple copper ions, the copper amine complex is broken down and free ammonia is regenerated and recycled for leaching. High purity copper cathodes are produced in a conventional sulfuric acid based electrowinning system. One scrubbing step is needed to separate the ammoniacal circuit from the acid circuit. Limiting copper dissolution to less than 50% also provides an opportunity to produce high grade concentrates by residue flotation. Copper recoveries in excess of 98% with precious metal values reporting to the final concentrate can readily be obtained. Complete breakdown of the copper mineral- pyrite middlings results in a final concentrate grade that can be even higher than the original feed material. The Escondida Process also provides an opportunity to accept lower grade copper concentrates producing improved copper recoveries in the mill and yet high quality concentrates for marketing. The Paul E. Queoeau International

Jan 1, 1993

By Derek J. Fray

"In order to extend the application of fused salts in\the electrowinning and electrorefining of metals, it is necessary to maximise the current density, minimise the voltage drop and greatly increase the area of electrode surface so as to compete with the space-time yield of pyrometallurgical reactions. The various designs of electrowinning cell are reviewed and it is shown that by the application of a modest centrifugal field it is possible to reduce the anode to cathode interelectrode spacing to 4 mm whilst still maintaining a current efficiency of 85-90%.The thermodynamic potential for electrorefining is far less than for electrowinning yet fused salt electrorefining is only applied in limited cases. The reasons for this are discussed and the important design parameters evaluated. It is concluded that by using packed bed electrodes, separated by a diaphragm, the possibility of electrorefining with very low energy consumption can be achieved. Carbothermically-produced metals are always cheaper than those produced by electrolysis but suffer from the disadvantage of low purity. It is proposed that fused salt electrorefining may offer an energy efficient way of upgrading the metal. IntroductionThe majority of metals can be deposited from fused salts (1,2) but as commercial production is restricted to the more reactive elements, it is worthwhile considering the advantages and disadvantages of fused salt electrolysis as' compared to smelting and aqueous electrolysis. The advantages over aqueous extraction are as follows:1) the much higher conductivities and diffusivities result in much lower IR losses and higher current densities can be achieved at modest voltages;2) the elevated temperatures of operation result in larger exchange currents which give rapid kinetics and lower activation polarisation for the electrode reactions;3) the absence of water as a solvent means that it is not necessary to consider the evolution of hydrogen as a competing cathodic reaction. Furthermore, alkali halide salts, often used as solvents in fused salt electrolytes, have high deposition potentials;4) molten salts generally are mutually soluble and, therefore, concentration polarisation effects are minimised."

Jan 1, 1988

By D. F. Suarez

Spontaneous nodulation leading to growth of well developed glossy spheroids (generally hemispheres) of up to 0.06 cm width in 120 min has been observed during copper electrodeposition with certain levels of glue, thiourea and C1-. Thiourea alone can produce spontaneous nodulation but addition of glue and/or Cl- is required for rapid and sustained growth. In most cases once the glossy nodules develop they consume the majority of the copper deposited; thus, the specific current densities (and hence copper electrodeposition rates) on the glossy nodules are about an order of magnitude or, more greater than on the adjacent planar surfaces. The texture of the adjaoent planar surfaces is not glossy in appearance but is well faceted showing the usual deposition grain structure for such additives. Cathode potentials when spontaneous nodulation occurs are about TOO my more negative than with usual copper electroplating. This fact associated with evidence of extremely high levels of cathode surface passivation based on cyclic voltammograms indicates that the conditions which lead to spontaneous nodulation result from a very tightly adsorbed additive surface film. This film breaks down in specific points initiating the glossy nodules which then grow at extremely rapid rates. Current density is also important in spontaneous nodulation. At equal deposition times a current density of 21.5 mA/cm produced much larger glossy nodules than at 48 mA/cm2. The surface concentration of the glossy nodules was much greater in the latter case, however. The role of current density is still not well understood. The role of it as well as the relative roles of the three additives, thiourea, glue and Cl- in spontaneous nodulation is presented. Preliminary results and some possible correlations of these to help explain spontaneous nodulation are presented. It is believed that tankhouse upsets where cathode nodulation occurs may be related to this phenomenon.

Jan 1, 1987

By W. G. Davenport

The flash furnace is used for smelting concentrate to (i) high-Cu matte and (ii) molten metallic copper. It is also used for converting solidified/crushed matte to molten metallic copper. This is flash converting. It consists (Table 20.1, Fig. 20.1) of: (a)tapping molten 65 to 72% Cu matte from a flash smelting furnace (b) granulating the molten matte to ?1/2 mm particles in a 103 m3/hour water torrent (c) crushing the granulated matte to 50 µm in a vertical roller mill (d)drying the crushed matte (e) feeding the dry particulate matte to a second flash furnace for oxidation converting to molten copper. In 2000, flash converting is being used by Kennecott Utah Copper (George, et al; 1995; Newman et al, 1998, 1999a,b). A second installation is being designed for the Chuquicamata smelter (www.outokumpu.com [October 12, 2000]), The potential uses of flash converting are: (a) as the second half of a flash smelting/flash converting coppermaking sequence (b) as a continuous converting alternative to batch submerged tuyere converting. This chapter uses our flash furnace matrix to determine the %O2-in-blast, industrial oxygen and oil requirements for converting solidified 65% and 72% Cu matte to molten copper. It then discusses choice of feed matte grade and other aspects of the process.

Jan 1, 2001

By Hiroshi Hashimoto

For the application of sodium carbonate slag treatment to product high purity copper on an industrial scale, the counter-flow batch process that reduces the amount of utilized slag is proposed from the viewpoint of the post-treatment of slag. Based on the distribution ratios of several impurities between the slag and molten copper determined previously, the effectiveness of this process is discussed using a mathematical model and confirmed experimentally. According to the model, the slag consumption to remove Sb to a required level in case of the counter-flow batch process with 3 reactors is calculated to be around 30 % of that in the case of an ordinary batch process, where pure sodium carbonate is used as a slag at every stage.

Jan 1, 2003

By Thomas P. Battle

Modern-day direct reduction of iron first developed as a small-scale, low capital and operating cost alternative to the blast furnace. Since commercialization of continuous DR technology in the late 1960s, the market for the products of direct reduction has grown to more than 74 million tonnes in 2012. The initial advantages of DR plants over BF facilities have grown over the years, for several reasons, including the increased size of DR modules, lower energy and emissions (particularly CO2), along with the flexibility to use a number of different reductants. The development of DR technology over the past forty years will be emphasized in this presentation, including recent developments that allow for even more direct sustainability comparisons with the iron blast furnace – and even combine the two technologies for improved synergies. Also briefly discussed will be the possibilities of using direct reduction for non-ferrous ores.

Jan 1, 2014

By G. Fazel Jahromi

Enargite, known as one of the major arsenic containing copper minerals, with approximately 19% arsenic, introduces challenges to typical processing options. In most hydrometallurgical processing methods, arsenic remediation occurs after the copper recovery in an autoclave or in a stepwise neutralization process. In this study, the in situ precipitation of scorodite was investigated during an atmospheric leaching process in the presence of carbon-based catalysts and chloride media. The effective parameters of initial ferric addition, temperature, catalyst addition, and oxygen sparging rate were studied and the ferric behaviour was monitored during the scorodite precipitation. The most influential parameters on efficient scorodite precipitation are found to be: initial ferric addition, catalyst to concentrate ratio, and temperature. A 99% scorodite precipitation yield was achieved in this process.

By D. H. Magoon

The zinc smelter of Cominco Ltd. at Trail, B.C. Is the largest In the western world. A total of 550.000 tonnes of concentrate are proceed at the smelter annually. Approximately 80% of the zinc concentrate is roasted and the remainder Is treated by aqueous oxidation preaaure leaching. The zinc concentrate roasting and sulphur dioxide gas processing plants have undergone many changes over the years. This paper describes the processes and equipment currently used for concentrate roasting, S02 gas cooling and cleaning, mercury removal, sulphuric acid production liquid S02 production, and tall gas S02 scrubbing. The recent Installation of an advanced process control system for the operation of these Integrated processes Is also described.

Jan 1, 1990

By M. W. Kennedy

Prediction of the thermal duties of copper coolers in freeze lined furnaces is challenging. Where copper coolers are immersed in liquid slag the heat transfer is often defined by a natural convection cell immediately adjacent to the wall, in the absence of other factors producing forced convection. Slag coolers are typically not fully immersed, slag temperature, liquidus and superheat can vary, and bath levels may change significantly with batch tapping, leading to substantial variations in radiation heat fluxes. Radiation heat transfer is discussed with reference to the non-obvious impact of slag liquidus on radiation losses in the exposed cooler sections. Reference is made to literature and the results of analytical and FEM models.

By Yoon-Bong Hahn

A mathematical model has been developed to analyze and predict the reduction process of iron ore particles in a two-stage fluidized bed system. This model includes the effect of particle degradation to elucidate its effect on reduction of iron oxides. Although the particle degradation is dependent on kind of iron ores, it was found that eighty to ninety percent of overall degradation is occurred in the prereduction stage mainly due to thermal stress and volume expansion. The degradation of particles in the?final stage is not much, but is mainly due to interparticle collision and abrasion. It was also found that to obtain a target reduction degree, it is of great importance to control the bed temperature and the residence time of paarticles in R1 rather than in R2. Optimum range of residence time was 15-20 minutes in the prereduction stage; 30-35 minutes in the final reduction stage.

Jan 1, 1996

By Andrzej Warczok

Intensive smelting of copper concentrate in Teniente Converter (CT) leads to the production of high grade matte and highly oxidized slag. Smelting slag is processed in Teniente vascular slag cleaning furnace. The slag composition and forms of copper affect the slag cleaning process and final copper content. Converting of high grade matte in Pierce-Smith converter faces some difficulties in proper slagging of iron oxides. Overblowing in copper making stage allows for slag liquidation but leads to high content of copper oxide in converter slag. Converter slag recycling into CT results in the increase of the participation of oxidic copper. Separate treatment of converter slag and its impact on the forms of copper in CT slag has been analyzed. Thermodynamic properties of a system and kinetic limitations pointed out the negative effect of converter slag recycling on the forms of copper and copper recovery in slag cleaning stage. Experimental results of slag cleaning tests in a crucible scale as well as microscopic examination of laboratory and industrial slag samples supported the above analysis and permitted to formulate recommendations of separate processing of converter slag. Keywords: copper, losses, slag, recycling

Jan 1, 2001

By Jinxing Ji

Several fundamental aspects related to the nickel electrowinning from chloride electrolytes have been addressed in this paper. The thermodynamic study includes the activity coefficient of the hydrogen ion and the speciation diagram of NiCI2 solutions. The activity coefficient of the hydrogen ion (YH+) was calculated and estimated experimentally using a combination glass pH electrode. It was found that YH+ was greater than one in concentrated NiCl2 solutions and increased significantly with increasing NiCl2 concentration. The speciation diagram for NiCl2 solutions was plotted with YH+ and the effect of the ionic strength on the equilibrium constants being taken into account. It was discovered that the predominant nickel species in the acidic region were Ni2+ and NiCI+ in 0.937 M NiCl2 solution at 25°C. Electrodeposition tests demonstrated that higher Nit' concentration in the electrolyte improved the current efficiency of nickel electrodeposition (CENi). The additions of H3BO3, and NH4Cl increased very little the current efficiency of nickel electrodeposition at pH 1.5 and temperature 60°C. However, the addition of sulfate decreased the current efficiency of nickel electrodeposition. Nickel electrodeposition was also found to be a steady-state process since the amount of acid added to the electrolyte at a constant pH increased linearly with time during galvanostatic electrodeposition. The cathode surface pH during nickel electrodeposition was measured using a flat-bottom combination glass pH electrode and a 500-mesh gold gauze as cathode. The cathode surface pH was found always to be higher than the pH in the bulk electrolyte, and if the current density was sufficiently large, it would eventually reach a level causing precipitation of insoluble Ni(OH)2(s) on the cathode surface. Rotating disc electrode studies revealed that the rate of nickel electrodeposition was first order with respect to the activity of nickel ion and zero order with respect to the activities of chloride and hydrogen ions. The rate of hydrogen evolution was found to be first order with respect to the activity of hydrogen ion and to be zero order with respect to the activities of nickel and chloride ions. These findings indicate that nickel deposition and hydrogen evolution proceed independently.

Jan 1, 1995

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 Minna Rämä

Iron containing leach residues like jarosite and goethite from electrolytic zinc production contain many valuable metals and harmful substances. These metals and substances should be removed in order to obtain an acceptable, stable and reusable product, and maximize economic feasibility as well as minimize environmental footprint. In this work, the processing of jarosite leach residue was studied in laboratory scale experiments under oxidizing and reducing conditions at high temperatures. First, the pretreated material was melted and oxidized to produce a melt of metal oxides. Second, the oxide melt was reduced in CO–CO2 atmosphere. Target after the reduction step was to obtain a clean slag and a liquid metal or speiss phase that collects the valuable metals, such as silver. The kinetics of the thermal processing were studied for determining optimal times and conditions for the aforementioned process steps. The preliminary results show that the process is thermodynamically feasible, and the desired phases can be obtained in the experimental conditions investigated.

By M. Oliazadeh

Spodumene [LiAl(Si2O6)] is the most common and desirable economic lithium-bearing mineral due to its high lithium content. In Canada, there are several spodumene deposits at the development stage that have the potential to help narrow the forecast lithium supply gap stemming from the widespread acceptance and increasing use of electric vehicles. Spodumene processing can be conducted using Dense Media Separation (DMS), flotation or combination of both. If spodumene liberation is sufficient at coarse particle sizes, DMS can be used for primary lithium concentrate production and silicate gangue minerals rejection. If liberation is not sufficient, flotation is then the main processing route for spodumene concentration. Even in cases where DMS is a viable beneficiation option, flotation may still be required to process the DMS middlings and/or the undersize fraction which is outside the particle size range for DMS. Considering flotation as a technique for spodumene beneficiation, there are several alternatives including the use of mechanical flotation cells, column flotation cells, coarse particle flotation cells, and/or Staged Flotation Reactors (SFR), either alone or in combination. Ore sorting can be incorporated at the start of the spodumene flowsheet to remove gangue minerals, particularly amphibole and pyroxene in the early stages. The main objective of flowsheet development for hard rock lithium deposits is to evaluate the ability of these options to produce a spodumene concentrate with a concentrate grade above 6% Li2O, lithium recovery of above 80%, and with the minimum operating and capital cost. This paper aims to describe the various processing options available for the beneficiation of spodumene from hard rock deposits and compare the associated operating and capital costs for each.