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By Alessandro Blasi, Massimo Morgana, Corradino Sposato, Pietro Garzone, Giuseppe Devincenzis

A comparison among (2-ethylhexyl)-mono (2-ethylhexyl) ester Phosphonic acid (P507), Secondary-octyl phenoxy acetic acid (CA-12) and Bis(2,4,4-trimethylpentyl) phosphinic acid (Cyanex272), in heavy rare earths separation via hydrometallurgical processes has been investigated. The separation coefficients, , were obtained and the extraction selectivity has been evaluated using a mixture of heavy rare earths from Samarium to Ytterbium. The experimental results indicated that P507 and Cyanex 272 display a greater affinity for heavier rare earths while CA12 proved to be more effective for the lighter rare earth metals.

Jan 1, 2014

By Rodney Hundermark, July Ndlovu, Lloyd Nelson, Phillimon Mukumbe, Paul van Manen, Whitey Seyanund, Bart Pieterse, Bertus de Villiers, Diale Mokwena

The 2003 redoubling in power to 68MW on the Polokwane Smelter furnace represented a significant intensification in platinum group metal (PGM) smelting. Combined with onerous ‘green’ PGM concentrate smelting requirements, this yielded conditions unusually corrosive to copper coolers and refractories. This presented unexpected operational and design challenges to reliable crucible operation and maintenance. Combined with specific operational control intervention, development of protective coatings has led to the life of water-cooled copper components improving from 9 to 40 months. The furnace matte endwall was extended in 2010 to address accelerated wear of refractories and the potential risk for contact of copper components by superheated matte. An 18 month planned endwall rebuild cycle has been demonstrated (versus catastrophic failure within 9 months). Finally, benefits including lower energy consumption, improved metal recoveries and higher productivity resulting from operational and in-house design developments will be described, that justify “Celebrating the Mega-scale” in PGM smelting.

Jan 1, 2014

By Chang Wei, Zhigan Deng, Minting Li, Cunxiong Li, Xingbin Li

A direct hydrometallurgical process of extraction molybdenum and nickel from molybdenum-nickel ore by pressure water leaching without reagent was studied. The extraction of Mo and Ni from molybdenum-nickel ore by oxygen pressure leaching, which exploit the characteristic of molybdenum-nickel minerals contain high concentration amorphous sulfide which has highly active, and make the most of easily oxide to sulfuric acid and sulfate at low temperature and excess oxygen presence of the amorphous sulfide. Under oxygen pressure conditions, considerable molybdenum and almost all the nickel were extracted into solution in the leaching process. The results show that with the leaching time for 3~4h, temperature at 150o C, liquid-to-solid ratio of 2mL/g, mineral granularity of 0.074mm, oxygen partial pressure of 0.4~0.5MPa without other reagent, molybdenum leaching percentage can be over 80% and nickel leaching percentage can be more than 97%. Furthermore, about 80% sulfur in the Mo-Ni ore has been transformed into sulfuric acid.

Jan 1, 2014

By Jonkion M. Font, Ramana G. Reddy

A thermodynamic model for a priori predictions of arsenic and antimony impurity capacity in Ni-Cu mattes and slags was developed based on the Reddy-Blander (RB) capacity model. The As and Sb capacities were calculated a-priori considering the RB capacity model in Ni-Cu mattes and FeO-FeO1.5-MgO-CuO0.5-NiO-SiO2 slag at 1573 K and 0.1 to 1 atm partial pressure of SO2. The results showed an excellent agreement between the model calculated and experimental data of arsenic and antimony capacities between the mattes and slag. The impurity capacity model developed here, can be extended for prediction of impurity capacities in multi-component base metal slags and base metal mattes. Such a priori predictions of impurity capacities can lead to develop or improve the efficiency of impurity removal from the base metal smelting, converting and refining processes.

Jan 1, 2014

By Pertti Koukkari, Nagendra Tripathi, Karri Penttilä, Justin Salmine

ChemSheet is a thermodynamic multi‐phase multi‐component simulation software, which is used as an Add‐in in Microsoft Excel. In ChemSheet, the unique Constrained Gibbs free energy method can be used to include dynamic constraints and reaction rates of kinetically slow reactions, yet retaining full consistency of the multiphase thermodynamic model. With appropriate data, ChemSheet models can be used to simulate reactors and processes in all fields of thermochemistry. The presentation will cover off‐line modeling of Cu‐flash smelters and advanced thermochemical simulation coupled with on‐line process control of Cu‐Ni smelting. The presentation will describe an off‐line model of Cu‐smelter based on critically assessed properties of the Al-Ca-Cu-Fe-O-S-Si –system (slag, matte and liquid metal) by using the quasichemical model. A four‐stage reactor model (shaft, settler, uptake and bath) is used for optimizing process parameters and feed particle distribution. As a second example, an advanced thermochemical model of a Ni-Cu sulphide smelting plant will be given. The on‐line model covers the operation of treating Ni-Cu-S concentrate via roasters, electric furnace and converters, producing a high grade Bessemer matte product for further refining. The model integrates the thermochemistry of the roasters and electric furnace, and predicts important process parameters such as degree of sulphur elimination in the fluid‐bed roasters, matte grade, iron metallization, slag losses and the iron to silica ratio in the electric furnace slag. Both models can be used to assist process engineers and operators in calculating the addition rates of coke, flux and air for different feed scenarios.

Jan 1, 2014

By Kenneth S. Coley, Michael Pomeroy, Elaine Chen

Recent work on modeling of BOF steelmaking is reviewed, highlighting the critical aspects of each approach. It is concluded that the most successful models should be based on a deep understanding of the mechanisms and kinetics of the critical reactions. The importance of the decarburization mechanism is discussed with particular reference to its role in droplet swelling or bloating which has a profound influence on the droplet residence time in the slag. Conditions which cause bloating are discussed and the rate determining step is proposed to be primarily nucleation of CO bubbles inside the metal droplet with some influence from growth by reaction at the bubble/metal interface. The discrepancy in the super-saturation ratio required for classical nucleation is discussed and an approach using a surface tension modifying parameter is illustrated. Finally, the role of CO nucleation in controlling the driving force for dephosphorization is discussed.

Jan 1, 2014

By Hong Yong Sohn

A novel flash ironmaking technology is under development at the University of Utah under the support of U.S. Department of Energy (DOE) and American Iron and Steel Institute (AISI). The history of the development from the conception of the idea to the current status will be discussed. The flash ironmaking process produces iron directly from fine iron ore concentrates without requiring cokemaking and pelletization/sintering, which will enable the technology to significantly reduce energy consumption and carbon dioxide emissions compared with blast furnace ironmaking. Unlike other gas-based ironmaking processes, this technology will not suffer from the problems of solid sticking and fusion. Current work is focused on the method of supplying the energy required to maintain the necessary temperature, as an intermediate step to determine the scalability for larger, industrial-scale pilot trials.

Jan 1, 2014

By Yotamu Stephen Rainford Hara, Animesh Jha

The investigation focuses on a low temperature recovery of Cu and Co from a 40 wt% SiO2-(30 wt%Fe,6 wt%Al)2O3-10wt% CaO-7wt%CuO-7wt%CoO slag over a temperature range of 1173K to 1323K. The alloy phases containing Cu-Co and Fe-Co alloy formed via the carbothermic reduction of oxides: MO + C = M + CO(g), where M represents metallic copper, cobalt or iron. In the direct reduction of oxides, the recovery of metallic phase was well below 90% at 1323K, due to the kinetic barrier which was analysed and attributed to oxygen and metal-ion transport in the slag. This barrier was overcome by adding CaSO4 and carbon, which yields a matte (MS) phase via MO + CaSO4 + 4C = MS + CaO + 4CO reaction. Lime thus produced in situ participates in metal oxide/metal sulphide reduction reactions, which are analysed with the help of X-ray powder diffraction, scanning electron microscopy, and thermogravimetric analysis.

Jan 1, 2014

By Oluwatosin A. Aladejebi, Apsara S. Jayasekara, Raymond J. Longbottom, Mark Reid, Marc in het Panhuis, Brian J. Monaghan

The coke analogue is a new research tool that has been developed to quantify and characterize the effect minerals in coke have on coke reactivity. The analogue material is made from a number of different carbon or carbon containing materials and minerals to in part replicate real industrial coke’s reactivity behavior. Elucidation of the effects of minerals on coke reactivity has proved difficult due to the complex and heterogeneous nature of industrial coke and the potential non-additive effects of minerals on coke reactivity. The coke analogue addresses this complexity and heterogeneity through control of its mineralogy, mineral size and mineral dispersion through the analogue, porosity and carbon structures. Initial studies using the analogue were focused on coke dissolution kinetics in liquid iron but recent work has focused in characterization of its porosity, carbon structure and rate of reaction.

Jan 1, 2014

By Jiangtao Li, Zhongwei Zhao, Xingyu Chen, Xuheng Liu

In tungsten ion-exchange process, excessive sodium impurity enters into ammonium tungstate solution. However, the Na content of the final ammonium paratungstate (APT) product must be strictly controlled. Consequently, it is necessary to remove Na from the ammonium tungstate solution during processing in order to obtain the required purity of APT. In this study, porous Na specific absorbent, Na1+xAlxTi2−x(PO4)3, is used to remove Na from the ammonium tungstate solution. Through experiments, the effect of reagent concentration of Na1+xAlxTi2−x(PO4)3, reaction time, reaction temperature and Na concentration on the Na removal were investigated. The results showed that under optimal reaction conditions of reagent amount of NATP 1.0 times of theoretical amount, reaction temperature 25 °C and reaction time 15 min, the Na removal from commercial (NH4)2WO4 solution can reach 98%. Na1+xAlxTi2−x(PO4)3 has a good applicability to different Na+ concentrations. The obtained APT product reaches the national standard purity of zero level.

Jan 1, 2014

By Dian Adisty, Leiv Kolbeinsen, Eli Ringdalen

In Si and FeSi production, the main Si source is SiO2, in the form of quartz. Reactions with SiO2 generate SiO-gas that further reacts with SiC to Si. During heating, quartz will transform to other SiO2 modifications with cristobalite as the stable high temperature phase. Transformation to cristobalite has been investigated and shown to be a slow process where the rate varies between the investigated quartz types. The effect of quartz versus cristobalite as SiO2 source has been studied for reaction (1) 2SiO2 + SiC = 3SiO + CO, by heating of pellets with SiO2 + SiC in Ar-gas. The reaction was faster with cristobalite than with quartz. Initial experiments indicates that this is the case only in Ar and not in CO-atmosphere The higher specific surface area of cristobalite is believed to contribute to the higher rate. The industrial consequences of the observed difference between quartz types are discussed.

Jan 1, 2014

By Terence Makanyire, Animesh Jha

The dissolution and chemical properties of vanadium, zirconium, and niobium in rutile lattice are analyzed by comparing the octahedral site preference energies, with respect to Ti4+ ion in the solvent phase. The oxides are often present in rutile lattice and interfere in achieving the quality of pigment grade TiO2 due to favourable Gibbs energy for dissolution in the solvent rutile matrix. Binary mixtures of V2O5 { TiO2; Nb2O5 { TiO2 and ZrO2 { TiO2 with compositions of 80, 85, 90, 95 and 97 wt% TiO2 were made, pelletized and sintered at 1100 °C for 24 hours. The solidsolution mixtures were then cooled and leached in 2M NaOH for 3 hours at 60 °C. Phase and lattice parameter characterizations, and microstructural and compositional analyses were then carried out using X-ray diraction and SEM/EDX, respectively. The leachates were analysed by Atomic Absorption Spectroscopy (AAS), using which the solute dissolution model for oxides were investigated.

Jan 1, 2014

By Alessandro Blasi, Massimo Morgana, Corradino Sposato, Pietro Garzone, Giuseppe Devincenzis

The rare earth elements are essential for a diverse and expanding array of high-technology applications, which constitute an important part of the industrial economy of the 21st century. As a matter of fact, rare earth has been listed in the category of strategic elements in many countries becoming a core business for international research. Experimental tests have been carried out on a bench scale battery of mixer settler composed of 24 stages, each one with a volume of 150 ml. These trials have been performed at room temperature checked by a micro-climatic control system. The battery was setted in two sections: extraction and scrubbing section. Rare earths concentrations were obtained by ICP-OES analysis made on aqueous phase and on the stripped from organic phase. We obtained a complete separation of light rare earth (La, Ce, Pr, Nd) in two sub-groups: La/Ce and Pr/Nd.

Jan 1, 2014

By Jiangtao Li, Zhongwei Zhao, Xingyu Chen, Xuheng Liu

In order to produce good quality ammonium paratungstate, Sn needs be removed efficiently from the tungstate processing solution. The nascent hydrous ferric oxide has excellent adsorption ability and is often used as an adsorbent to remove metal ions from aqueous solution. In this paper, nascent hydrous ferric oxide is used to remove Sn from tungstate solution. Through experimental, the effects of pH value, reagent amount of adsorbent, reaction temperature and reaction time on the Sn removal are investigated. The study shows that 98% of Sn can be removed effectively from sodium tungstate solution and only 2% of W is lost during process under the conditions of pH 9~12, reagent amount of Fe addition 40 times Sn amount, reaction time 30min and room temperature. As the Fe addition reaches 90 times of Sn concentration in the ammonium tungstate solution, 99% of Sn is removed and APT with zero level purity national standard is obtained.

Jan 1, 2014

By Hu Meilong, Liu Lu, Bai Chenguang

Extracting perovskite from high titanium-bearing blast furnace (BF) slag is a green and potential method to recover the second titanium resource. The non-isothermal crystallization process of perovskite in synthesized high titanium-bearing slag was studied in situ by confocal scanning laser microscope (CSLM) with cooling rate of 20 K/min. The results showed that perovskite was the primary phase formed during cooling process in the titanium-bearing synthesized slag (TiO2=23%). Perovskite started to precipitate at 1719 K and finally presented an orthogonal straight lines morphology.

Jan 1, 2014

By E. Bélisle, Christopher W. Bale, S. Petersen, C. Robelin, K. Hack, J. Melançon, G. Eriksson, A. D. Pelton, P. Chartrand, S. A. Decterov, I. H. Jung, A. Gheribi

The FactSage® package consists of a series of information, database and calculation modules that enable one to access pure substances and solution databases and perform thermochemical equilibrium calculations. FactSage was originally founded by process pyrometallurgists and has since expanded its applications to include hydrometallurgy, electrometallurgy, corrosion, glass technology, combustion, ceramics, geology, environmental studies, etc. With the various modules one can perform a wide variety of thermochemical calculations and generate tables and graphs of complex chemical equilibria and phase diagrams for multicomponent systems. This paper presents examples of recent and current developments in FactSage in areas of particular interest to Dr. David Robertson. These include both ferrous and non-ferrous processing, as well as solidification and refining simulation. The paper also includes reference to the Internet Fact-Web education package.

Jan 1, 2014

By Dong Joon Min, Joo Hyun Park, Mi Sun Choi, Jae Hong Shin

Sublimation of ZrCl4 is important for the production of nuclear grade metallic Zr in Kroll’s process. The sublimation kinetics of ZrCl4 was investigated by TGA under both isothermal and non-isothermal conditions. The sublimation rate of ZrCl4 increased with increasing temperature under isothermal conditions. ZrCl4 sublimation was confirmed to be a zero-order process under isothermal conditions, whereas it was first-order kinetics under non-isothermal conditions. The activation energy of ZrCl4 sublimation under isothermal conditions was 21.7 kJ/mol. The activation energy for non-isothermal sublimation was 101.4 kJ/mol and 108.1 kJ/mol with the Kissinger method and Flynn- Wall-Ozawa method, respectively. These non-isothermal activation energies were very close to the heat of sublimation (103.3 kJ/mol). Sublimation occurs by two elementary steps: surface reaction and desorption. Therefore, the overall activation energy of ZrCl4 sublimation is 104.8(±3.4) kJ/mol. The activation energy of the surface reaction and desorption steps are proposed to be 83.1 kJ/mol and 21.7 kJ/mol, respectively.

Jan 1, 2014

By P. J. Mackey

Over the course of Dr. Robertson’s career, the ferrous and non-ferrous plants have seen enormous changes in technology and increases in plant capacity, essentially amounting to a “technological revolution”. In iron and steel, the “mega” blast furnace of some 6,000 m3 working volume is now standard (~10,000 tonnes (mt) of pig iron/day). Similar huge changes in process technology and plant size have occurred in the non-ferrous industry. As an example, the fuelfired reverberatory furnace, once the mainstay of the copper industry, has disappeared - replaced by large capacity flash and bath smelting technologies. The energy consumption per unit mass of metal produced has also been reduced considerably. Our understanding of the thermodynamics and mechanisms of metallurgical reactions, a field to which Dr. Robertson has significantly contributed, has made great strides. This paper reviews these changes with particular reference to the copper smelting industry, providing also comments on expected future trends.

Jan 1, 2014

By Michele L. Bustamante, Gabrielle Gaustad

In recent years, t h e future supply of tellurium has been called into question due to the anticipated rapidly increasing demand from thin film cadmium telluride photovoltaics. Since tellurium is produced as a byproduct of other extractive processes – principally, the electrolytic refining of primary copper sulfide ore – it is important to explore the dynamics of the parent metal extraction and processing – in this case copper – when attempting to answer this question. This research explores the changing landscape of global copper production; introducing system diagramming and the concept of byproduct intensity (BPI) to illustrate concerning downward trends in tellurium supply potential. Upon closer inspection, it is concluding that, while a likely contributor to these downward trends, the increased use of non- traditional copper production techniques alone are not responsible; other factors include market substitution and incomplete data reporting. Additionally, a review of literature on tellurium recovery processing reveals a promising outlook for future supplies; highlighting potential for improvements in yield, which allow producers to make better use of what is available, even in the face of suppressed BPI.

Jan 1, 2014

By Jae-Chun Lee, Jinki Jeong, Manis Kumar Jha, Divika Gupta, Pankaj Kumar Choubey

Rare metal indium (In) is mostly used as electroluminescent material in liquid crystal displays (LCD) monitors. Present paper describes leaching studies for the recovery of In from waste LCD monitors in presence of different other impurities. The leaching studies showed that more than 85% of In was leached out using 20% sulfuric acid at 60oC in mixing time 30 min at fixed pulp density 25 g/L. The solution could be purified using SX/IX and from the pure solution metal/ salt could be produced by evaporation, precipitation, electrolysis, crystallization processes.

Jan 1, 2014