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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 C. P. Broadbent

The process metallurgy of many nickel laterite smelting operations is controlled largely by the physical chemistry of the slag system. Consequently, accurate phase diagram information and physicochemical property data are essential to interpret and predict the behaviour and optimisation of the overall process. The system (SiO2 - MgO - FeO) first described by Bowen et al. between 1914 and 1935 and the system (SiO2 - MgO - FeO - Fe2O3) determined by Muan and Osborne in 1956 are of particular relevance to the study of nickel laterite smelting slags as these systems form a reasonable approximation of many industrial slags. This paper will review the literature for these (and other relevant) phase systems. In addition data available from the ternary and (quasi)ternary phase diagrams will be compared with data obtained from industrial slags. The physico-chemical properties under consideration will include; melting and crystallisation behaviour (solidus and liquidus temperatures), viscosity - temperature relationships, heat flux considerations, electrical conductivity, surface and interfacial tension.

Jan 1, 1993

By C. Allen

A series of zinc chloride electrowinning tests was carried out in a laboratory scale cell to evaluate the effect of temperature, current density, electrolyte composition, gas sparging and additives on the performance of the cell with respect to current efficiency, voltage, specific energy consumption and deposit morphology. The anode material was DSA for chlorine evolution and the cathode was made of aluminum. At 400 A/m2 current density, a current efficiency of 90.9%, a voltage of 3.4 V and an energy consumption of 2.78 kWh/kg were observed. Air sparging was found beneficial but was not pursued for health and safety reasons. Various additives in the same chemical family as tetrabutyl ammonium chloride (TBAC1) were tested. Both TBAC1 and tetrabutyl ammonium bromide were found to be equally effective. Attempts to carry out the electrolysis at 1200 A/m2 were not as successful.

Jan 1, 2000

By Mehmet Bu daycı, Onuralp Yücel, Ahmet Turan, Murat Alkan

In this study, iron based alloys (Fe, Fe-Cr-Ni-Mo, etc.) were produced by using metallothermic methods starting from Mill Scales obtained continuous casting processes. During the process, the combustion was realized by ignition and the produced wave propagates throughout the reactant mixture yielding the desired product. In this work, Mill scale used as an iron source, which includes +2, +3 values iron oxides. Aluminum, Magnesium and Silicon were used as reductants. In these metallothermic experiments, different ratios of reductants were examined, and their effects on the metal recovery and alloy compositions were investigated. The samples were characterized by using chemical analysis (AAS), XRD and XRF techniques.

Jan 1, 2016

By Wenjie Zhu

Chromite ore processing residue (COPR) is a hazardous waste containing high concentration of chromium. We describe here a pioneer trial of detoxification of COPR in column reactor with an indigenous chromate reducing bacterium Leucobacter sp. Ch1, which showed high chromate reducing ability at high pH. Under the optimum conditions, at 30°C and pH 10.0, pH of leachate decreased from 10.3 to 8.3, and Cr(VI) concentration in solution decreased to zero mg L-1, and 76.4% of Cr(VI) was removed from COPR samples. The leaching toxicity of detoxified residue was 1.1 mg L-1 that was lower than national standard of China.

Jan 1, 2008

By Evgueni Jak

Pyrometallurgy is an important sector of modern industrial society actively participating in solving current environmental, economic, materials scarcity and other challenges. Recent advances in analytical methods, experimental techniques, thermodynamic, phase equilibria and process modelling tools provide new opportunities to increase the productivity of pyrometallurgical reactors, the treatment of complex feeds and metal recoveries. Fundamental theoretical models can now be used to make a significant next step towards the development and implementation of computerised models describing real industrial processes—Virtual Reactors, and computer-aided smart-decision-making systems that may be called Pyro-GPS by analogy to GPS; these developments can facilitate knowledge-based improvement and optimisation strategies. The implementation of these improvements require ongoing collaboration between researchers, industry and government.

By Shun Myung Shin, Kang Jeong, Kyoungkeun Yoo, Jin Koo, Dong Hyo Yang, Soo Sohn

"The optimum discharging condition to dismantle the batteries without explosion was investigated to recycle the lithium primary batteries, which could be exploded by heating too much or crushing. The 3 waste lithium primary battery cells were discharged with 500 cm3 of 0.5 kmol·m-3 sulfuric acid. Fe concentration and pH increased rapidly after 3 days at 35? and after 1 day at 50?. Chromium concentration increased by 4 days at 35? and 2 day at 50?and then decreased, and nickel concentration was very low. Because Li concentration increased gradually, Li became dissolved after the dissolution of cover material. When the discharged batteries were shredded, the batteries discharged at 50°C were not exploded and those discharged during 3 days at 35°C were exploded. This result shows that the waste batteries could be stabilized within 1 day at 50°C and 4 days at 35°C. Introduction Lithium has some advantages for battery e.g. it is the lightest metals and also has the highest electrochemical potential at 3.04V[1]. For over thirty years lithium primary batteries became famous for their performance in various applications such as IT, medical, and military[2,3]. They gained a reputation for their long shelf life, constant voltage, wide operating temperature range, and low self-discharge characteristics[3-5]. World primary lithium battery market was expected to grow from $820.6 million in 2003 to $1,1355.3 million in 2010 (http://www.frost.com, Frost & Sullivan)[2-4]. The lithium primary batteries have very various sizes and components. Lithium batteries are made with lithium metal as anode active material and non-aqueous solvent as electrolyte. As cathode active material, various kinds of materials were used such as manganese dioxide (nominal voltage, 3.5V), thionyl chloride (3.6V), and carbon monofluoride (3.0V). In Korea, 50 % of the spent lithium primary batteries must be recycled because spent lithium primary batteries have been listed in EPR (Extended Producer Responsibility) of the enforcement degree of the act on the promotion of saving and recycling of resources. However, the batteries have been landfilled since there is no economic method to recycle the batteries in Korea[2,3]. When the batteries were heated too much, charged, pierced, over discharged, or short-circuited, the batteries explode because lithium reacts violently with water or air and because contents such as lithium, electrolyte, and sulfur become flammable by high temperature[4]. Therefore, it is so difficult to recycle safely the spent lithium primary batteries."

Jan 1, 2008

By Ho-Sang Sohn

Copper concentrate particles of 200 to 300 mesh size were fed from the top of vertical reaction tube of 2.8 cm ID and 2 m long with an O2-N2 gas mixture. The reaction tube was heated to 900 K to 1100 K. The residence time of the particles in the reaction tube was about 1 second. The copper concentrate particles were very rapidly oxidized and melted down during their descent in the reaction tube. The particle temperature were calculated by combining an un-reacted core model, mass transfer between gas and particles, and heat transfer between gas, particles and tube wall. The particle temperature reached its maximum within a distance of 60 cm from the top of reaction tube, and it attained at 2000 K at higher oxygen partial pressure. The most particles were melted at the oxygen partial pressure above 20 kPa. An appreciable amount of As, Sb and Pb in the concentrate particles was eliminated in the upper portion of the reaction tube and the rate of elimination are explained by the rate of mass transfer of volatilized species through the gas film on the particle surface and the variation of particle temperature during the descent.

Jan 1, 2006

By Brajendra Mishra

Molten Salt electrolytic processes offer unique opportunities to extract and refine metals where gaseous or metallothemlic reduction, hydrometallurgical extraction and aqueous electrolytic methods are thermodynamically constrained. Production of aluminum and magnesium by molten salt electrolysis are well known commercial processes. Several other reactive metals, such as lanthanides and actinides, as well as beryllium and calcium, make use of molten salt processing for extraction and refining. This presentation describes the science of molten salt chemistry and electrochemistry for winning and refining of several metals. In addition, recovery of metals from waste process salts by molten salt reduction as well as oxidation have been discussed. Material issues in design of molten salt reactors have been included. Various applications have been presented through case studies. Experimental data have been included to justify the suitability as well as limitations of these specific processes.

Jan 1, 2003

By Hideaki Tokuyama

Recovery of Ni from acidic wastewater of metal surface treatment has been investigated for reuse of the metal and water. Ion exchange equilibria between Ni ion and a strong acid cation resin, DIAION SKIB, and effective diffusivity in resin particle have been studied and they related to the concentration of HCI. The amount of adsorbed Ni for unit quantity of resin decreases with the increase in HCI concentration. This trend is remarkable for acid concentration above 0.1 kmol/m3,. The exchanging ratio of Ni2+ to H+ in resin particle is I/2 and the values of equilibrium coefficient K and maximum exchange capacity Q are I.62 and 3.16 keq/m3 -dry resin, respectively. Effective diffusivity D. determined from the observed breakthrough curve increases with increasing concentration of DC!. A prototype of moving bed has been developed and applied for the recovery of Ni from model solutions of wastewater prepared by mixing HCl and NiCl2. This apparatus allows us to control the resin flow rate by changing the cross sectional area of hole I the Teflon plate installed at the bottom of resin bed. Characteristics of Ni recovery have been clarified under various liquid flow rates. In any case for Q1, Ni ion has been effectively recovered on SKIB resin and the removed fraction was more than 99.5 %. Higher loading ratio of ion is attained at larger liquid flow rate.

Jan 1, 2003

By Adam Powell, Salvador Barriga, Matthew Earlam

"The inert anode is a key enabling technology for dramatic energy and emissions reduction in extractive metallurgy. In molten salts, the materials challenge is nearly insurmountable: the anode must conduct electrons at high temperature in a pure oxygen and molten salt environment. A solid electrolyte, e.g. zirconia, between the salt and anode removes the molten salt stability constraint, and can act as a container for a liquid metal anode. This can be liquid silver for oxygen-generating inert anodes, or several metals for natural gas-fueled anodes; it is possible to switch between these modes. The solid electrolyte brings several other benefits: it eliminates molten salt contamination of the anode gas, creates a reducing environment enabling low-cost steel vessels, increases current efficiency, and eliminates carbon contamination of the product. New developments presented here, including current collector and low-cost anode designs, amplify these benefits for producing aluminum, magnesium, rare-earths, and other metals.IntroductionReactive metals such as magnesium, aluminum and rare-earths play increasing roles in efficient transportation and clean energy. In response to new fuel economy standards, automotive OEMs are planning large increases in use of aluminum and magnesium to reduce vehicle weight. Rareearth permanent magnet motors and generators exhibit better power-to-weight and efficiency than induction motors and other designs, making this today's primary motor technology for hybrid and electric vehicles, and for wind turbines. Nickel metal hydride (NiMH) batteries with lanthanum are dominant in hybrids. In 2011, transportation comprised 28.6 out of 103.1 EJ of US energy consumption [1] and 1,845 out of 5,471 million metric tonnes (MMT = 109 kg) CO2e of US greenhouse gas (GHG) emissions [1], creating big targets for economy-wide reductions.Unfortunately processes for making reactive metals for these applications are very inefficient and heavily-polluting. In primary aluminum production, Hall-Heroult cell electricity use [2] is more than double the reaction enthalpy due to heat losses through frozen cryolite side-walls and anode gases, graphite anode plants add significant energy use and GHG emissions [2] (see Table 1). Magnesium is even worse: silicothermic reduction by the Pidgeon process in China produces about 85% of the world's magnesium using coal or coke gas [3]. Chloride electrolysis begins with high-purity MgO and requires carbochlorination or hydrochlorination and costly chloride dehydration [4]—rendered unnecessary for aluminum by the Hall-Heroult cell. Production of neodymium and lanthanum with graphite anodes leads to inconsistent carbon content: small cells make 1 kg batches for analysis, sorting and sale by carbon content, with very high labor and analysis costs. And vertical electrodes give no incentive to reduce anode effect: some reports indicate that China's rare-earth metal industry emits more CF4 and C2F6—with global warming potential (GWP) 6500 and 9200 times CO2 respectively—than China's aluminum industry [5]."

Jan 1, 2014

By M. Vijayalakshmi, S. Saroja, C. Sudha, T. N. Prasanthi

"Ti-5Ta-2Nb alloy and 304L austenitic stainless steel were joined by explosive cladding process. Investigations on 'as received' explosive clad revealed high hardness very near the interface due to martensitic transformation of 304L steel base plate. To improve ductility, explosive clads were heat treated in the temperature range of 823 to 1073 K for 1 to 20 h. Consequent change in the microstructure and microchemistry of the clad interface was studied. No change in the interface microstructure was observed for heat treatment at 823 K. Increase in temperature lead to the formation of various reaction zones at the interface, their number and width increase with temperature and time of thermal exposure. Growth kinetics of the reaction zones was monitored and activation energy required for formation was calculated. From elemental redistribution profiles, effective inter-diffusivities of alloying elements were calculated as a function of concentration and activation energy required for inter-diffusion was evaluated.IntroductionFor engineering components exposed to highly oxidizing and corrosive environments, a titanium based alloy i.e Ti-5Ta-2Nb (Ti-Ta-Nb) is often chosen as a structural material [1,2]. For economic consideration, vessels and piping exposed to non-oxidizing conditions are fabricated from 304L austenitic stainless steel (304L SS). Hence, dissimilar joint of Ti-5Ta-2Nb alloy and austenitic stainless steel becomes unavoidable. Fusion welding processes are not suitable for joining Ti and Fe based alloys due to the propensity for the formation of intermetallic phases and subsequent reduction in the bond strength [3,4]. Hence, explosive cladding, a solid state welding technique, was used to achieve high integrity, corrosion resistant joints between the two alloys."

Jan 1, 2012

By Mark Osborne, Ray D. Peterson, C. Edward Eckert

"The theoretical melting energy requirement for a typical hypoeutectic aluminum-silicon alloy is approximately 520 BTU/lb. It has been demonstrated, however, that even a state of the art secondary processing-automated lost foam casting operation can exceed this value by at least an order of magnitude when the actual thermal energy input from melting to solidification is monitored. Metal transfer and holding operations constitutes over 65% of this expenditure. The authors present relative benchmark energy expenditure information by unit operation for an offsite melting/lost foam casting line with a daily throughput in excess of 100,000 lbs. Efficiency improvements through optimization of the current process, and anticipated energy values at the culmination of a U.S. Department of Energy sponsored project to develop, integrate and demonstrate an advanced melting, transportation, and dispensation system will be cited.IntroductionThe size of the U.S. aluminum remelt pool was approximated to be 14.21 billion kg (31.27 billion pounds) by a recent study?, with the engineered castings (foundry) sector accounting for 3.25 billion kg (7.16 billion pounds) or 23% of that total. This study considered overall process yield and all major contributors to scrap. The values cited, therefore, are more meaningful than simply tabulating annual pounds shipped by sector.The foundry sector consists of Sand Castings, PM Castings and Die Castings categories appearing in Figure 1. All other categories comprise the wrought alloy sector. Wrought alloy production enjoys an energetic benefit from both scale and a relatively continuous operation. Many foundry operations, however, operate in batch mode at less than design metal throughput with characteristically longer melt holding periods. Since any detention of molten metal beyond melting represents an overhead use of energy, melt holding (secondary) energy expenditures can appreciably inflate melting energy requirements in the foundry."

Jan 1, 2009

By J. S. Kirkaldy

A theoretical procedure is demonstrated for calculating two-dimensional binary cellular single-valued interfaces and extended to triple-valued (remelt) shapes. The numerical calculations for the single-valued local equilibrium problem which yield unique shapes as functions of the supersaturation parameter a and the partition coefficient k are reviewed. The cell amplitude L and wavelength A scale identically as the inverse velocity to the 112 power and the aspect ratio r is a constant equal to 312, independently of a and k for a < 0.5.. For 0.5 < a < m, L, A and r decrease asymptotically to zero indicating the finite amplitude nature of the instability at a = 1 and the existence of sub-marginal states which converge to a flat interface at a- m (Glv- m). Scaling comparisons between equilibrium single-valued and triple-valued and deep-rooted non- equilibrium cells are made.

Jan 1, 1992

By Tang Chaobo

According to the principles of simultaneous chemical equilibrium and electronic charge neutrality, the system of Mg(II)-NH3-CO32--SO42--H2O at 25°C has been thermodynamically analyzed. And the rule of solubility of MgCO3(s) in the system is discovered, the high dissolution field of MgCO3(s) is discovered too. Furthermore, the solubility of MgCO3(s) is increased with the increase of the concentration of SO42-, but it is decreased first then increased with the increase of the concentration of all the CO32- and the total concentration of ammonia and ammonium, and decreased with the value of pH being higher. Those results will has important significance on prepare magnesium chemical products and other salts carbonate that are strict with the content of magnesium with carburization method.

Jan 1, 2006

By Shulan Wang, Xuan Liu, Li Li

"Electrochemistry of Fe(III) in 69CaCl2-12CaF2-19KF and 81CaCl2-19KF (mole percentage, %) was investigated at 827 oC on molybdenum electrode by cyclic voltammetry, chronoamperometry and galvanostatic electrolysis using Fe2O3 as the Fe(III) source. The reduction of Fe(III) to Fe was conducted in one step and controlled by diffusion process. Fe(III) shown greater reduction rate and diffusion coefficient in molten 81CaCl2-19KF than in 69CaCl2- 12CaF2-19KF. Galvanostic electrolysis of Fe was performed in both molten salts with a cylindrical cathode rotating at 200 r/min and dendritic iron deposit was obtained.Keywords: iron; electrolysis; electrochemistry; molten saltIntroductionThe production of iron and steel causes huge emissions of CO2. Iron electrowinning in molten salts with dissolved Fe2O3 using an inert oxygen evolving anode is an alternative process to reduce or eliminate the formation of CO2. Research on novel process of producing metal has been reported recently [1-2] by using CaCl2 as the main electrolyte and dissolving CaO in CaCl2 due to the high solubility of CaO in the melt. This process has been used in preparing many active metals and alloys [3-14]. In the present work, the electrochemical behavior of iron in CaCl2-KF was studied and transport property of iron ion in the melt was discussed.ExperimentalCaCl2,CaF2 and KF (in analytical purity) were dried in air for 48 h. Mixed salts used in experiments were placed in a graphite crucible (??58 mm inner diameter). The graphite crucible together with the salts was heated at 473 K for 12 h in a furnace with flowing Ar (99.99%) before further heating. Temperature inside the furnace was measured by an S type thermocouple. Electrochemical measurements, such as cyclic voltammetry and chronocoulometry, were performed in a three electrode cell by EG&G PAR273A potentiostat/galvanostatand. Galvanostatic electrodepositon of iron was conducted in a two electrode cell. Molybdenum (??2 mm) and iron (??5 mm) were used as the working electrode (WE) and the reference electrode, respectively. A graphite crucible and a magnetite rod (??25 mm ) consisted of 100% magnetite and sintered at 950 oC in argon atmosphere for 2 h with electrical conductivity of 366 O-1m-1 at room temperature were used as the counter electrodes in the galvanostatic electrolysis experiment. Carbon (??10 mm) was used as the counter electrode in electrochemical measurement. The deposits were washed in distilled water bubbled with argon and dried in air before being characterized by X-ray diffraction (PW3040/60 diffractometer) and scanning electron microscope (SEM, SSX-550)."

Jan 1, 2014

By Yoichi Takeda

Copper solubility in SiO2-CaO-FeOx slag equilibrated with copper matte in 10% SO2 atmosphere at 1573K was estimated. Essential parameters are activity coefficients of copper oxide and sulfide, oxygen and sulfur potentials and activity of copper in the slag-matte system. A large number of experiments provide proper parameters to calculate copper solubility in slag, A classical thcrmodynamic model postulating CuO0.5 and CuS0.5 moleculcs assists in estimating copper solubility in slag. Additions of Si02 and CaO reduce copper solubility almost in any condition. Copper loss, that is function copper solubility and slag volume, in the silica saturated SiO2-FeO. binary slag is minimally equilibrated with less than 66% copper matte while copper loss in the 50% FeO.-SiO2-CaO ternary slag saturated with 2CaOSiO2 is minimally equilibrated with over 66% copper matte. This slag composition has potential for continuous copper converting, direct copper production or high-grade matte production.

Jan 1, 2003

By Guanghui Li

In the paper, the recovery technology of gallium from zinc-leaching residue by cold-bonded coal-based direct reduction process following magnetic separation was developed. The results show that the scattered metal Ga can be concentrated obviously after the reduction of zinc-leaching residue briquette and magnetic separation of reduced product. At the same time, the volatilization of Zn in the residue is enhanced during the reduction. When the residue, bear¬ing 18.60% Zu.21.18% Fe and 527 g/t Ga, was reduced with coal at 1100°C for 150 min, the results of Zn volatilization of 9842% and Ga recovery of 89. 10% were obtained in reduction. After magnetic separation of the reduced product, the concentration of Ga in sponge iron is 2164 g/t, and the separation recovery of Ga reaches 92.42%. The enriched mechanism of Ga during reduction -separation process was studied by using electron microscope, scanning elec¬tron microscope, energy spectrum and mineralogical analysis. The investigations show that there is no formation of independent phase of Ga during reduction process. The Ga occurs mainly in metallic iron phase (the concentration of Ga in metallic iron phase is 0.04%-0,4%), in addition, there exists a little Ga in poorly crystalline sulphide (o.08%-0./5Y& Ow). But Go does not exist in most of glass and silicate phase. The affinity of Ga for metallic iron is the enrichment basis of Go in reduction, and it is also in favor of recovering Go during magnetic separation. Key Words: Gallium Zinc-leaching Residue Cold- Bonded Direct Reduction

Jan 1, 2003

By Zhang Chuanfu, Tan Pengfu

"A thermodynamic model is developed to predict the distribution behaviors of Ni, Co, Sn, Pb, Zn, As, Sb, Bi, Au and Ag in copper pyrometallurgical process. In this model, as more as 21 elements (Cu, S, Fe, Ni, Co, Sn, As, Sb, Bi, Pb, Zn, Au, Ag, 0, N, C, H, Ca, Mg, Al, and Si) and 72 compounds (in fayalite-slag-making system) or 74 compounds (in ferrite-slag-making system) are considered. Accessory-element behavior is studied for two types of slag , fayalite and ferrite, and two levels of oxidation. The allowance is also made to account for physical entrainment in the melts.-Model simulations are carried out to study the effects of controllable process parameters such as feed composition, smelting temperature, degree of oxygen enrichment and volume of oxygen enriched air. The model can be used in copper flash process, Mitsubishi process and Noranda process. The predictions by the present computer model are compared with the known industrial data from Gui Xi Smelter in China, Home Smelter in Canada and Naoshima Smelter in Japan and excellent agreement between calculations and industrial data is obtained. In this paper, the effects of oxygen enrichment, matte grade, smelting temperature, and types of slag on accessory-element behavior among matte, slag and gaseous phase have been elucidated.I . IntroductionThe presence of trace quantities of minor elements such as As, Sb and Bi in copper significantly reduces its ductility, electrical conductivity, and lowers its thermal conductivity. Embrittlement of copper also occurs due to impurity-phase precipitates at the copper grain boundary interfaces. They deteriorate not only the electrical conductivity of copper but its workability in hot working."

Jan 1, 1998

By Peter K. Everett

One of the major driving forces behind the development of the Intec Copper Process has been the increasingly stringent regulations governing SO2 emissions and, in some parts of the world, a declining H2SO4 market. Other incentives include operating cost (9.2 US c/lb Cu), capital cost (US $1400/annual tonne Cu compared with smelter cost of US$3-4000/annual tonne Cu) and the ability to treat low grade and contaminated concentrates. With such advantageous features, widespread use of the process is expected over time, leading to the production of large amounts of residues containing around 25% elemental sulfur, together with approximately 50-60 % akaganeite (FeOOH) and the ganggue minerals originally present in the concentrate feed. This paper briefly describes the Intec process chemistry involved in the formation of elemental sulfur, thereby avoiding atmospheric sulfur dioxide pollution, and the investigations to be carried out either to extract it or to turn the residue into a valuable by-product while minimising any adverse environmental effects, The process is being developed jointly by a group of fifteen major international mining companies.

Jan 1, 1996